JP6911885B2 - Manufacturing method of liquid crystal alignment film and manufacturing method of liquid crystal element - Google Patents

Description

The present invention relates to a method for producing a liquid crystal alignment film and a method for producing a liquid crystal element.

Liquid crystal elements are widely used in televisions, mobile devices, various monitors, and the like. Further, in the liquid crystal element, a liquid crystal alignment film having a liquid crystal alignment regulating force is used in order to orient the liquid crystal molecules in the liquid crystal cell. As a method for obtaining a liquid crystal alignment film, a method of rubbing an organic film, a method of obliquely depositing silicon oxide, a method of forming a monomolecular film having a long-chain alkyl group, and a method of irradiating a photosensitive organic film with light ( Photo-orientation method) is known.

Since the photo-alignment method can impart uniform liquid crystal orientation to a photosensitive organic film while suppressing the generation of static electricity and dust, and can also precisely control the liquid crystal orientation direction, various studies have been conducted in recent years. (See, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2004-163646

However, when the photo-alignment method is applied, there is a problem that the orientation-regulating force of the obtained liquid crystal alignment film is not sufficient, and the image is likely to be burned due to this. Further, the reliability of the liquid crystal element tends to be inferior due to the change of the orientation regulating force with time. In recent years, large-screen, high-definition LCD TVs have become the mainstream, and small display terminals such as smartphones and tablet PCs have become widespread, and the demand for high-definition LCD panels is increasing. There is a demand for even higher quality liquid crystal elements.

The present invention has been made in view of the above problems, and one object of the present invention is to provide a method for producing a liquid crystal alignment film capable of obtaining a liquid crystal element having good reliability and afterimage characteristics.

The present inventor has studied diligently to achieve the above-mentioned problems of the prior art, and produced a liquid crystal alignment film by using a polymer composition having a specific compounding composition and by a method including a specific step. We have found that the problem can be solved and have completed the present invention. Specifically, the present invention provides the following means.

1. 1. A step [A] of applying the polymer composition of the following [2] onto a substrate to form a coating film, and a step of irradiating the coating film obtained in the step [A] with polarized radiation [ A method for producing a liquid crystal alignment film, which comprises a step [B] and a step [C] of heating the coating film after irradiation in the step [B] and at least during the irradiation.
[2] At least one polymer (P) selected from the group consisting of polyamic acids, polyamic acid esters, polyimides, polysiloxanes, and polymers obtained by addition polymerization, and radically polymerizable groups, cyclic ether groups, and cyclic thioether groups. , Oxazine ring-containing group, oxazoline group, isocyanate group, blocked isocyanate group, silanol group, methylol group, etherified methylol group and cyclic carbonate group. And a polymer composition containing a low molecular weight compound (R) having a photoorientation site and a molecular weight of 2,000 or less.

2. Above 1. A liquid crystal element provided with a liquid crystal alignment film obtained by the production method described in 1.
3. 3. Above 1. A step of constructing a liquid crystal cell by arranging a pair of substrates on which a liquid crystal alignment film is formed by the manufacturing method described in the above method so as to face each other with the liquid crystal alignment film facing each other via a liquid crystal layer, and an unpolarized light crystal cell. A method of manufacturing a liquid crystal element including a step of irradiating radiation.

According to the method for producing a liquid crystal alignment film of the present invention, a liquid crystal element having good reliability and afterimage characteristics can be obtained.

Hereinafter, a method for producing a liquid crystal alignment film according to the present invention will be described, and a liquid crystal element manufactured by using the manufacturing method will be described.
≪Polymer composition≫
The liquid crystal alignment film in the present invention is produced by using a polymer composition containing a polymer component. Specifically, the following polymer composition of [1] or [2] is used.
[1] A liquid crystal having at least one polymer (P) selected from the group consisting of a polyamic acid, a polyamic acid ester, a polyimide, a polysiloxane, and a polymer obtained by addition polymerization, a crosslinkable group, and a photoalignable moiety. A polymer composition containing a sex compound (QR).
[2] A polymer composition containing the above-mentioned polymer (P), a liquid crystal compound (Q) having a crosslinkable group, and a low molecular weight compound (R) having a photoalignment site and having a molecular weight of 2,000 or less. ..
The liquid crystal compound (Q) and the small molecule compound (R) contained in the polymer composition of the above [2] are different compounds.

<Polymer (P)>
The polymer (P) blended in the polymer compositions [1] and [2] is at least one selected from the group consisting of polyamic acids, polyamic acid esters, polyimides, polysiloxanes and polymers obtained by addition polymerization. Is.
(Polyamic acid)
The polyamic acid according to the present invention can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine.
(Tetracarboxylic dianhydride)
Examples of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid include an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, and an aromatic tetracarboxylic dianhydride. .. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetichydride, 5- (2,5-di). Oxotetrahydrofuran-3-yl) -3a,4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- (2,5-dioxotetrahydrofuran-3-yl) -8 -Methyl-3a, 4,5,9b-tetrahydronaphthan [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro -3'-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3 , 5,6-tricarboxy-2-carboxymethylnorbornan-2: 3,5: 6-dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4, 6: 8-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetrahydrofuran, cyclohexanetetracarboxylic acid dianhydride, etc.;

（式（Ｂ−１）中、Ｘ^１及びＸ^２は、それぞれ独立に単結合、酸素原子、硫黄原子、−ＣＯ−、＊−ＣＯＯ−、＊−ＯＣＯ−、＊−ＣＯ−ＮＲ^２２−、＊−ＮＲ^２２−ＣＯ−（ただし、Ｒ^２２は水素原子又は炭素数１〜６の１価の炭化水素基である。「＊」は、Ｒ^２１との結合手を示す。）である。Ｒ^２１は、炭素数１〜１０のアルカンジイル基、当該アルカンジイル基の炭素−炭素結合間に−Ｏ−を含む２価の基、シクロヘキシレン基、フェニレン基又はビフェニレン基である。）
などを；それぞれ挙げることができるほか、特開２０１０−９７１８８号公報に記載のテトラカルボン酸二無水物を用いることができる。 Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 4,4'-(hexafluoroisopropyridene) diphthalic anhydride, and the following formula (B-1).

