TWI701283B - Polarized ultraviolet anisotropic material, composition for polarized ultraviolet anisotropic material, manufacturing method of polarized ultraviolet anisotropic material, and composition for manufacturing polarized ultraviolet anisotropic material - Google Patents

Abstract

The present invention provides a polarized ultraviolet anisotropic material (for example, a liquid crystal alignment film, a retardation film, or a hologram) that exhibits anisotropy by polarized ultraviolet irradiation, which has no alignment at all The time-dependent change or the time-dependent change is reduced, and the alignment stability is excellent.

The polarized ultraviolet anisotropic material provided by the present invention that exhibits anisotropy by polarized ultraviolet irradiation is a material with the following polymer, which has the following formula (I) or (II) Side chain,

(In the formula, A ₁ represents -O-, -COO-, -NHCO-, etc., n represents an integer from 1 to 16, and a part of the methylene group (-CH ₂ -) may be substituted with -O-, -COO- , -OOC-, -NHCO-, etc., X represents -CH=N- or -N=CH-, R represents an alkyl group with carbon number 1 to 3, n ₁₁ and n ₁₂ each independently represent an integer of 0 to 4, R ', R ₁₁ and R ₁₂ each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, etc.).

Description

Polarized ultraviolet anisotropic material, composition for polarized ultraviolet anisotropic material, manufacturing method of polarized ultraviolet anisotropic material, and composition for manufacturing polarized ultraviolet anisotropic material

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

Liquid crystal display elements are known as light-weight, thin-shaped and low-power-consumption display devices, and in recent years they have been used in large-scale television applications and so on. The liquid crystal display element is configured by sandwiching a liquid crystal layer between a pair of transparent substrates provided with one of the electrodes, for example. In addition, the liquid crystal display element uses an organic film made of an organic material as the liquid crystal alignment film to make the liquid crystal in a desired alignment state between the substrates.

That is, the liquid crystal alignment film is a component of the liquid crystal display element, formed on the surface adjacent to the liquid crystal of the substrate sandwiching the liquid crystal, and plays a role of aligning the liquid crystal between the substrates in a certain direction. Moreover, in addition to the role of aligning the liquid crystal in a certain direction, such as a direction parallel to the substrate, the liquid crystal alignment film is sometimes required to play a role in controlling the pretilt angle of the liquid crystal. The ability to control the alignment of the liquid crystal in such a liquid crystal alignment film (hereinafter referred to as (Orientation control ability) is provided by performing an alignment treatment 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, a rubbing method has been known in the past. However, the rubbing method of wiping the surface of the liquid crystal alignment film made of polyimide or the like has the problem of generating dust or static electricity. In addition, in recent years, due to the high-definition of liquid crystal display elements, or the unevenness caused by the electrodes on the corresponding substrate or the switching active element for liquid crystal driving, it is impossible to wipe the surface of the liquid crystal alignment film uniformly with a cloth. , Sometimes it is impossible to achieve uniform liquid crystal alignment.

Therefore, the photo-alignment method is actively reviewed as another alignment treatment method for liquid crystal alignment films without rubbing.

There are various methods for the photo-alignment method, but linear polarized light or collimate 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 main optical alignment method, a decomposition type optical alignment method is known. For example, a polyimide film is irradiated with polarized ultraviolet rays, and the polarization direction dependence of the ultraviolet absorption of the molecular structure is used to generate anisotropic decomposition. In addition, the polyimide remaining undecomposed is used to align the liquid crystal (see, for example, Patent Document 1).

In addition, a photo-alignment method of photo-crosslinking type or photo-isomerization type is also known. For example, using polyvinyl cinnamate, irradiating polarized ultraviolet light, dimerization reaction (crosslinking reaction) occurs in the double bond portion of the two side chains parallel to the polarized light. Next, the liquid crystal is aligned in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1). In addition, when using a side chain type polymer with azobenzene on the side chain, irradiate polarized ultraviolet light on the side parallel to the polarized light The azobenzene part of the chain causes an isomerization reaction to align the liquid crystal in a direction orthogonal to the polarization direction (for example, refer to Non-Patent Document 2).

As in the above example, the alignment treatment method of the liquid crystal alignment film by the photo-alignment method does not require rubbing, and there is no doubt about generating dust or static electricity. Moreover, even the substrates of liquid crystal display elements with uneven surfaces can be subjected to alignment processing, which becomes a suitable alignment processing method for liquid crystal alignment films in industrial production processes.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3893659

[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, as an alignment treatment method for liquid crystal display elements, does not require the rubbing step itself as compared with the rubbing method used in the industry in the past, and therefore has great advantages. Moreover, compared to the use of friction to make the alignment control a certain friction method, the optical alignment method can be modified. The irradiated amount of polarized light is changed to control the alignment control performance.

However, in the photo-alignment method, after the liquid crystal display element is manufactured, the photoreactive group remaining in the liquid crystal alignment film in the element will react with natural light or the backlight in the liquid crystal display element, which will damage the liquid crystal alignment. The stability of the situation. In particular, when using the photo-alignment of the isomerization of the azobenzene skeleton, this problem occurs significantly.

The purpose of the present invention is to solve the aforementioned problems.

Specifically, the object of the present invention is to provide a polarized ultraviolet anisotropic material (such as a liquid crystal alignment film, preferably a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element, The retardation film, or hologram, has no time-dependent change or reduced time-dependent change in alignment at all, and has excellent alignment stability.

Furthermore, the object of the present invention is to provide a method for manufacturing the above-mentioned material and a composition for manufacturing the above-mentioned material.

In order to achieve the above-mentioned problems, the team of the present invention conducted active reviews and found the following inventions.

<1>. A polarized ultraviolet anisotropic material exhibiting anisotropy by polarized ultraviolet irradiation, which is a material having the following polymer, the polymer having the following formula (I) or (II) Side chain,

(In the formula, A ₁ represents -O-, -COO-, -NHCO-, -CONH-, -NHCONH-, -NHCOO-, -OCONH- or -OCO-, n represents an integer from 1 to 16, methylene A part of (-CH ₂ -) can be substituted with -O-, -COO-, -OOC-, -NHCO-, -CONH-, -NHCONH-, -NHCOO-, -OCONH-, -C=C- or -C≡C- (but the methylene group (-CH ₂ -) adjacent to A ₁ or -O- is not substituted by these groups), X represents -CH=N- or -N=CH-, R Represents an alkyl group with 1 to 3 carbons, n ₁₁ and n ₁₂ each independently represent an integer from 0 to 4, and R', R ₁₁ and R ₁₂ each independently represent a linear or branched alkyl group with 1 to 6 carbons , Halogen atom, nitro group, cyano group, linear or branched alkoxy group with 1 to 6 carbon atoms).

<2>. In the above <1>, A ₁ represents -O-, -COO- or -OCO-, preferably -O-; n represents an integer from 1 to 8, preferably 6; methylene is not The above-mentioned substituents are preferred; R is preferably methyl, and n ₁₁ and n _{12 are} preferably 0.

<3> In the above <1> or <2>, the polymer preferably further has any liquid crystal side chain selected from the group consisting of the following formulas (21) to (31):

(In the formula, A and B each independently represent 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 and the other is 0; Y ₃ is selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Heterocycles and alicyclic hydrocarbons with 5 to 8 carbons, and groups of these groups, the hydrogen atoms bonded to these groups can be independently -NO ₂ , -CN, halogen, and carbon number 1~5 alkyl group or C1~5 alkyloxy group; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, Halogen, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon with 5 to 8 carbons, alkyl with 1 to 12 carbons, or 1 to 12 carbons 1 represents an integer from 1 to 12, m represents an integer from 0 to 2, but in formulas (23) to (24), the total of all m is 2 or more, in formulas (25) to (26), The total of all m is 1 or more, m1, m2, and m3 each independently represent an integer of 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, halogen group, monovalent benzene ring, naphthalene ring, and biphenyl ring , Furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbons with 5 to 8 carbon atoms, and alkyl or alkyloxy groups; Z ₁ , Z ₂ represent a single bond, -CO-, -CH ₂ O-,- CH=N-, -CF ₂ -).

<4>. In any one of the above <1>~<3>, the material is preferably used in one selected from the group consisting of liquid crystal alignment agents, retardation films, and holographic films, preferably used in liquid crystal alignment Agent or retardation film, better used in liquid Crystal alignment agents are best used in liquid crystal alignment films for lateral electric field-driven liquid crystal display elements.

<5>. A composition for polarized ultraviolet anisotropic material, which has (A) a polymer and (B) an organic solvent, and (A) the polymer has a side chain represented by the above formula (I) or (II) .

<6> In the above <5>, A ₁ represents -O-, -COO- or -OCO-, preferably -O-; n represents an integer of 1 to 8, preferably 6; methylene is not The above-mentioned substituents are preferred; R is preferably methyl, and n ₁₁ and n _{12 are} preferably 0.

<7> In the above <5> or <6>, the polymer preferably further has any liquid crystal side chain selected from the group consisting of the above formulas (21) to (31).

<8>. In any one of the above <5>~<7>, the material is preferably used for one selected from the group consisting of liquid crystal alignment agent, retardation film, and holographic film, preferably used for liquid crystal alignment It is better to use a liquid crystal alignment agent or a retardation film, and is best used in a liquid crystal alignment film for a transverse electric field driven liquid crystal display element.

<9>. A method for manufacturing a polarized ultraviolet anisotropic material, which has the following steps to obtain a polarized ultraviolet anisotropic material that exhibits anisotropy by polarized ultraviolet irradiation: [I] will have (A) The step of applying a polymer and (B) an organic solvent polarized ultraviolet anisotropic material composition on a substrate to form a coating film; and [II] the step of irradiating the coating film obtained in [I] with polarized ultraviolet light; Among them, the aforementioned (A) polymer has a side chain represented by the aforementioned formula (I) or (II).

<10>. In the above <9>, it is preferable to further have the following step: [III] a step of heating the coating film obtained in [II].

<11>. In the above <9> or <10>, A ₁ represents -O-, -COO- or -OCO-, preferably -O-; n represents an integer from 1 to 8, preferably 6; The methyl group is preferably not substituted by the above-mentioned substituents; R is preferably methyl, and n ₁₁ and n _{12 are} preferably 0.

<12>. In any one of the above-mentioned <9> to <11>, the polymer preferably further has any liquid crystal side chain selected from the group consisting of the above-mentioned formulas (21) to (31).

<13>. In any of the above items <9>~<12>, the material is preferably used in one selected from the group consisting of liquid crystal alignment agents, retardation films, and holographic films, and is preferably used in liquid crystal alignment It is better to use a liquid crystal alignment agent or a retardation film, and is best used in a liquid crystal alignment film for a transverse electric field driven liquid crystal display element.

<14>. A composition for manufacturing polarized ultraviolet anisotropic material, which has a monomer represented by the following formula [RM1] or [RM2], or [RM1’] or [RM2’],

(In the formula, R ₂₁ is F, Cl or CN, and R ₂₂ is F, Cl, CN or t-Bu).

<15> In the above-mentioned <14>, the polarized ultraviolet anisotropic material is preferably used in one selected from the group consisting of liquid crystal alignment agents, retardation films, and holographic films, and preferably used in liquid crystal alignment agents or phases. The difference film is better used for liquid crystal alignment agents, and is best used for liquid crystal alignment films for lateral electric field driven liquid crystal display elements.

On the other hand, the following invention was discovered.

<P1>. A polarized ultraviolet anisotropic material that exhibits anisotropy by irradiation with polarized ultraviolet light, which is a material having a polymer having a side chain represented by the following formula (I),

(In the formula, A ₁ represents -O-, -COO-, -NHCO-, -CONH-, -NHCONH-, -NHCOO-, -OCONH- or -OCO-, n represents an integer from 1 to 16, methylene A part of (-CH ₂ -) can be substituted with -O-, -COO-, -OOC-, -NHCO-, -CONH-, -NHCONH-, -NHCOO-, -OCONH-, -C=C- or -C≡C- (but the methylene group (-CH ₂ -) adjacent to A ₁ or -O- is not substituted by these groups), X represents -CH=N- or -N=CH-, R Represents an alkyl group with 1 to 3 carbons, n ₁₁ and n ₁₂ each independently represent an integer from 0 to 4, and R ₁₁ and R ₁₂ each independently represent a linear or branched alkyl group with 1 to 6 carbons, and a halogen atom , Nitro, cyano, linear or branched alkoxy with 1 to 6 carbons).

<P2>. In the above <P1>, A ₁ represents -O-, -COO- or -OCO-, preferably -O-; n represents an integer from 1 to 8, preferably 6; methylene is not The above-mentioned substituents are preferred; R is preferably methyl, and n ₁₁ and n _{12 are} preferably 0.

<P3>. In the above <P1> or <P2>, the polymer preferably further has any liquid crystal side chain selected from the group consisting of the following formulas (21) to (31):

(In the formula, A and B each independently represent 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 and the other is 0; Y ₃ is selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Heterocycles and alicyclic hydrocarbons with 5 to 8 carbons, and groups of these groups, the hydrogen atoms bonded to these groups can be independently -NO ₂ , -CN, halogen, and carbon number 1~5 alkyl group or C1~5 alkyloxy group; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, Halogen, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon with 5 to 8 carbons, alkyl with 1 to 12 carbons, or 1 to 12 carbons L represents an integer from 1 to 12, m represents an integer from 0 to 2, but in formulas (25) to (26), the total of all m is 2 or more, in formulas (27) to (28), The total of all m is 1 or more, m1, m2, and m3 each independently represent an integer of 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, halogen group, monovalent benzene ring, naphthalene ring, and biphenyl ring , Furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbons with 5 to 8 carbon atoms, and alkyl or alkyloxy groups; Z ₁ , Z ₂ represent a single bond, -CO-, -CH ₂ O-,- CH=N-, -CF ₂ -).

<P4>. In any of the above <P1>~<P3>, the material should be selected from the group consisting of liquid crystal alignment agent, retardation film, and holographic film One of the group is preferably used in liquid crystal alignment agents or retardation films, more preferably used in liquid crystal alignment agents, and most preferably used in liquid crystal alignment films for lateral electric field driven liquid crystal display elements.

<P5>. A composition for polarized ultraviolet anisotropic material, which has (A) a polymer and (B) an organic solvent, and the (A) polymer has a side chain represented by the above formula (I).

<P6>. In the above <P5>, A ₁ represents -O-, -COO- or -OCO-, preferably -O-; n represents an integer from 1 to 8, preferably 6; methylene is not The above-mentioned substituents are preferred; R is preferably methyl, and n ₁₁ and n _{12 are} preferably 0.

<P7>. In the above <P5> or <P6>, the polymer preferably further has any liquid crystal side chain selected from the group consisting of the above formulas (21) to (31).

<P8>. In any of the above <P5>~<P7>, the material is preferably used in one selected from the group consisting of liquid crystal alignment agents, retardation films, and holographic films, preferably used in liquid crystal alignment It is better to use a liquid crystal alignment agent or a retardation film, and is best used in a liquid crystal alignment film for a transverse electric field driven liquid crystal display element.

<P9>. A manufacturing method of polarized ultraviolet anisotropic material, which has the following steps to obtain a polarized ultraviolet anisotropic material that exhibits anisotropy by polarized ultraviolet irradiation: [I] will have (A) The step of coating the composition of the polarized ultraviolet anisotropic material of polymer and (B) organic solvent on the substrate to form a coating film; and [II] A step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; wherein the aforementioned (A) polymer has a side chain represented by the aforementioned formula (I).

<P10>. In the above <P9>, it is preferable to further have the following step: [III] The step of heating the coating film obtained in [II].

<P11>. In the above <P9> or <P10>, A ₁ represents -O-, -COO- or -OCO-, preferably -O-; n represents an integer from 1 to 8, preferably 6; The methyl group is preferably not substituted by the above-mentioned substituents; R is preferably methyl, and n ₁₁ and n _{12 are} preferably 0.

<P12>. In any one of the above <P9> to <P11>, the polymer preferably further has any liquid crystal side chain selected from the group consisting of the above formulas (21) to (31).

<P13>. In any of the above <P9>~<P12>, the material is preferably used in one selected from the group consisting of liquid crystal alignment agents, retardation films, and holographic films, preferably used in liquid crystal alignment It is better to use a liquid crystal alignment agent or a retardation film, and is best used in a liquid crystal alignment film for a transverse electric field driven liquid crystal display element.

<P14>. A composition for the manufacture of polarized ultraviolet anisotropic material, which has a monomer represented by the following formula [RM1] or [RM2],

(In the formula, Me represents a methyl group).

<P15>. In the above <P14>, the polarized ultraviolet anisotropic material is preferably used in one selected from the group consisting of liquid crystal alignment agents, retardation films, and holographic films, preferably used in liquid crystal alignment agents or phase The difference film is better used for liquid crystal alignment agents, and is best used for liquid crystal alignment films for lateral electric field driven liquid crystal display elements.