(In the formula ^{(B-1), X} 1 and ^{X 2} are each independently a single bond, an oxygen atom, a sulfur atom, -CO -, * - COO - , * - OCO -, * - CO-NR 22 -, * -NR ^22- CO- (where R ²² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. "*" Indicates a bond with ^{R 21). Reference numeral 21} denotes an alcandiyl group having 1 to 10 carbon atoms, a divalent group containing —O— between carbon-carbon bonds of the alcandiyl group, a cyclohexylene group, a phenylene group, or a biphenylene group).
In addition to the above, the tetracarboxylic dianhydride described in JP-A-2010-97188 can be used.

なお、上記テトラカルボン酸二無水物は、１種を単独で又は２種以上組み合わせて使用することができる。 Specific examples of the alkanediyl group having 1 to 10 carbon atoms R ²¹ in the above formula (B-1), such as methylene group, ethylene group, propylene group, butanediyl group, pentanediyl group, hexanediyl group, Heputanjiiru group, octane Examples thereof include a diyl group, a nonandiyl group, a decandiyl group and the like, and these may be linear or branched. It is preferably linear. In a divalent group containing -O- between carbon-carbon bonds of an alkanediyl group, the number of oxygen atoms may be one or two or more.
Specific examples of the compound represented by the above formula (B-1) include compounds represented by each of the following formulas (B-1-1) to (B-1--4).

The tetracarboxylic dianhydride may be used alone or in combination of two or more.

The tetracarboxylic dianhydride used in the synthesis preferably contains an alicyclic tetracarboxylic dianhydride, and at least one moiety selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure and a cyclohexane ring structure. It is more preferable to contain a tetracarboxylic dianhydride having a structure. Specifically, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetracarboxylic dianhydride), 5- (2,5-dioxotetracarboxylic dianhydride) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- (2,5-dioxotetraki-tetra-3-yl) -8-methyl-3a, 4, 5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, cyclopentanetetracarboxylic dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic It is particularly preferable to contain at least one compound (T) selected from the group consisting of acid dianhydride and cyclohexanetetracarboxylic dianhydride.
The amount of these preferable compounds (T) to be used (the total amount when two or more kinds are used) is 10 mol% or more based on the total amount of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid. It is preferably 20 mol% or more, more preferably 30 mol% or more.

(Diamine)
Examples of the diamine used for the synthesis of the polyamic acid include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, and a diaminoorganosiloxane. Specific examples of these include, as aliphatic diamines, m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane and the like;
As the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine) and the like;

（式（Ｅ−１）中、Ｘ^I及びＸ^IIは、それぞれ独立に、単結合、−Ｏ−、＊−ＣＯＯ−又は＊−ＯＣＯ−（ただし、「＊」はＸ^Ｉとの結合手を示す。）であり、Ｒ^Ｉは炭素数１〜３のアルカンジイル基であり、Ｒ^ＩＩは単結合又は炭素数１〜３のアルカンジイル基であり、ａは０又は１であり、ｂは０〜２の整数であり、ｃは１〜２０の整数であり、ｄは０又は１である。但し、ａ及びｂが同時に０になることはない。）
で表される化合物などの配向性基含有ジアミン： As aromatic diamines, for example, dodecanoxidiaminobenzene, tetradecanoxidiaminobenzene, pentadecanoxidiaminobenzene, hexadecanoxidiaminobenzene, octadecanoxidiaminobenzene, cholestanyloxydiaminobenzene, cholesteryloxydiaminobenzene. , Cholestanyl diaminobenzoate, Cholesteryl diaminobenzoate, Ranostanyl diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholesterol, 3,6-bis (4-aminophenoxy) cholesterol, 1,1-bis (4) -((Aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) Phenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, N- (2,4-diaminophenyl) -4- (4-Heptylcyclohexyl) benzamide, the following formula (E-1)

(In the formula (E-1), X ^I and X ^II are independently single-bonded, -O-, * -COO- or * -OCO- (where "*" is a bond with ^{X I.} shown.), and, ^{R I} is an alkanediyl group having 1 to 3 carbon ^{atoms, R II} is a single bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is 0 It is an integer of ~ 2, c is an integer of 1 to 20, d is 0 or 1. However, a and b cannot be 0 at the same time.)
Orientation group-containing diamines such as compounds represented by:

p-Phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfide, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, 1 , 5-bis (4-aminophenoxy) pentane, 1,7-bis (4-aminophenoxy) heptane, bis [2- (4-aminophenyl) ethyl] hexanedioic acid, N, N-bis (4-amino) Phenyl) methylamine, 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 1,5-diaminonaphthalene, 2 , 2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,7-diaminofluorene, 2,2-bis [4- ( 4-Aminophenoxy) Phenyl] Propane, 9,9-Bis (4-Aminophenyl) Fluolene, 2,2-Bis [4- (4-Aminophenoxy) Phenyl] Hexafluoropropane, 2,2-Bis (4-Aminophenyl) Aminophenyl) hexafluoropropane, 4,4'-(p-phenylenediisopropyridene) bisaniline, 4,4'-(m-phenylenediisopropyriden) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, etc.;
Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane; and the diamine described in JP-A-2010-97188 can be used.

In the above formula (E-1) ^{"-X I - (R I -X II} ) d - " Examples of the divalent group represented by the alkanediyl group having 1 to 3 carbon atoms, * - O -, * -COO- or _{* -O-C 2 H 4 -O-} ( where bond marked with "*" is bonded to the diamino phenyl group.) is preferably. Examples of the group "-C _c H _{2c + 1} " include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group and a tetradecyl group. Examples thereof include a group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group, an eikosyl group and the like, and these are preferably linear. The two amino groups in the diaminophenyl group are preferably at the 2,4- or 3,5-position with respect to the other groups.

Specific examples of the compound represented by the above formula (E-1) include compounds represented by each of the following formulas (E-1-1) to (E-1-4). ..

When applied to a liquid crystal alignment agent for a TN type, STN type or vertically oriented type liquid crystal display element, a group capable of imparting liquid crystal alignment ability to a coating film without irradiating light on the side chain of polyamic acid (liquid crystal alignment). Sex groups) may be introduced. Examples of the liquid crystal oriented group include an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a group having a steroid skeleton having 17 to 51 carbon atoms, and a polycyclic ring. Examples thereof include groups having a structure. The polyamic acid having a liquid crystal oriented group can be obtained, for example, by polymerization containing an oriented group-containing diamine in the monomer composition. When an orientation group-containing diamine is used, the blending amount thereof is preferably 3 mol% or more, preferably 5 to 70 mol%, based on the total diamine used for synthesis from the viewpoint of liquid crystal orientation. Is more preferable.

The polymer (P) is a nitrogen-containing heterocycle (excluding the imide ring of polyimide), and is at least one nitrogen-containing structure selected from the group consisting of a secondary amino group and a tertiary amino group (hereinafter, "nitrogen-containing"). It is also referred to as "structure"). Since the polymer (P) has a nitrogen-containing structure, it is preferable in that the effect of improving the reduction of seizure due to the DC voltage of the liquid crystal display element can be enhanced. The polymer (P) having a nitrogen-containing structure can be obtained by using a monomer having a nitrogen-containing structure as at least a part of a raw material. Examples of the monomer include diamines having a nitrogen-containing structure.

（式（Ｎ−１）中、Ｒ^６は水素原子又は炭素数１〜１０の１価の炭化水素基である。「＊」は炭化水素基に結合する結合手である。） In the diamine having a nitrogen-containing structure, examples of the nitrogen-containing heterocycle that the diamine may have include pyrol, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indol, benzimidazole, purine, quinoline, and the like. Examples thereof include isoquinoline, naphthylidine, quinoxalin, phthalazine, triazole, carbazole, aclysine, piperidine, piperazine, pyrrolidine, hexamethyleneimine and the like. Among them, it is preferable to have at least one selected from the group consisting of pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole and acridine.
The secondary amino group and the tertiary amino group that the diamine having a nitrogen-containing structure may have are represented by, for example, the following formula (N-1).

(In the formula (N-1), R ⁶ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. “*” Is a bond that binds to the hydrocarbon group.)

In the above formula (N-1), the ^{monovalent hydrocarbon group of R 6} includes, for example, an alkyl group such as a methyl group, an ethyl group and a propyl group; a cycloalkyl group such as a cyclohexyl group; a phenyl group, a methylphenyl group and the like. The aryl group of the above can be mentioned. R ⁶ is preferably a hydrogen atom or a methyl group.

Specific examples of the amine having a nitrogen-containing structure include 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, and N-methyl-3,6-diamino. Carbazole, 1,4-bis- (4-aminophenyl) -piperazin, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N' -Bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, the following formulas (D-2-1) to (D-2-8) Examples thereof include compounds represented by each of the above.

In the synthesis of polyamic acid, the ratio of diamine having a nitrogen-containing structure is 0.1 mol% or more with respect to the total amount of diamine used in the synthesis from the viewpoint of sufficiently obtaining the effect of improving the reliability of the liquid crystal display element. It is preferably 1 mol% or more, and further preferably 2 mol% or more. The upper limit of the usage ratio is preferably 60 mol% or less, more preferably 50 mol% or less, and further preferably 40 mol% or less. The diamine having a nitrogen-containing structure may be used alone or in combination of two or more.

(Synthesis of polyamic acid)
The polyamic acid can be obtained by reacting the tetracarboxylic dianhydride as described above with a diamine, if necessary, with a molecular weight modifier. The ratio of tetracarboxylic acid dianhydride and diamine used in the polyamic acid synthesis reaction is 0.2 to 2 for the acid anhydride group of tetracarboxylic acid dianhydride with respect to 1 equivalent of the amino group of the diamine. The ratio of equivalents is preferable, and the ratio of 0.3 to 1.2 equivalents is more preferable.

Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, and monoisocyanate compounds such as phenylisocyanate and naphthylisocyanate. Can be mentioned. The ratio of the molecular weight adjusting agent used is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine used.

The polyamic acid synthesis reaction is preferably carried out in an organic solvent. The reaction temperature at this time is preferably −20 ° C. to 150 ° C., more preferably 0 to 100 ° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.
Examples of the organic solvent used in the reaction include an aprotic polar solvent, a phenol-based solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenolic solvent (organic solvent of the first group), or one or more selected from the organic solvent of the first group. It is preferable to use a mixture of one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents of the second group). In the latter case, the proportion of the organic solvent used in the second group is preferably 50% by weight or less, more preferably 40% by weight, based on the total amount of the organic solvent in the first group and the organic solvent in the second group. It is less than or equal to, more preferably 30% by weight or less.

Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol. It is preferable to use one or more selected from the group consisting of and halogenated phenol as a solvent, or to use a mixture of one or more of these and another organic solvent in the above ratio range. Examples of other organic solvents used at this time include butyl cellosolve, 2-butoxy-1-propanol, diethylene glycol diethyl ether and the like. The amount of the organic solvent used (a) shall be such that the total amount (b) of the tetracarboxylic dianhydride and the diamine is 0.1 to 50% by weight based on the total amount (a + b) of the reaction solution. Is preferable.

As described above, a reaction solution obtained by dissolving a polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the polymer composition, the polyamic acid contained in the reaction solution may be isolated and then used for the preparation of the polymer composition, or the isolated polyamic acid may be used. After purification, it may be used for preparation of a polymer composition. Isolation and purification of the polyamic acid can be carried out according to a known method.

(Polyamic acid ester)
The polyamic acid ester in the present invention is, for example, [I] a method of reacting a polyamic acid obtained by the above synthetic reaction with an esterifying agent, [II] a method of reacting a tetracarboxylic dianester with a diamine, [III]. It can be obtained by a method of reacting a tetracarboxylic dianester dihalide with a diamine, or the like.
In the present specification, the "tetracarboxylic dianester" means a compound in which two of the four carboxyl groups of the tetracarboxylic acid are esterified and the remaining two are carboxyl groups. The "tetracarboxylic acid diester dihalogenate" means a compound in which two of the four carboxyl groups of the tetracarboxylic acid are esterified and the remaining two are halogenated.

Examples of the esterifying agent used in the method [I] include hydroxyl group-containing compounds, acetal-based compounds, halides, and epoxy group-containing compounds. Specific examples of these include, for example, alcohols such as methanol, ethanol and propanol, and phenols such as phenol and cresol as hydroxyl group-containing compounds; for example, N, N-dimethylformamide diethyl acetal, N, as acetal compounds. N-diethylformamide diethyl acetal and the like; as halides such as methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like; containing epoxy groups. Examples of the compound include propylene oxide and the like.