According to the present invention, it is possible to provide a polarized ultraviolet anisotropic material (such as a liquid crystal alignment film, preferably a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element, a retardation film, Or holographic film), which has no chronological change of alignment or reduction of chronological change, and excellent alignment stability.

Furthermore, according to the present invention, in addition to or in addition to the above-mentioned effects, it is possible to provide a method of manufacturing the above-mentioned material and a composition for manufacturing the above-mentioned material.

Fig. 1 is a graph showing the change in the absorption spectrum when the polymer P1 film of Example 3 is irradiated with light of 313 nm (intensity: 10 mW/cm ² ).

2 is a graph showing the change in the polarization absorption spectrum when the P1 film prepared in Example 4 is irradiated with a linearly polarized ultraviolet light of 313 nm of 10 J/cm ² .

Fig. 3 shows the optical path diagram when performing the holographic exposure of Example 5 (Fig. 3a), and the heights of two types of surface undulations formed by the holographic image (Fig. 3b and Fig. 3c).

[Best form for implementing invention]

The present invention provides a polarized ultraviolet anisotropic material, a composition for the material, a method for manufacturing the material, a composition for manufacturing the material, and the like. Hereinafter, they will be explained in order.

<Polarized ultraviolet anisotropic material>

The present invention is to provide a polarized ultraviolet anisotropic material that exhibits anisotropy by polarized ultraviolet radiation, which is a material with a polymer having a side chain represented by the following formula (I) or (II) .

In formulas (I) and (II), A ₁ represents -O-, -COO-, -NHCO-, -CONH-, -NHCONH-, -NHCOO-, -OCONH- or -OCO-, n represents 1~16 Integer, a part of the methylene group (-CH ₂ -) can be substituted with -O-, -COO-, -OOC-, -NHCO-, -CONH-, -NHCONH-, -NHCOO-, -OCONH-, -C=C- or -C≡C- (but the methylene group (-CH ₂ -) adjacent to A ₁ or -O- is not substituted by these groups), X represents -CH=N- or- N=CH-, R represents an alkyl group with 1 to 3 carbons, n ₁₁ and n ₁₂ each independently represent an integer from 0 to 4, and R', R ₁₁ and R ₁₂ each independently represent a straight chain with 1 to 6 carbons Or branched alkyl, halogen atom, nitro, cyano, straight or branched alkoxy with 1 to 6 carbon atoms.

In particular, in formulas (I) and (II), A ₁ represents -O-, -COO- or -OCO-, preferably -O-; n represents an integer from 1 to 8, preferably 6; methylene The group is preferably not substituted by the above-mentioned substituents; R is preferably methyl, and n ₁₁ and n _{12 are} preferably 0.

The polymer having a side chain represented by the above formula (I) or (II) exhibits anisotropy by irradiation with polarized ultraviolet rays.

In particular, a polymer having a side chain represented by the above formula (I) or (II) exhibits anisotropy by irradiating polarized ultraviolet rays with a wavelength of 100 to 400 nm. Furthermore, those having a side chain represented by the above formula (I) or (II) For polymers, it is better to exhibit liquid crystallinity by heating in a temperature range of 40 to 300°C.

The molecular weight of the (A) polymer of the present invention should be considered as For the material of the purpose, 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 GPC (Gel Permeation Chromatography) method is preferably 2000 to 1,000,000 , More preferably 5000~100000.

Has the height of the side chain represented by the above formula (I) or (II) The molecule preferably further has a liquid crystal side chain, and the aforementioned liquid crystal side chain is one having a mesogenic group exhibiting liquid crystallinity. In particular, liquid crystal side chains exhibiting liquid crystallinity in the temperature range of 40 to 300°C are preferred. In addition, if the target material is a liquid crystal alignment film, a liquid crystal side chain that exhibits liquid crystallinity in a temperature range of 100 to 300°C is preferred.

As these liquid crystal side chains, any liquid crystal side chain selected from the group consisting of the following formulas (21) to (31) is suitable. In the formula, A and B each independently represent 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 and the other is 0; Y ₃ is selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing hetero Ring and alicyclic hydrocarbons with 5 to 8 carbon atoms, and groups of these combinations, the hydrogen atoms bonded to these groups can be independently -NO ₂ , -CN, halogen, and carbon number 1. ~5 alkyl group, or substituted by alkyloxy group with carbon number 1~5; 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 heterocyclic ring, alicyclic hydrocarbon with 5 to 8 carbons, alkyl with 1 to 12 carbons, or 1 to 12 carbons Alkoxy; l represents an integer from 1 to 12, m represents an integer from 0 to 2, but in formulas (23) to (24), the total of all m is 2 or more, in formulas (25) to (26), all The total of m is 1 or more, m1, m2, and m3 each independently represent an integer from 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, and alicyclic hydrocarbon with carbon number of 5-8, and alkyl or alkyloxy; Z ₁ , Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH =N-, -CF ₂ -.

The material having the above-mentioned polymer (which has the side chain represented by the above-mentioned formula (I) or (II)) is suitable for use in one selected from the group consisting of liquid crystal alignment agents, retardation films, and holographic films , Preferably used in liquid crystal alignment agents or retardation films, more preferably used in liquid crystal alignment agents, and most preferably used in liquid crystal alignment films for lateral electric field driven liquid crystal display elements.

<Composition for Polarized Ultraviolet Anisotropic Material>

The present invention provides a composition for polarized ultraviolet anisotropic material, which has (A) a polymer and (B) an organic solvent, and (A) the polymer has a side chain represented by the above formula (I) or (II) .

<<Organic Solvent>>

The composition for polarized ultraviolet anisotropic material used in the present invention is not particularly limited as long as the organic solvent used therein can dissolve the above-mentioned (A) polymer component. Specific examples are listed below.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactone, 2-pyrrolidone, N- Ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfide, tetramethyl urea, pyridine, dimethyl sulfide, hexamethyl sulfide, γ-butyrolactone, 3-methoxy- N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-di Methyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, ethylene carbonate Propyl ester, diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tertiary 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 can be used alone or in combination.

The composition for polarized ultraviolet anisotropic material used in the present invention may contain components other than the above-mentioned (A) and (B) components.

The composition of the present invention is other than the above-mentioned (A) and (B) components The component of, may have a polymer exhibiting liquid crystallinity, and may contain other polymers other than it. Examples of other polymers include poly(meth)acrylate, polyamide acid, or polyimide, but are not limited to these.

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.

In addition to the components (A) and (B), examples include solvents or compounds that improve film thickness uniformity or surface smoothness when the composition is applied. When the material is a liquid crystal alignment film, etc., the liquid crystal alignment film and the substrate Compounds with improved adhesion are used as examples of the composition that can be contained in the present invention, but they are not limited thereto.

As a specific example of the solvent (weak solvent) which improves the uniformity of the film thickness or surface smoothness, the following can be mentioned, for example.

For example, isopropanol, methoxymethylpentanol, methyl siloxu, ethyl siloxu, butyl siloxu, methyl siloxu acetate, ethyl siloxu acetate, Butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, Propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tertiary 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, 1-hexanol, n-hexane, n-pentane, n-octane Alkane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-methoxy Methyl propionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid Propyl ester, 3-methoxybutyl propionate, 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, two Solvents with low surface tension such as propylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc.

One of these weak solvents can be used or multiple use. When using the above-mentioned solvent, it is preferable that the solubility of the entire solvent contained in the composition is not significantly reduced, and it is 5% to 80% by mass of the entire solvent, more preferably 20% to 60% by mass .

As a compound to improve the uniformity of film thickness or surface smoothness Examples of substances include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

More specific examples include EF TOP (registered trademark) 301, EF303, EF352 (manufactured by TOCHEM PRODUCTS), MEGAFAC (registered trademark) F171, F173, R-30 (manufactured by DIC Corporation), FLORARD FC430, FC431 (manufactured by Sumitomo 3M) ), ASAHI GUARD (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 Corporation), etc. The use ratio of the surfactants is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass relative to 100 parts by mass of the polymer (A) contained in the composition .

If the material is a liquid crystal alignment film, etc., Specific examples of the compound for the adhesion between the alignment film and the substrate include the following compounds containing functional silanes.

Examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-urea Propyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyl Triethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1, 4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate , Acetic acid 9-triethoxysilyl-3,6-diazanonyl ester, N-benzyl-3-aminopropyl trimethoxysilane, N-benzyl-3-aminopropyl three Ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3- Aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, etc.