The tetracarboxylic dianhydride used in the method [II] can be obtained, for example, by opening the ring of the tetracarboxylic dianhydride exemplified in the synthesis of the polyamic acid with alcohols such as methanol and ethanol. Moreover, as the diamine used in the method [II], the diamine exemplified in the synthesis of the polyamic acid can be mentioned. The reaction of method [II] is preferably carried out in an organic solvent in the presence of a suitable dehydration catalyst. Examples of the organic solvent include organic solvents exemplified as those used for the synthesis of polyamic acids. Examples of the dehydration catalyst include 4- (4,6-dimethoxy-1,3,5-triazine-2-yl) -4-methylmorpholinium halide, carbonylimidazole, phosphorus-based condensing agent and the like. The reaction temperature at this time is preferably -20 to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

The tetracarboxylic dianester dihalide used in the method [III] can be obtained, for example, by reacting the tetracarboxylic dianester obtained as described above with an appropriate chlorinating agent such as thionyl chloride. Moreover, as the diamine used in the method [III], the diamine exemplified in the synthesis of the polyamic acid can be mentioned. The reaction of method [III] is preferably carried out in an organic solvent in the presence of a suitable base. Examples of the organic solvent include organic solvents exemplified as those used for the synthesis of polyamic acids. As the base, for example, tertiary amines such as pyridine and triethylamine; alkali metals such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium and potassium can be preferably used. The reaction temperature at this time is preferably -20 to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

The polyamic acid ester contained in the polymer composition may have only an amic acid ester structure, or may be a partial esterified product in which the amic acid structure and the amic acid ester structure coexist. The reaction solution obtained by dissolving the polyamic acid ester may be used as it is for the preparation of the polymer composition, or the polyamic acid ester contained in the reaction solution may be isolated and then used for the preparation of the polymer composition. Alternatively, the isolated polyamic acid ester may be purified and then used for preparation of the polymer composition. Isolation and purification of the polyamic acid ester can be carried out according to a known method.

(Polyimide)
The polyimide can be obtained, for example, by dehydrating and ring-closing the polyamic acid synthesized as described above to imidize it.
The polyimide may be a completely imidized product in which all of the amic acid structure possessed by its precursor polyamic acid is dehydrated and ring-closed, and only a part of the amic acid structure is dehydrated and ring-closed to form an amic acid structure and an imide. It may be a partially imidized product in which a ring structure coexists. The polyimide used in the reaction preferably has an imidization ratio of 20% or more, more preferably 30 to 99%, and even more preferably 40 to 99%. This imidization ratio is expressed as a percentage of the ratio of the number of imide ring structures to the total of the number of amic acid structures and the number of imide ring structures of polyimide. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably carried out by a method of heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating as necessary. .. Of these, the latter method is preferable.

In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a solution of polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 1 mol of the amic acid structure of the polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, colidin, lutidine, and triethylamine can be used. The amount of the dehydration ring closure catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring closure reaction include organic solvents exemplified as those used in the synthesis of polyamic acids. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

In this way, a reaction solution containing polyimide is obtained. This reaction solution may be used as it is for the preparation of the polymer composition, or may be used for the preparation of the polymer composition after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and the polyimide is isolated. The polymer composition may be prepared in the above, or the isolated polyimide may be purified and then used for the preparation of the polymer composition. These purification operations can be performed according to known methods. In addition, polyimide can also be obtained by imidization of a polyamic acid ester.

The polyamic acid, polyamic acid ester, and polyimide obtained as described above preferably have a solution viscosity of 10 to 800 mPa · s when made into a solution having a concentration of 10% by weight, and are preferably 15 to 500 mPa · s. It is more preferable that the solution has the viscosity of. The solution viscosity (mPa · s) of the polymer is based on a polymer solution having a concentration of 10% by weight prepared using a good solvent of the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). , A value measured at 25 ° C. using an E-type rotational viscometer.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of polyamic acid, polyamic acid ester and polyimide is preferably 1,000 to 500,000, more preferably 2,000 to 2,000. It is 300,000. The molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less.

(Polyorganosiloxane)
The polyorganosiloxane according to the present invention can be obtained, for example, by hydrolyzing and condensing a hydrolyzable silane compound.

Examples of the silane compound used for the synthesis of polyorganosiloxane include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxy. Alkoxysilane compounds such as silane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane , 3-Aminopropyltriethoxysilane, N- (3-cyclohexylamino) propyltrimethoxysilane and other nitrogen / sulfur-containing alkoxysilane compounds;
Epyl group-containing silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane Compound;
3- (Meta) acryloxypropyltrimethoxysilane, 3- (meth) acryloxipropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxipropylmethyldiethoxysilane, vinyl An unsaturated bond-containing alkoxysilane compound such as trimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane; trimethoxysilylpropyl succinic anhydride and the like can be mentioned. As the hydrolyzable silane compound, one of these can be used alone or in combination of two or more. In addition, "(meth) acryloxy" has a meaning including "acryloxy" and "methacryloxy".

The above hydrolysis / condensation reaction can be carried out by reacting one or more of the above silane compounds with water, preferably in the presence of a suitable catalyst and organic solvent. In the hydrolysis / condensation reaction, the ratio of water used is preferably 0.5 to 100 mol, more preferably 1 to 30 mol, based on 1 mol of the silane compound (total amount).

Examples of the catalyst used in the hydrolysis / condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, and zirconium compounds. The amount of the catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, and should be set appropriately, but is preferably 0.01 to 3 times the molar amount of the total amount of the silane compound, for example. , More preferably 0.05 to 1 times the molar amount.
Examples of the organic solvent used in the above hydrolysis / condensation reaction include hydrocarbons, ketones, esters, ethers, alcohols and the like. Of these, it is preferable to use a water-insoluble or poorly water-soluble organic solvent. The proportion of the organic solvent used is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of the total silane compound used in the reaction.

The above hydrolysis / condensation reaction is preferably carried out by heating in, for example, an oil bath. During the hydrolysis / condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C. The heating time is preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During heating, the mixture may be agitated or placed under reflux. Further, after the reaction is completed, it is preferable to wash the organic solvent layer separated from the reaction solution with water. In this cleaning, it is preferable to use water containing a small amount of salt (for example, an aqueous solution of ammonium nitrate of about 0.2% by weight) to facilitate the cleaning operation. The washing is carried out until the water layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve, and then the solvent is removed. The polyorganosiloxane to be obtained can be obtained. The method for synthesizing polyorganosiloxane is not limited to the above-mentioned hydrolysis / condensation reaction, and may be carried out by, for example, a method of reacting a hydrolyzable silane compound in the presence of oxalic acid and alcohol.