Furthermore, if the material is a liquid crystal alignment film, etc., in addition to improving In addition to the adhesion between the substrate and the liquid crystal alignment film, for the purpose of preventing the degradation of electrical characteristics caused by the backlight when constructing the liquid crystal display element, the following phenolic plastic (phenoplast) or epoxy-containing Compound additives. Specific phenolic plastic additives are listed below, but they are not limited to this structure.

As a specific epoxy-containing compound, exemplified Such as: 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, glycerol 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-4,4'-diaminodiphenylmethane, etc.

When using a compound that improves the adhesion to the substrate, it makes The amount used is preferably 0.1 parts by mass to 30 parts by mass, and more preferably 1 part by mass to 20 parts by mass relative to 100 parts by mass of the aforementioned (A) polymer component contained in the composition.

A photosensitizer can also be used as an additive. Preferred are colorless sensitizers and triplet sensitizers.

As photosensitizers, there are, for example, aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy 4-methylcoumarin), keto coumarin Ketones, carbonyl biscoumarins, aromatic 2-hydroxy ketones, and aromatic 2-hydroxy ketones substituted with amino groups (2-hydroxy benzophenone, mono- or di-p-(dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzoanthrone, thiazoline (2-benzylmethylene-3-methyl-β- Naphththiazoline, 2-(β-naphthylmethylene)-3-methylbenzothiazoline, 2-(α-naphthylmethylene)-3-methylbenzothiazoline, 2-( 4-Bisphenol-methylene)-3-methylbenzothiazoline, 2-(β-naphthylmethylene)-3-methyl-β-naphthylthiazoline, 2-(4-biphenol Methylene)-3-methyl-β-naphthylthiazoline, 2-(p-fluorobenzylmethylene)-3-methyl-β-naphthylthiazoline), oxazoline ( 2-benzylmethylene-3-methyl-β-naphthyloxazoline, 2-(β-naphthylmethylene)-3-methylbenzoxazoline, 2-(α- Naphthylmethylene)-3-methylbenzoxazoline, 2-(4-biphenolylmethylene)-3-methylbenzoxazoline, 2-(β-naphthylmethylene) Ylmethylene)-3-methyl-β-naphthoxazoline, 2-(4-biphenolylmethylene)-3-methyl-β-naphthoxazoline, 2-(p- Fluorobenzylmethylene)-3-methyl-β-naphthoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitro Aniline) or nitroacenaphthylene (5-nitroacenaphthylene), (2-[(m-hydroxy -P-methoxy)styryl)benzothiazole, benzoyl alkyl ether, N-alkylated phthalone (phthalone), acetophenone ketal (2,2-dimethoxybenzene) Ethyl ketone), naphthalene, anthracene (2-naphthalene methanol, 2-naphthalene carboxylic acid, 9-anthracene methanol and 9-anthracene carboxylic acid), benzopyran, azoindolidine, furocoumarin (furocoumarin) Wait.

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

In addition to the above, for the purpose of changing the characteristics of the materials obtained Yes, the composition may also contain various compounds. For example, if the material is a liquid crystal alignment film, for the purpose of changing the electrical properties of the liquid crystal alignment film such as the dielectric rate or conductivity, a dielectric or conductive material can also be added, and furthermore, to improve the production of the liquid crystal alignment film For the purpose of film hardness or density, crosslinking compounds can also be added.

<Method for manufacturing polarized ultraviolet anisotropic material>

The polarized ultraviolet anisotropic material of the present invention can be manufactured by, for example, the following method.

The following steps are used to obtain the polarized ultraviolet anisotropic material endowed with alignment control ability: [I] Coating the polarized ultraviolet anisotropic material composition with (A) polymer and (B) organic solvent on the substrate The step of forming a coating film; and [II] the step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; wherein the aforementioned (A) polymer has a side chain represented by the above formula (I) or (II) (In the formula, A ₁ , n, X, and R have the same definitions as above).

(A) The polymer, and (B) the organic solvent, and the composition having these are the same as above.

The above method may further have the following step [III]: [III] A step of heating the coating film obtained in [II].

In terms of materials, in order to obtain a liquid crystal alignment film, particularly when obtaining a liquid crystal alignment film for a liquid crystal display element, it is preferable to use a substrate having a conductive film (the first substrate) as the substrate of [I]. In addition, the above-mentioned [I] and [II] are carried out using a substrate (second substrate) with or without a conductive film, and the above-mentioned [III] is preferably carried out as the case may be. Furthermore, the method of manufacturing a liquid crystal display element may have the following steps [IV]: [IV] A step of obtaining a liquid crystal display element, which is opposed to the liquid crystal alignment films of the first and second substrates obtained above via liquid crystals In this way, the first and second substrates are arranged to face each other.

Thus, a liquid crystal display element can be obtained.

Hereinafter, each step of [I] and [II], and [III] and [IV] of the manufacturing method of the present invention will be described.

<Step [I]>

Step [I] is a step of applying the above-mentioned composition on a substrate to form a coating film.

<Substrate>

The substrate is not particularly limited, as long as it is selected according to the intended material. For the liquid crystal alignment film, especially in the case of a liquid crystal alignment film for liquid crystal display devices, and when the manufactured liquid crystal display device is of a transmissive type, it is preferable to use a highly transparent substrate. In this 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 addition, considering the application of reflective liquid crystal display elements, opaque substrates such as silicon wafers can also be used.

What's more, if the target material is liquid for liquid crystal display When crystal alignment film is used, the substrate preferably has a conductive film. As this conductive film, when the liquid crystal display element is a transmissive type, 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, the conductive film may be a material capable of reflecting light such as aluminum, but it is not limited to these. The method of forming the conductive film on the substrate can use the conventional method.

<<(A) Preparation method of polymer>>

The above (A) polymer can be obtained by polymerizing the following monomers: a photoreactive side chain monomer having a side chain represented by the above formula (I) or (II), and as desired (21)~(31) The liquid crystal side chain monomer of the side chain.

The so-called "light reflection with a side chain represented by the above formula (I) or (II) "Responsive side chain monomer" refers to a monomer that can form a side chain represented by the above formula (I) or (II) at the side chain portion of the polymer when a polymer is formed. As a more specific example of the photoreactive side chain monomer, it is selected from the group consisting of hydrocarbon, (meth)acrylate, itaconic acid ester (itaconate), fumaric acid ester, maleic acid ester, α-methylene -Gamma-butyrolactone, styrene, vinyl, maleimide, norbornene, and other radical polymerizable groups composed of at least one of the group consisting of silicone, and the above The structure of the side chain represented by formula (I) or (II).

[Liquid crystal side chain monomer]

The so-called "liquid crystal side chain monomer" means that the polymer derived from the monomer exhibits liquid crystallinity, and the polymer is a monomer that can form a mesogenic group at the side chain site.

The mesogenic group possessed by the side chain may be a group that forms a mesogenic group alone with biphenyl or phenyl benzoate, or may be formed by hydrogen bonding the side chains such as benzoic acid. The base of mesogen-based structure. The mesogenic group possessed as a side chain preferably has the following structure.

As a more specific example of the liquid crystal side chain monomer, the Free hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, The structure of a polymerizable group composed of at least one of the group consisting of a free radical polymerizable group such as camphene and silicone, 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 aforementioned photoreactive side chain monomer.

The (A) polymer of the present invention, more specifically, can be produced from a composition for producing a polarized ultraviolet anisotropic material having monomers, the single system having the following formula [RM1] or [RM2], or [ RM1'] or [RM2'] (wherein R ₂₁ is F, Cl or CN, and R ₂₂ is F, Cl, CN or t-Bu).

The present invention also provides the composition for manufacturing the polarized ultraviolet anisotropic material Things.

The polymer (A) of the present invention can be It is obtained by the copolymerization of a crystalline photoreactive side chain monomer and a liquid crystal side chain monomer, or the copolymerization of a photoreactive side chain monomer exhibiting liquid crystallinity and a liquid crystal side chain monomer. Moreover, it can be copolymerized with other monomers without compromising the display performance of liquid crystallinity.

As other monomers, for example, commercially available monomers that can undergo radical polymerization reactions are listed.

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

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid. Examples of acrylate compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2 acrylate -Trifluoroethyl, 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 Ester and 8-ethyl-8-tricyclodecyl acrylate, etc.

Examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, methyl Anthryl methyl acrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methyl 2-Methoxyethyl acrylate, 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-methyl methacrylate Ethyl-8-tricyclodecyl ester and the like. Glycidyl (meth)acrylate, (3-methyl-3-oxetanyl)methyl (meth)acrylate and (3-ethyl-3-oxetanyl) (meth)acrylate can also be used (Meth)acrylate compounds having cyclic ether groups such as butyl) methyl esters.

Examples of vinyl compounds include vinyl ethers, Methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether, etc.

Examples of styrene compounds include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

Regarding the manufacturing method of (A) polymer of this embodiment and It is not particularly limited, and widely used methods adopted in industry can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using vinyl groups of liquid crystal side chain monomers or photoreactive side chain monomers. Among these, based on the viewpoint of easy reaction control, etc., radical polymerization is particularly preferred.

As a polymerization initiator for radical polymerization, it can be used freely Base polymerization initiator, reversible addition-chain scission type chain transfer (RAFT) polymerization reagents and other conventional compounds.

The radical thermal polymerization initiator is heated to the decomposition temperature The above is a compound that generates free radicals. As the radical thermal polymerization initiator, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide) Oxides, benzyl peroxide, etc.), hydrogen peroxides (hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl hydroperoxides (di- Tributyl peroxide, dicumyl peroxide, dilaurin peroxide, etc.), peroxyketals (dibutylperoxycyclohexane) Etc.), alkyl peresters (tert-butyl peroxy neodecanoate, t-butyl peroxy pivalate, t-pentyl peroxy 2-ethylcyclohexanoate, etc.), persulfuric acid Salts (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2'-bis(2-hydroxyethyl)azobisisobutyronitrile, etc.) ). This radical thermal polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

Radical photopolymerization initiator, as long as it is opened by light irradiation The compound that initiates radical polymerization is sufficient, and is not particularly limited. Examples of the radical photopolymerization initiator include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, and thioxanthone , Isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl- 4'-isopropyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzene ether, isobutyl benzene ether, 2,2-diethoxy acetophenone, 2,2- Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone (benzanthrone), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane- 1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 4-dimethylaminoethyl benzoate, 4-dimethylamino Isoamyl benzoate, 4,4'-bis(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tris(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-Dimethoxystyrene Yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine , 2-(4'-pentoxybenzene Vinyl)-4,6-bis(trichloromethyl)-s-triazine, 4-[p-N,N-bis(ethoxycarbonylmethyl)]-2,6-bis(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)benzothiazole, 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'-tetra(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-dimethylaminopropyl)carbazole, 3,6-bis(2-methyl 2-morpholinyl propionyl)-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(tert-butylperoxycarbonyl)benzophenone , 3,3',4,4'-tetra(third hexylperoxycarbonyl) benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(third butylper Oxycarbonyl) benzophenone, 3,4'-bis(methoxycarbonyl)-4,3'-bis(tertiary butylperoxycarbonyl)benzophenone, 4,4'-bis(methyl Oxycarbonyl)-3,3'-bis(tert-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphthalene-2 -Yl-ethanone, or 2-(3-methyl-1,3-benzothiazole-2(3H)-ylidene)-1-(2-benzyl)ethanone, etc. These compounds may be used alone or in combination of two or more kinds.

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

As a photosensitive side chain polymer that exhibits liquid crystallinity The organic solvent used in the polymerization reaction is not particularly limited as long as it can dissolve the polymer produced. Specific examples are listed below.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactone, dimethyl sulfide, tetramethyl urea, pyridine, dimethyl sulfide, hexamethyl sulfide Sulphur, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl Base isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylenedi Alcohol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tertiary 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 Base 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 Ketones, 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 acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3 -Ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropyl propionate, 3-methoxybutyl propionate, diglyme, 4-hydroxy-4-methyl -2-pentanone, 3-methoxy-N,N-dimethylpropaneamide, 3-ethoxy-N,N-dimethylpropaneamide, 3-butoxy-N,N- Dimethyl propane amide and so on.

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 mixed and used with the above-mentioned organic solvent within a range that does not precipitate the produced polymer.

In addition, since oxygen in the organic solvent in radical polymerization is a cause of hindering the polymerization reaction, the organic solvent is preferably degassed to the extent possible.

The polymerization temperature during radical polymerization can be any temperature from 30°C to 150°C, but it is preferably in the range of 50°C to 100°C. In addition, the reaction can be carried out at any concentration, but when the concentration is too low, it is difficult to obtain a high molecular weight polymer. When the concentration is too high, the viscosity of the reaction solution becomes too high and it is difficult to stir uniformly, so the monomer concentration is preferably 1 mass % To 50% by mass, more preferably 5 to 30% by mass. The initial reaction is performed at a high concentration, and then an organic solvent can be added.

In the above-mentioned radical polymerization reaction, when the ratio of the radical polymerization initiator to the monomer is larger, the molecular weight of the polymer obtained becomes smaller, and when the ratio of the polymer is smaller, the molecular weight of the polymer obtained becomes larger. The ratio is preferably 0.1 mol% to 10 mol% relative to the polymerized monomer. In addition, various monomer components, solvents, initiators, etc. may be added during polymerization.

[Recycling of polymers]

When recovering the produced polymer from the reaction solution obtained by the above reaction, it is only necessary to put the reaction solution into a weak solvent to precipitate the obtained polymer. Weak solvents 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, water, etc. After the polymer deposited in the weak solvent is recovered by filtration, it can be dried under normal pressure or reduced pressure at normal temperature or by heating. Moreover, when the polymer recovered by precipitation is re-dissolved in an organic solvent, and the operation of re-precipitation recovery is repeated 2 to 10 times, the impurities in the polymer can be reduced. As the weak solvent at this time, for example, alcohols, ketones, hydrocarbons, etc. can be cited. When three or more kinds of weak solvents selected from these are used, the purification efficiency can be further improved, so it is preferable.

[Composition of composition]

The composition of the present invention is preferably prepared into a coating liquid in a manner suitable for the formation of a liquid crystal alignment film. The composition of the present invention is preferably prepared into (A) polymer components and other solutions dissolved in organic solvents. Here, the "(A) polymer component and others" refers to a resin component including a polymer having a side chain represented by formula (I) or (II) and other polymers. In 100% by mass of the composition of the present invention, the content of the (A) polymer component is 1-20% by mass, preferably 3-15% by mass, more preferably 3-10% by mass.

The method of coating the above composition on the substrate is not special limit.

The coating method is generally carried out by screen printing, offset printing, flexographic printing or inkjet method in the industry. As for other coating methods, there are dipping method, roll coating method, slit coating method, spin coating method (spin coating method), spray method, etc., and these can be used according to the purpose.

After the composition is coated on the substrate, a heating means such as a heating plate, a thermal cycle oven or an IR (infrared) oven can be used to evaporate the solvent at 50 to 200°C, preferably 50 to 150°C to obtain a coating film.

The thickness of the coating film varies depending on the target material, for example, 5~10000nm, preferably 10~5000nm. If used as a liquid crystal alignment film, for example, 5~300nm, preferably 10~200nm; if used as a retardation film or holographic film, preferably 500~10000nm, more preferably 500~5000nm.

Furthermore, after step [I] and before step [II], a step of cooling the substrate with the coating film to room temperature may also be provided.

<Step [II]>

Step [II] is to irradiate the coating film obtained in step [I] with polarized ultraviolet rays. When irradiating the film 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 used, ultraviolet rays with a wavelength of 100nm~400nm can be used. It is preferable to select the most appropriate wavelength through a filter or the like according to the type of coating film used. Moreover, in a way that can induce selective photoisomerization reaction, ultraviolet rays with a wavelength of 290nm~400nm are selected. As ultraviolet rays, examples can be used Such as the light emitted from a high-pressure mercury lamp.

When step [III] is performed after step [II], the polarized ultraviolet The radiation amount of the line is related to the coating film used. The irradiation amount is preferably to achieve the maximum value of the difference between the absorbance of ultraviolet rays in the direction parallel to the polarization direction of the polarized ultraviolet rays and the absorbance of ultraviolet rays in the vertical direction (ie △A) (hereinafter also referred to as △Amax) in the coating film. It is in the range of 1% to 70% of the amount of ultraviolet rays, and more preferably in the range of 1% to 50%.

<Step [III]>

Step [III] is to heat the coating film irradiated with polarized ultraviolet light in step [II]. By heating, the alignment control performance can be imparted to the coating film.

Heating can use heating means such as heating plate, thermal cycle oven or IR (infrared) oven. The heating temperature can be determined by considering the temperature of the coating film used to exhibit liquid crystallinity.