By using an epoxy group-containing silane compound as at least a part of the raw material in the above condensation reaction, a polyorganosiloxane having an epoxy group in the side chain can be obtained. Further, the obtained epoxy group-containing polyorganosiloxane may be further reacted with a carboxylic acid having a liquid crystal oriented group. By this reaction, a polyorganosiloxane having a liquid crystal oriented group in the side chain can be obtained. The reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid can be carried out according to a known method.

For the polyorganosiloxane according to the present invention, the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC is preferably in the range of 100 to 50,000, more preferably in the range of 200 to 10,000. .. When the weight average molecular weight of the polyorganosiloxane is in the above range, it is easy to handle when producing a liquid crystal alignment film, and the obtained liquid crystal alignment film has sufficient material strength and properties.

(Polymer obtained by addition polymerization)
The polymer obtained by the above addition polymerization (hereinafter, also referred to as "polymer (PMA)") can be obtained by polymerizing a monomer having a polymerizable unsaturated bond. Examples of the polymerizable unsaturated bond include a (meth) acryloyl group, a vinyl group, a styryl group, a maleimide group, and the like. Specific examples of the monomer having such a polymerizable unsaturated bond include (meth) acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, vinyl benzoic acid and the like. Saturated carboxylic acid: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic Benzyl acid, -2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, methoxyethyl (meth) acrylate, -N, N-dimethylamino (meth) acrylate Ethyl, (meth) methoxypolyethylene glycol acrylate, (meth) octoxypolyethylene glycol acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) Unsaturated carboxylic acid esters such as acrylic acid 3,4-epoxycyclohexylmethyl, (meth) acrylic acid 3,4-epoxybutyl, acrylic acid 4-hydroxybutylglycidyl ether: maleic anhydride, itaconic anhydride, citraconic anhydride, Unsaturated polyvalent carboxylic acid anhydrides such as cis-1,2,3,4-tetrahydrophthalic acid anhydrides: (meth) acrylic compounds such as;
Aromatic vinyl compounds such as styrene, methylstyrene and divinylbenzene;
Conjugated diene compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene;
Maleimide group-containing compounds such as N-methylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide; and the like. As the monomer having a polymerizable group unsaturated bond, one type can be used alone or two or more types can be used in combination.

As the polymer (PMA), poly (meth) acrylate, which is a polymer of a monomer containing a (meth) acrylic compound, is preferable from the viewpoint of transparency and material strength. In the synthesis of the polymer (PMA), the ratio of the (meth) acrylic compound used is preferably 50 mol% or more, preferably 60 mol% or more, based on the total amount of the monomers used in the synthesis. More preferably, it is more preferably 70 mol or more.

The polymer (PMA) can be obtained, for example, by polymerizing a monomer having a polymerizable group unsaturated bond in the presence of a polymerization initiator. Examples of the polymerization initiator used include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-azobis (4-methoxy-2). , 4-Dimethylvaleronitrile) and other azo compounds; benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1'-bis (t-butylperoxy) cyclohexane and other organic peroxides; hydrogen peroxide; these Examples thereof include a redox-type initiator composed of a peroxide and a reducing agent. Of these, azo compounds are preferred. As the polymerization initiator, one of these can be used alone or in combination of two or more.
The proportion of the polymerization initiator used is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of all the monomers used in the reaction.

The polymerization reaction is preferably carried out in an organic solvent. Examples of the organic solvent used in the reaction include alcohols, ethers, ketones, amides, esters, hydrocarbon compounds and the like. Among these, it is preferable to use at least one selected from the group consisting of alcohol and ether, and examples thereof include diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate. The organic solvent can be used alone or in combination of two or more.

In the above polymerization reaction, the reaction temperature is preferably 30 ° C. to 120 ° C., more preferably 60 to 110 ° C. The reaction time is preferably 1 to 36 hours, more preferably 2 to 24 hours. The amount of the organic solvent used (a) is such that the total amount (b) of the monomers used in the reaction is 0.1 to 60% by weight with respect to the total amount (a + b) of the reaction solution. It is preferable to do so.

The polymer (PMA) may be a polymer having a liquid crystal oriented group in the side chain. The method for synthesizing the polymer is not particularly limited, but for example, by using an epoxy group-containing compound as at least a part of the raw material, a polymer having an epoxy group in the side chain is synthesized, and then the epoxy group is used in the side chain. Examples thereof include a method of reacting the polymer contained in the above with a carboxylic acid having a liquid crystal oriented group. As for various conditions in the reaction between the polymer having an epoxy group in the side chain and the carboxylic acid, the description of the method for synthesizing the orientation group-containing polyorganosiloxane can be applied.

For the polymer (PMA), the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC improves the liquid crystal orientation of the formed liquid crystal alignment film and secures the stability of the liquid crystal orientation over time. From such a viewpoint, it is preferably 250 to 500,000, more preferably 500 to 100,000, and even more preferably 1,000 to 50,000.

The polymer composition according to the present invention is a single polymer (P) selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, and a polymer obtained by addition polymerization. Or in combination of two or more. The mode of containing the polymer (P) in the polymer composition can be appropriately selected depending on the intended use and environment, and preferred examples for achieving the effects of the present invention include the following [a] to []. d] and the like.
[A] An embodiment in which the polymer (P) is at least one selected from the group consisting of polyamic acid, polyimide and polyamic acid ester.
[B] An embodiment in which the polymer (P) contains at least one selected from the group consisting of polyamic acid, polyimide and polyamic acid ester, and polyorganosiloxane.
[C] An embodiment in which the polymer (P) is a polyorganosiloxane.
[D] An embodiment in which the polymer (P) is a poly (meth) acrylate.
Of these, the aspect of [a] or [b] is preferable from the viewpoint of more preferably obtaining the effect of the present invention. In the case of the above [b], the total content of the polyamic acid, the polyimide and the polyamic acid ester may be 5% by weight or more with respect to the total amount of the polymer (P) contained in the polymer composition. It is preferably 10% by weight or more, more preferably 20% by weight or more. The upper limit of the content is preferably 99% by weight or less, and more preferably 97% by weight or less.