The thickness of the coating film formed after heating may be the same thickness as in step [I].

By having the above steps, the manufacturing method of the present invention can efficiently introduce the anisotropy of the coating film. Therefore, the method of the present invention can efficiently manufacture materials, such as substrates with liquid crystal alignment films.

<Step [IV]>

If the target material is a liquid crystal alignment film for liquid crystal display elements, the use step [IV] can obtain a liquid crystal alignment film for liquid crystal display elements.

Here, as a substrate system used on the substrate with a lateral electric field drive The conductive film substrate of the above-mentioned [I]~[III] can be used to obtain a substrate (first substrate) having a liquid crystal alignment film on the conductive film for lateral electric field driving. In addition, a substrate without the conductive film is used instead of a substrate with a conductive film for driving the transverse electric field on the substrate, and the above-mentioned [I]~[III] can be used to obtain a liquid crystal alignment film without the conductive film The substrate (the second substrate).

Step [IV] is to arrange the first and second substrates facing each other through the liquid crystal to make the two liquid crystal alignment films face each other, and fabricate a liquid crystal cell by a conventional method to fabricate a transverse electric field drive type liquid crystal display element step.

If one example of the production of a liquid crystal cell or a liquid crystal display element is given, the first and second substrates described above are prepared, and spacers are spread on the liquid crystal alignment film of one substrate so that the liquid crystal alignment film surface becomes the inside. The method of combining the other substrate, injecting liquid crystal under reduced pressure and sealing, or dropping the liquid crystal on the surface of the liquid crystal alignment film spread with spacers, bonding the substrate and sealing, etc. In this case, it is preferable to use a substrate having a comb-tooth structure for driving a lateral 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. The diameter of the spacer will determine the distance between a pair of substrates sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.

The method of manufacturing a substrate with a coating film is to apply the composition on the substrate to form a coating film, and then irradiate it with polarized ultraviolet rays. Next, the introduction of anisotropy to the side chain type polymer film can be achieved efficiently by heating, and a substrate with a liquid crystal alignment film can be manufactured that can control the alignment of liquid crystals.

The following examples are used to illustrate the present invention in detail, but the present invention does not It is not limited to the embodiment.

[Example]

The abbreviations used in the examples are as follows.

(Methacrylic acid 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 2L four-necked flask, and stirred at room temperature. Reaction tracking was performed by HPLC, after confirming the completion of the reaction, the precipitated solid was filtered, washed with distilled water and ethanol in this order, and the solid was dried under reduced pressure to obtain 175.7 g of compound [C] (yield 94%).

¹ H-NMR (400MHz, DMSO-d6, δppm): 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 2L four-necked flask was added the compound [C] (175.7g, 773mmol), 6-chloro-1-hexanol (116.2g, 851mmol), potassium carbonate (128.3g, 928mmol), potassium iodide (1.28g, 7.73mmol), N,N-dimethylformamide (hereinafter abbreviated as "DMF") (880g), heated and stirred at 80°C. Reaction tracking was performed by HPLC, and after confirming the completion of the reaction, the reaction solution was cooled to around room temperature, and then the reaction solution was poured into 4 L of distilled water. After filtering the separated solids, they were sequentially washed with methanol and ethyl acetate, and the solids were dried under reduced pressure to obtain 196.6 g of compound [D] (yield 78%).

¹ H-NMR (400MHz, DMSO-d6, δppm): 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] (196.6 g, 600 mmol), triethylamine (85.1 g, 841 mmol) and tetrahydrofuran (hereinafter referred to as THF) (1100 g) obtained above were added to a 2L four-necked flask, and the reaction solution was cooled. In this reaction solution, a solution of methacrylic acid chloride (75.3 g, 720 mmol) in THF (100 g) was added dropwise while paying attention so that the internal temperature did not exceed 10°C. After the dropwise addition was completed, the reaction solution was brought to 23°C, and the reaction proceeded. The reaction was tracked by HPLC. After confirming the completion of the reaction, the reaction solution was poured into 7.2L of distilled water, the precipitated solid was filtered, and washed with distilled water and ethyl acetate/hexane mixed solvent in order to reduce the solids. It was press-dried to obtain 168 g of compound [RM1] (yield 71%).

¹ H-NMR (400MHz, DMSO-d6, δppm): 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 1'>

The compound represented by the following formula [RM1'] (wherein R ₂₁ is F, Cl or CN) is synthesized by the same synthetic process as that of the above compound [RM1].

R ₂₁ =F

¹ H-NMR (400MHz, CDCl3, δppm): 8.36 (1H, s), 7.84-7.80 (2H, m), 7.19-7.15 (2H, m), 7.10-7.04 (2H, m), 6.98-6.95 ( 2H, m), 6.10 (1H, s), 5.55-5.54 (1H, m), 4.17 (2H, t), 4.03 (2H, t), 1.95-1.94 (3H, m), 1.87-1.80 (2H, m), 1.76-1.69 (2H, m), 1.56-1.43 (4H, m).

R ₂₁ =Cl

¹ H-NMR (400MHz, CDCl3, δppm): 8.35 (1H, s), 7.84-7.82 (2H, m), 7.35-7.32 (2H, m), 7.14-7.12 (2H, m), 6.98-6.96 ( 2H,m),6.11(1H,s),5.56-5.55(1H,m),4.19-4.15(2H,m),4.04(2H,t),1.95-1.94(3H,m),1.87-1.81( 2H, m), 1.77-1.70 (2H, m), 1.58-1.44 (4H, m).

R ₂₁ =CN

¹ H-NMR (400MHz, CDCl3, δppm): 8.32 (1H, s), 7.85-7.83 (2H, m), 7.68-7.67 (2H, m), 7.22-7.20 (2H, m), 7.01-6.96 ( 2H,m),6.11-6.10(1H,m),5.56-5.55(1H,m),4.16-4.11(2H,m),4.04(2H,t),1.95(3H, s),1.88-1.81( 2H, m), 1.77-1.68 (2H, m), 1.59-1.43 (4H, m).

<Synthesis Example 2> Synthesis of compound [RM2]

In a 3L four-necked flask, add the compound 4-nitrophenol [E] (300.0g, 2.16mol), 6-chloro-1-hexanol (324.1g, 2.37mol), potassium carbonate (358.2g, 2.59mol), Potassium iodide (3.59 g, 21.6 mmol) and DMF (1500 g) were heated and stirred at 80°C. Reaction tracking was performed by HPLC, and after confirming the completion of the reaction, the reaction solution was cooled to around room temperature, and then the reaction solution was poured into 4 L of distilled water. After filtering the respective precipitated solids, they were sequentially washed with methanol and ethyl acetate, and the solids were dried under reduced pressure to obtain 506.4 g of compound [F] (yield 98%).

¹ H-NMR (400MHz, CDCl ₃ , δppm): 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).

Add compound [F](198.0g, 828 mmol), THF (1200 g), distilled water (800 g), tin chloride (392.0 g, 2.07 mol) was added, and heated and stirred at 70°C. After confirming the completion of the reaction, the THF was almost halved by concentration with an evaporator, and the residue was poured into 2 L of ethyl acetate. While paying attention to foaming, add sodium bicarbonate to neutralize it. 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 (400MHz, DMSO-d6, δppm): 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-methoxybenzaldehyde (65.1 g, 478 mmol), and ethanol (1000 g) were added to a 2L four-necked flask, and the reaction was carried out under heating under reflux. After the reaction, the reaction solution was allowed to cool to room temperature, and the precipitated solid was filtered and washed with ethanol. After that, the solid was dried under reduced pressure to obtain 112.4 g of compound [H] (yield 72%).

¹ H-NMR (400MHz, DMSO-d6, δppm): 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] (105.6 g, 323 mmol), triethylamine (48.6 g, 480 mmol), and THF (570 g) obtained above were added to a 2L four-necked flask, and the reaction solution was cooled. In this reaction solution, a solution of methacrylic acid chloride (40.5 g, 387 mmol) in THF (70 g) was added dropwise while taking care that the internal temperature did not exceed 10°C. After the dropwise addition was completed, the reaction solution was brought to 23°C, and the reaction proceeded. The reaction was followed by HPLC. After confirming the completion of the reaction, the reaction solution was poured into 4L of distilled water, the precipitated solid was filtered, and washed with distilled water, ethyl acetate/hexane mixed solvent in order, and the solid was decompressed After drying, 105 g (yield 82%) of compound [RM2] was obtained.

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).