In the polymer composition of the present invention, the blending ratio of the polymer (P) (the total amount when two or more kinds are blended) is a solid component in the polymer composition (a component other than the solvent of the polymer composition). ), It is preferably 5% by weight or more, more preferably 10 to 99.9% by weight, and even more preferably 30 to 99.5% by weight.

<Liquid crystal compound (QR)>
The liquid crystal compound (QR) is a liquid crystal compound having a crosslinkable group and a photo-oriented site. Here, the "liquid crystal compound" in the present specification refers to a compound having a rigid mesogen moiety and a flexible moiety. Rigid mesogen sites include, for example, cycloalkanes having 3 to 30 carbon atoms and aromatic rings having 5 to 30 carbon atoms (however, any carbon atom in the cycloalkane and aromatic rings is replaced with an oxygen atom, a nitrogen atom or a sulfur atom. The hydrogen atom bonded to the carbon atom may be substituted with an arbitrary monovalent substituent.) It is a structure containing 1 to 10 ring structures of at least one selected from the above. preferable.
The flexible moiety includes, for example, a saturated chain hydrocarbon group, an oligoethylene oxide structure and an oligosiloxane structure (however, any carbon atom may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom, and the carbon atom may be used. The hydrogen atom to be bonded may be substituted with an arbitrary monovalent substituent.) It is preferable that the hydrogen atom has at least one structure selected from the group consisting of.
Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), cyano group, nitro group, alkyl group, alkoxy group and the like.

Examples of the crosslinkable group contained in the liquid crystal compound (QR) include a functional group exhibiting crosslinkability by at least one of light and heat. Specifically, for example, a radically polymerizable group, a photocrosslinkable group, a cyclic ether group, a cyclic thioether group, an oxazine ring-containing group, an oxazoline group, an isocyanate group, a blocked isocyanate group, a silanol group, a methylol group, an etherified methylol group and It is preferably at least one selected from the group consisting of cyclic carbonate groups. The (meth) acryloyl group means to include an acryloyl group and a methacryloyl group.

Here, examples of the radically polymerizable group include (meth) acryloyl group, styryl group, maleimide group, vinyl group, vinyl ether group, allyl group, ethynyl group and the like. Of these, a (meth) acryloyl group, a vinyl group or an allyl group is preferable, and a (meth) acryloyl group is more preferable.
The photocrosslinkable group is preferably a group having a structural site that dimerizes by light irradiation, for example, a benzoyl (meth) acrylic group containing benzoyl (meth) acrylic acid or a derivative thereof as a basic skeleton, cinnamic acid or A cinnamic acid-containing group containing the derivative as a basic skeleton, a cinnamide-containing group containing cinnamide or a derivative thereof as a basic skeleton, a chalcone-containing group containing calcon or a derivative thereof as a basic skeleton, and coumarin or a derivative thereof as a basic skeleton. Examples thereof include a coumarin-containing group, a timine-containing group containing timine or a derivative thereof as a basic skeleton, and a uracil-containing group containing uracil or a derivative thereof as a basic skeleton. Of these, a cinnamic acid-containing group, a benzoyl (meth) acrylic group, or a coumarin-containing group is preferable.
Examples of the cyclic ether group include an epoxy group and an oxetanyl group.
The blocked isocyanate group may be any group obtained by reacting the isocyanate group with a blocking agent such as a compound having active hydrogen or an active methylene compound to make it inactive at room temperature. As the blocking agent, a known one can be used.
Among these, the crosslinkable group of the liquid crystal compound (QR) is preferably a radically polymerizable group or a cyclic ether group, and preferably a (meth) acryloyl group, an epoxy group, or an oxetanyl group. The number of crosslinkable groups contained in the liquid crystal compound (QR) is not particularly limited, but is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2.

As the photoalignment site of the liquid crystal compound (QR), a structure exhibiting anisotropy by photoisomerization, photodimerization, photodecomposition, photofries rearrangement, or the like can be adopted. Specifically, for example, an azo-containing group containing an azo compound or a derivative thereof as a basic skeleton, a katsura acid-containing group containing katsura acid or a derivative thereof as a basic skeleton, and a cinnamide-containing group containing cinnamide or a derivative thereof as a basic skeleton. , Stilben-containing group containing stillben or its derivative as a basic skeleton, chalcone-containing group containing calcon or its derivative as a basic skeleton, benzophenone-containing group containing benzophenone or its derivative as a basic skeleton, coumarin or its derivative as a basic skeleton Examples thereof include a coumarin-containing group contained therein. Among these, a cinnamic acid-containing group or an azo-containing group is preferable in terms of good photo-orientation. In the liquid crystal compound (QR), the number of photooriented portions is not particularly limited, and may be one or two or more.

The liquid crystal phase of the liquid crystal compound (QR) is not limited, but a nematic phase or a smectic phase is preferable from the viewpoint of orientation. Of these, the nematic phase is preferable.
The molecular weight of the liquid crystal compound (QR) is not particularly limited, but is preferably 2,000 or less, more preferably 1,000 or less, and further preferably 800 or less.
Specific examples of the liquid crystal compound (QR) include compounds represented by the following formulas (QR-1) to (QR-12). The liquid crystal compound (QR) may be used alone or in combination of two or more.

The blending ratio of the liquid crystal compound (QR) in the polymer composition of the above [1] is 1 to 1,000 parts by weight with respect to 100 parts by weight of the polymer (P) in the polymer composition. It is preferably 5 to 500 parts by weight, more preferably 10 to 300 parts by weight. If the blending ratio is less than 1 part by weight, it is difficult to sufficiently obtain the effect of improving the reliability and afterimage characteristics of the liquid crystal display element, and if it is more than 1,000 parts by weight, the electrical characteristics tend to deteriorate.

<Liquid crystal compound (Q)>
The liquid crystal compound (Q) is a liquid crystal compound having a crosslinkable group. As for the crosslinkable group contained in the liquid crystal compound (Q), an example of the crosslinkable group contained in the liquid crystal compound (QR) and a description of a preferable specific example can be applied. However, the liquid crystal compound (Q) is different from the liquid crystal compound (QR) in that it does not have a photoalignment site.
The liquid crystal phase of the liquid crystal compound (Q) is preferably a nematic phase or a smectic phase, and more preferably a nematic phase. The molecular weight of the liquid crystal compound (Q) is not particularly limited, but is preferably 2,000 or less, more preferably 1,000 or less, and further preferably 800 or less.
Specific examples of the liquid crystal compound (Q) include compounds represented by the following formulas (Q-1) to (Q-7). The liquid crystal compound (Q) may be used alone or in combination of two or more.

<Small molecule compound (R)>
The small molecule compound (R) is not particularly limited as long as it is a compound having a photoalignment site and having a molecular weight of 2,000 or less. As the photo-oriented site of the small molecule compound (R), an example of the photo-oriented site of the liquid crystal compound (QR) and a description of a preferable specific example can be applied. However, the small molecule compound (R) differs from the liquid crystal compound (QR) in that it does not have a crosslinkable group. The molecular weight of the small molecule compound (R) is preferably 1,000 or less, more preferably 800 or less.
Specific examples of the small molecule compound (R) include compounds represented by the following formulas (R-1) to (R-13). The small molecule compound (R) can be used alone or in combination of two or more.

The compounding ratio of the liquid crystal compound (Q) and the small molecule compound (R) in the polymer composition of the above [2] is such that the total amount of the liquid crystal compound (Q) and the small molecule compound (R) is the polymer composition. It is preferably 1 to 1,000 parts by weight, more preferably 5 to 500 parts by weight, and 10 to 300 parts by weight with respect to 100 parts by weight of the polymer (P) in the substance. More preferred. If the blending ratio is less than 1 part by weight, it is difficult to sufficiently obtain the effect of improving the reliability and afterimage characteristics of the liquid crystal display element, and if it is more than 1,000 parts by weight, the electrical characteristics tend to deteriorate.
Further, for each of the liquid crystal compound (Q) and the small molecule compound (R), the blending ratio of the liquid crystal compound (Q) in the polymer composition is 0 with respect to 100 parts by weight of the polymer (P). It is preferably .8 to 800 parts by weight, more preferably 3.5 to 300 parts by weight, and even more preferably 8 to 200 parts by weight. The blending ratio of the small molecule compound (R) is preferably 0.2 to 200 parts by weight, more preferably 1.2 to 150 parts by weight, based on 100 parts by weight of the polymer (P). , 2 to 100 parts by weight is more preferable.

The polymer composition of the above [1] includes an embodiment containing at least one of a liquid crystal compound (Q) and a small molecule compound (R) together with the liquid crystal compound (QR). In this case, the total amount of the liquid crystal compound (QR), the liquid crystal compound (Q) and the small molecule compound (R) in the polymer composition is 100 parts by weight of the polymer (P) in the polymer composition. On the other hand, it is preferable that the compounding ratio is in the range of 1 to 1,000 parts by weight.

The polymer composition according to the present invention contains a polymer (P) and a compound having a photo-orientation site, and in these components, the polymer (P) has a first functional group and is photo-orientated. The compound having a sex site has a second functional group, and one of the first and second functional groups is selected from the group consisting of a hydroxyl group, a carboxyl group, a phosphoric acid group and a sulfonic acid group. It is preferably at least one, and the other group is preferably at least one selected from the group consisting of a tertiary amino group and a nitrogen-containing heterocyclic group. In this case, it is preferable in that the effect of improving the afterimage characteristics can be obtained even when the irradiation amount of the polarized ultraviolet rays is small. The "compound having a photo-oriented site" includes a liquid crystal compound (QR) and a small molecule compound (R). By doing the above, it is presumed that an intermolecular interaction acts between the polymer (P) and the compound having a photo-oriented site.

（式（Ｎ−２）中、Ｒ^７は置換又は無置換の１価の炭化水素基である。「＊」は炭化水素基に結合する結合手である。） Specifically, the tertiary amine structure as the first functional group or the second functional group is represented by, for example, the following formula (N-2).

(In formula (N-2), R ⁷ is a substituted or unsubstituted monovalent hydrocarbon group. “*” Is a bond that binds to a hydrocarbon group.)

In the above formula (N-2), it is preferable that the monovalent hydrocarbon group R ⁷ is from 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a linear or butyl group Examples thereof include a chain-like or branched alkyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group and a methylphenyl group; and an aralkyl group such as a benzyl group. Examples of the substituent that R ⁷ may have include a halogen atom, a cyano group, an alkylsilyl group, an alkoxysilyl group and the like.
R ⁷ is preferably an alkyl group having 1 to 5 carbon atoms, a cyclohexyl group, a phenyl group or a benzyl group, and more preferably an alkyl group having 1 to 5 carbon atoms, a cyclohexyl group or a benzyl group.

Examples of the nitrogen-containing heterocyclic group include pyrol, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indol, benzimidazole, 1H-pyrrolo [2,3-b] pyridine, purine, quinoline, isoquinoline, and naphthylidine. , I-valent groups obtained by removing i hydrogen atoms from nitrogen-containing heterocycles such as phenazine, quinoxalin, phthalazine, triazole, carbazole, acrydin, piperidine, piperazine, pyrrolidine and hexamethyleneimine. However, a substituent may be introduced into the nitrogen-containing heterocycle. Examples of the substituent contained in the nitrogen-containing heterocycle include an alkyl group having 1 to 5 carbon atoms and an alkoxy group. The nitrogen-containing heterocycle is preferably at least one selected from the group consisting of pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, imidazole, 1H-pyrrolo [2,3-b] pyridine and acridine.

Regarding the first functional group and the second functional group, preferably, the compound (P) having a carboxyl group and a photo-oriented site is selected from the group consisting of a tertiary amino group and a nitrogen-containing heterocyclic group. It is preferable to have at least one of these.
The carboxyl group contained in the polymer (P) may be a carboxyl group generated by ring opening of the tetracarboxylic dianhydride, or may be a carboxyl group derived from a carboxyl group-containing diamine. Examples of the carboxyl group-containing diamine include 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, and 4,4'-. Monocarboxylic acids such as diaminodiphenylmethane-3-carboxylic acid, 4,4'-diaminodiphenylethane-3-carboxylic acid;
4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3, 3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylethane-3,3'-dicarboxylic acid, 4,4 Dicarboxylic acids such as'-diaminodiphenyl ether-3,3'-dicarboxylic acid; etc. may be mentioned.

In the synthesis of polyamic acid, polyamic acid ester and polyimide, the ratio of carboxyl group-containing diamine used is 5 mol% or more with respect to the total amount of diamine used in the synthesis from the viewpoint of sufficiently obtaining the effect of improving the afterimage characteristics. It is preferable that the content is 10 mol% or more, and more preferably 20 mol% or more. The upper limit of the usage ratio is not particularly limited, but from the viewpoint of voltage retention, it is preferably 90 mol% or less, preferably 80 mol% or less, based on the total amount of diamine used for synthesis. Is more preferable. As the carboxyl group-containing diamine, one of the above can be used alone or two or more thereof can be appropriately selected and used.