<Synthesis example 2'>

The compound represented by the following formula [RM2'] (where R ₂₂ is F, Cl, CN, or t-Bu) is synthesized by the same synthetic process as the above-mentioned compound [RM2].

R ₂₂ =F

¹ H-NMR (400MHz, CDCl3, δppm): 8.45 (1H, s), 7.90-7.87 (2H, m), 7.23-7.13 (2H, m), 6.94-6.90 (2H, m), 6.90 (1H, s), 5.55-5.54 (1H, m), 4.17 (2H, t), 3.98 (2H, t), 1.96-1.95 (3H, m), 1.84-1.69 (4H, m), 1.56-1.45 (4H, m).

R ₂₂ =Cl

¹ H-NMR (400MHz, CDCl3, δppm): 8.45 (1H, s), 7.82-7.80 (2H, m), 7.43-7.41 (2H, m), 7.22-7.20 (2H, m), 6.91-6.89 ( 2H, m), 6.10 (1H, s), 5.53 (1H, m), 4.15 (2H, t), 3.96 (2H, t), 1.93-1.92 (3H, m), 1.84-1.69 (4H, m) , 1.56-1.45 (4H, m).

R ₂₂ =CN

¹ H-NMR (400MHz, CDCl3, δppm): 8.52 (1H, s), 8.00-7.98 (2H, m), 7.76-7.73 (2H, m), 7.30-7.26 (2H, m), 6.96-6.92 ( 2H,m),6.11-6.10(1H,m),5.56-5.54(1H,m), 4.17(2H,t), 3.99(2H,t),1.95-1.94(3H,m),1.86-1.68( 2H, m), 1.57-1.43 (4H, m).

R ₂₂ =t-Bu

¹ H-NMR (400MHz, CDCl3, δppm): 8.45 (1H, s), 7.83-7.81 (2H, m), 7.52-7.48 (2H, m), 7.26-7.19 (2H, m), 6.93-6.90 ( 2H,m),6.10(1H,s),5.55(1H,s),4.17(2H,t),3.98(2H,t),1.95(3H,s),1.85-1.69(4H,m),1.61 -1.45 (4H, m), 1.36 (9H, s).

<Organic Solvent>

THF: Tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BC: Ding Cerlusu.

<Polymerization initiator>

AIBN: 2,2’-Azobisisobutyronitrile

<Synthesis Example 3-Preparation of Liquid Crystal Alignment Agent (A1)>

RM1 (11.8 g, 30.0 mmol) was dissolved in THF (70.0 g), and after degassing with a diaphragm pump, AIBN (0.04 g, 0.9 mmol) was added and degassed again. Subsequently, the reaction was carried out at 60°C for 12 hours to obtain a polymer solution of methacrylate. The polymer solution was added dropwise to diethyl ether (1000 ml), and the resulting precipitate was filtered. The precipitate was washed with diethyl ether, and dried under reduced pressure in an oven at 40°C to obtain methacrylate polymer powder.

54.0 g of NMP was added to 6.0 g of the obtained powder, and stirred at room temperature for 3 hours. Furthermore, 40.0 g of BCS was added to this solution and stirred at room temperature for 1 hour to obtain a polymer solution (A1) with a solid content concentration of 6.0% by weight. This polymer solution was directly used as a liquid crystal alignment agent (A1) for forming a liquid crystal alignment film.

<Synthesis Example 4-Preparation of Liquid Crystal Alignment Agent (A2)>

Except that RM2 was used instead of RM1 in the above <Synthesis Example 3>, the same method as the above <Synthesis Example 3> was used to obtain a polymer solution (A2) with a solid content concentration of 6.0 wt%. This polymer solution was directly used as a liquid crystal alignment agent (A2) for forming a liquid crystal alignment film.

<Example 1> [Production of Liquid Crystal Cell]

Using the liquid crystal alignment agent (A1) obtained in <Synthesis Example 3>, liquid crystal cells were produced in the order shown below.

The substrate is a glass substrate with a size of 30mm×40mm and a thickness of 0.7mm, and a comb-shaped pixel electrode formed by patterning an ITO film is used. The pixel electrode has a comb-tooth shape formed by a plurality of arrays of electrode elements whose central part is bent into a U shape. The width of each electrode element in the short-side direction is 10 μm, and the interval between the electrode elements is 20 μm. The pixel electrode forming each pixel is formed by arranging a plurality of electrode elements whose central part is bent in the shape of "U". Therefore, the shape of each pixel is not a rectangular shape, but has a similar bold "face" that is curved at the center of the electrode elements. shape. Then, each pixel has a first area on the upper side and a second area on the lower side of the curved portion divided vertically with the curved portion in the center as an interface. When comparing the first area and the second area of each pixel, it becomes the pixel electrode that constitutes them The electrode elements are formed in different directions. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the first area of the pixel is formed as the electrode element of the pixel electrode at an angle of +15° (clockwise), and the second area of the pixel is formed as the angle of the pixel electrode. The electrode element becomes an angle of -15° (clockwise). That is, the first area and the second area of each pixel are the directions of the rotation action (in-plane switching) of the liquid crystal in the substrate surface induced by the voltage applied between the pixel electrode and the counter electrode They are constructed in opposite directions.

Spin the liquid crystal alignment agent (A1) obtained in <Synthesis Example 3> Coated on the prepared substrate with electrodes. Then, it was dried on a hot plate at 70° C. for 90 seconds to form a liquid crystal alignment film with a thickness of 100 nm. Next, the coating film surface was irradiated with 313 nm ultraviolet rays 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.

In addition, a coating film was formed in the same manner as a glass substrate of a columnar spacer with a height of 4 μm, which was not formed with electrodes, and was subjected to an alignment treatment.

Print a sealant (XN-1500T manufactured by Kyoritsu Chemical) on the liquid crystal alignment film of one of the substrates. Next, after bonding the other substrate so that the alignment direction to which the liquid crystal alignment film surface faces becomes 0°, the sealant is thermally cured to produce hollow cells. Liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the hollow cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell having the configuration of a liquid crystal display element of IPS (In-Planes Switching) mode. After the obtained liquid crystal cell was fired at 120°C for 30 minutes, it was confirmed that it exhibited good alignment.

<Example 2> [Production of Liquid Crystal Cell]

Except that the liquid crystal alignment agent (A2) obtained in <Synthesis Example 4> was used instead of the liquid crystal alignment agent (A1) of <Example 1>, a liquid crystal cell was produced by the same method as <Example 1>.

After the obtained liquid crystal cell was fired at 120°C for 30 minutes, it was confirmed that it exhibited good alignment.

<<Synthesis of polymer P1 from RM1 (Compound 3)>>

The polymer P1 was synthesized according to the following procedure.

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

<Polymer P1 Film>

The polymer P1 (Mn=21,000, Mw/Mn=1.9) exhibits a nematic liquid crystal phase at 41 to 111°C.

0.3 g of polymer P1 was dissolved in 10 ml of dichloromethane as a solution, and the solution was spin-coated on a quartz substrate to obtain a thin film of polymer P1 (film thickness: 100-750 nm). Use this film to evaluate the behavior of light-induced realignment and holography.

<Example 3> <Visible and ultraviolet absorption spectrum of polymer P1 film>

The polymer P1 film is transparent in the visible region, and exhibits a photoreaction by ultraviolet irradiation. Fig. 1 is a graph showing the change in the absorption spectrum when light of 313 nm (intensity: 10 mW/cm ² ) is irradiated to the polymer P1 film. If the irradiation amount is changed from 0J/cm ² to 300J/cm ² , the absorption at the wavelengths of 283nm and 332nm will change and become smaller. In particular, when the irradiation amount to 50J / far cm ^2, the change is gradually changed, but the exposure time of more than 100J cm ² /, the peak of 332nm disappears, and a new peak appeared in the vicinity of 260nm.

After light irradiation, the film is transparent in the visible region. Furthermore, after irradiation (irradiation>100J/cm ² ), the film becomes insoluble in organic solvents. This system is considered to be the photoisomerization represented by the following formula (X) as the main part of the photoreaction at the beginning of light irradiation, but when further irradiation, photoisomerization and other photoreactions such as photocrosslinking will occur Wait.

<Example 4> <Measurement of S value and application possibilities for retardation film>

By irradiating with linearly polarized ultraviolet rays at 313nm, the P1 film induces an axis-selective photoreaction, and at the same time produces molecular realignment. Fig. 2 is a graph showing the change in the polarization absorption spectrum of the P1 film after irradiating 10J/cm ² of linearly polarized ultraviolet rays at 313 nm. After irradiation, the absorbance As in the vertical direction for the electric field vector of polarized ultraviolet rays increases, but the absorbance Ap in the parallel direction for the electric field vector of polarized ultraviolet rays decreases. This teaches that after the axial selective light anisotropy is generated, it will induce the realignment of molecules perpendicular to the electric field vector of the polarized ultraviolet light. The S value at 332nm is 0.41, and the birefringence value (Δn) at 514nm is 0.11. It can be seen from these results that the P1 film can be applied to retardation films.

Furthermore, the value of S at a certain wavelength λ is S _λ , which can be determined by As (for polarized ultraviolet (λ) electric field vector, the absorbance in the vertical direction) and _Ap (for polarized ultraviolet (λ) electric field vector, which is parallel The absorbance in the direction) is obtained by the following formula. Still, depending on the magnitude of the measured value of As and the measured value of Ap, it can be obtained by dividing into the following i) or ii).

[Number 1] i) A _s >A _p : S _λ =(A _s -A _p )/(A _s +2A _p ) ii) A _s <A _p : S _λ =(A _p -A _s )/( A _p +2A _s )

<Example 5> <Evaluation of Holography>

、各光束)來進行全像曝光(尚，用來全像曝光的光路圖請參考圖3a)。將晶格間距設為3.15μm，2光束為具有5.9°之角度。圖3b係表示經由使用210秒鐘、2個p偏光(pp)光束之強度全像術曝光後的P1薄膜之偏光光學顯微鏡像。周期性亮線(Λ=3.15μm)係與垂直於晶格向量的分子再配向區域一致。又，表面起伏係以78nm之高度所形成。使用2個s偏光(ss)的強度全像術及2個圓偏光(2CP)時，亦得到相同結果。但表面起伏之高度係依附於偏光，ss時之高度為20nm，2CP時之高度為60nm。 Using a 325nm He-Cd laser (20mW/5mm

, Each beam) for holographic exposure (still, the light path diagram used for holographic exposure, please refer to Figure 3a). Set the lattice spacing to 3.15μm, and the 2 beams have an angle of 5.9°. Fig. 3b shows the polarized optical microscope image of the P1 film after exposure using the intensity holography of 2 p-polarized (pp) beams for 210 seconds. The periodic bright line (Λ=3.15μm) is consistent with the molecular realignment area perpendicular to the lattice vector. In addition, the surface undulations were formed with a height of 78 nm. The same result is also obtained when using the intensity holography of 2 s-polarized light (ss) and 2 circularly polarized light (2CP). However, the height of the surface undulation depends on the polarized light, the height is 20nm for ss and 60nm for 2CP.

Polarized holography is based on the interference polarization pattern, and simultaneously forms both surface undulation formation and periodic molecular realignment. When two circularly polarized light beams with opposite circularly polarized light (±CP) are used, a periodic bright line with a half pitch (Λ=1.58μm) can be observed in the polarized optical microscope image, and the height of the formed surface undulation is 200nm (Figure 3c) ).

From these results, we can see that the P1 film can be applied to holographic films.

Claims (9)

A polarized ultraviolet anisotropic material exhibiting anisotropy by polarized ultraviolet irradiation, which is a material with a polymer having a side chain represented by the following formula (I),

(In the formula, A ₁ represents -O-, -COO- or -OCO-, n represents an integer from 1 to 8, and a part of the methylene group (-CH ₂ -) can be substituted with -O-, -COO-, -OOC-, -NHCO-, -CONH-, -NHCONH-, -NHCOO-, -OCONH-, -C=C- or -C≡C- (but the methylene group adjacent to A ₁ or -O- ( -CH ₂ -) is not substituted by these groups), X represents -CH=N- or -N=CH-, R represents methyl, n ₁₁ and n ₁₂ represent 0, R ₁₁ and R ₁₂ each independently represent Linear or branched alkyl with 1 to 6 carbons, halogen atoms, nitro, cyano, linear or branched alkoxy with 1 to 6 carbons), the aforementioned polymers are further selected from Any liquid crystal side chain in the group consisting of the following formulas (25)~(28):

(In the formula, A each independently represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or- O-CO-CH=CH-; 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 heterocyclic ring, alicyclic hydrocarbon with 5 to 8 carbons, alkyl with 1 to 12 carbons, or alkoxy with 1 to 12 carbons; l represents an integer from 1 to 12 , M represents an integer from 0 to 2, but in formulas (25) to (26), the total of all m is 1 or more, and m3 represents an integer from 1 to 3). The material of claim 1, wherein the aforementioned material is used in one selected from the group consisting of liquid crystal alignment agents, retardation films, and holograms. A composition for polarized ultraviolet anisotropic material, which has (A) a polymer and (B) an organic solvent, (A) the polymer has a side chain represented by the following formula (I) and is irradiated by polarized ultraviolet Exhibiting anisotropic polymers,

(In the formula, A ₁ represents -O-, -COO- or -OCO-, n represents an integer from 1 to 8, and a part of the methylene group (-CH ₂ -) can be substituted with -O-, -COO-, -OOC-, -NHCO-, -CONH-, -NHCONH-, -NHCOO-, -OCONH-, -C=C- or -C≡C- (but the methylene group adjacent to A ₁ or -O- ( -CH ₂ -) is not substituted by these groups), X represents -CH=N- or -N=CH-, R represents methyl, n ₁₁ and n ₁₂ represent 0, R ₁₁ and R ₁₂ each independently represent Linear or branched alkyl with 1 to 6 carbons, halogen atom, nitro, cyano, linear or branched alkoxy with 1 to 6 carbons), the aforementioned (A) polymer Having any liquid crystal side chain selected from the group consisting of the following formulas (25) to (28):

(In the formula, A each independently represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or- O-CO-CH=CH-; 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 heterocyclic ring, alicyclic hydrocarbon with 5 to 8 carbons, alkyl with 1 to 12 carbons, or alkoxy with 1 to 12 carbons; l represents an integer from 1 to 12 , M represents an integer from 0 to 2, but in formulas (25) to (26), the total of all m is 1 or more, and m3 represents an integer from 1 to 3). The composition of claim 3, wherein the aforementioned material is used for one selected from the group consisting of liquid crystal alignment agents, retardation films, and holograms. A manufacturing method of polarized ultraviolet anisotropic material, which has the following steps to obtain polarized ultraviolet anisotropic material that exhibits anisotropy by polarized ultraviolet irradiation: [I] will have (A) polymer and ( B) The step of coating the composition for polarized ultraviolet anisotropic material of organic solvent on the substrate to form a coating film; and [II] the step of irradiating the coating film obtained in [I] with polarized ultraviolet light; wherein, the aforementioned ( A) The polymer has a side chain represented by the following formula (I),

(In the formula, A ₁ represents -O-, -COO- or -OCO-, n represents an integer from 1 to 8, and a part of the methylene group (-CH ₂ -) can be substituted with -O-, -COO-, -OOC-, -NHCO-, -CONH-, -NHCONH-, -NHCOO-, -OCONH-, -C=C- or -C≡C- (but the methylene group adjacent to A ₁ or -O- ( -CH ₂ -) is not substituted by these groups), X represents -CH=N- or -N=CH-, R represents methyl, n ₁₁ and n ₁₂ represent 0, R ₁₁ and R ₁₂ each independently represent Linear or branched alkyl with 1 to 6 carbons, halogen atom, nitro, cyano, linear or branched alkoxy with 1 to 6 carbons), the aforementioned (A) polymer Having any liquid crystal side chain selected from the group consisting of the following formulas (25) to (28):

(In the formula, A each independently represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or- O-CO-CH=CH-; 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 heterocyclic ring, alicyclic hydrocarbon with 5 to 8 carbons, alkyl with 1 to 12 carbons, or alkoxy with 1 to 12 carbons; l represents an integer from 1 to 12 , M represents an integer from 0 to 2, but in formulas (25) to (26), the total of all m is 1 or more, and m3 represents an integer from 1 to 3). The method of claim 5, which further includes the following step: [III] a step of heating the coating film obtained in [II]. The method of claim 5 or 6, wherein the aforementioned material is used for one selected from the group consisting of liquid crystal alignment agents, retardation films, and holograms. A composition for the manufacture of polarized ultraviolet anisotropic material, which has the following formula [RM1] or [RM2],

The composition of claim 8, wherein the polarized ultraviolet anisotropic material is used for one selected from the group consisting of liquid crystal alignment agents, retardation films, and holograms.

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