When a compound having a second functional group is used as the compound having a photo-oriented site, the content ratio of the compound having a second functional group in the liquid crystal aligning agent is relative to the total amount of the compounds having a photo-oriented site. It is preferably 50 mol% or more, and more preferably 60 mol% or more.

<Other ingredients>
The polymer composition in the present invention may contain other components other than the above, if necessary, as long as it does not interfere with the purpose and effect of the present invention. Other components that may be blended in the polymer composition include, for example, other polymers other than the above polymer (P), compounds having at least one epoxy group in the molecule, functional silane compounds, and surface activity. Examples thereof include agents, fillers, pigments, defoamers, sensitizers, dispersants, antioxidants, adhesion aids, antioxidants, leveling agents, antibacterial agents and the like.
Examples of the other polymers include polyamic acid, polyimide, polyamic acid ester, polysiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, and poly (meth) acrylate. The skeleton is mentioned. The blending ratio of the other compounds can be appropriately selected according to various compounds as long as the object and effect of the present invention are not impaired.

<Solvent>
The polymer composition in the present invention is prepared as a liquid composition in which the polymer (P) and other components used as necessary are preferably dispersed or dissolved in a suitable organic solvent. ..

Examples of the organic solvent used include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-1-imidazolidinone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide. , N, N-dimethylacetamide, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropaneamide, N, N, 2-trimethylpropaneamide, 1-butoxy-2-propanol, Diacetone alcohol, propylene glycol diacetate, dipropylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropione- G, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether , Diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, etc. Can be mentioned. These can be used alone or in admixture of two or more.

The solid content concentration in the polymer composition (the ratio of the total weight of the components other than the solvent of the polymer composition to the total weight of the polymer composition) is appropriately selected in consideration of viscosity, volatility and the like. , Preferably in the range of 1-10% by weight. That is, the polymer composition is applied to the surface of the substrate as described later, and preferably heated to form a resin film. At this time, if the solid content concentration is less than 1% by weight, the film thickness of the coating film becomes too small and it becomes difficult to obtain a good resin film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes excessive and it is difficult to obtain a good resin film, and the viscosity of the polymer composition increases and the coatability deteriorates. There is a tendency.

The range of particularly preferable solid content concentration depends on the method used when applying the polymer composition to the substrate. For example, when the spinner method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, whereby the solution viscosity is in the range of 3 to 15 mPa · s. The temperature at which the polymer composition is prepared is preferably 10 to 50 ° C, more preferably 20 to 30 ° C.

≪Liquid crystal alignment film≫
By using the above polymer composition, a liquid crystal alignment film as a resin film can be produced. Specifically, the liquid crystal alignment film in the present invention can be produced by a step including the following steps [A] to [C]. In the step [A], the substrate used differs depending on the desired operation mode of the liquid crystal display element. Step [B] and step [C] are common to each operation mode.
Step [A]: A step of applying the above polymer composition onto a substrate to form a coating film.
Step [B]: A step of irradiating the coating film obtained in the step [A] with polarized radiation.
Step [C]: A step of heating the coating film at least after the irradiation in the step [B] and at the time of the irradiation.

[Step [A]: Formation of coating film]
First, the polymer composition of the above [1] or [2] is applied onto a substrate, and then the coated surface is preferably heated to form a coating film on the substrate.
(A-1) For example, in the case of manufacturing a TN (Twisted Nematic) type, STN type or VA type liquid crystal display element, first, two substrates provided with a patterned transparent conductive film are paired and each transparent. The polymer composition prepared above is preferably applied on the surface on which the sex conductive film is formed by an offset printing method, a spin coating method, a roll coater method or an inkjet printing method, respectively. As the substrate, for example, glass such as float glass and soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (aliphatic olefin) can be used.

As the transparent conductive film provided on one surface of a substrate, NESA film (US PPG registered trademark) made of tin oxide (SnO _2), indium oxide - such as an ITO film made of tin oxide _{(In 2} O 3 -SnO ₂₎ the Can be used. To obtain a patterned transparent conductive film, for example, a method of forming a transparent conductive film without a pattern and then forming a pattern by photo-etching; a method of using a mask having a desired pattern when forming the transparent conductive film; And so on. When applying the polymer composition, in order to further improve the adhesiveness between the substrate surface and the transparent conductive film and the coating film, a functional silane compound and functional titanium are applied to the surface of the substrate on which the coating film is formed. Pretreatment may be performed in which a compound or the like is applied in advance.

After the polymer composition is applied, preheating is preferably performed for the purpose of preventing dripping of the applied polymer composition. The prebake temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-baking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. The heating method is not particularly limited, and examples thereof include a method of heating the substrate on a hot plate and a method of heating in an oven.

(A-2) When manufacturing an in-plane switching type (IPS type) or FFS (Fringe Field Switching) type liquid crystal display element, an electrode made of a transparent conductive film or a metal film patterned in a comb-tooth shape is provided. A liquid crystal alignment agent is applied to each of the electrode-forming surface of the substrate and one surface of the opposing substrate on which the electrode is not provided, and then each coated surface is heated to form a coating film. The materials of the substrate and the transparent conductive film used at this time, the coating method, the heating conditions after coating, the patterning method of the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferable film thickness of the coating film to be formed are described above. It is the same as (A-1). As the metal film, a film made of a metal such as chromium can be used.

[Step [B]: Irradiation of polarized radiation]
Next, the coating film obtained in the above step [A] is irradiated with polarized radiation to impart liquid crystal alignment ability to the coating film. As the radiation to irradiate the coating film, for example, ultraviolet rays including light having a wavelength of 150 to 800 nm and visible light can be used. The radiation used may be linearly polarized light or partially polarized light. Further, the irradiation may be performed from a direction perpendicular to the substrate surface, may be performed from an oblique direction, or may be performed in combination of these.
As the light source to be used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. Ultraviolet rays in a preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter, a diffraction grating, or the like. The irradiation amount of radiation is preferably 100 to 50,000 J / m ² , and more preferably 300 to 20,000 J / m ² .

[Step [C]: Heating of coating film]
Step [C] is polarized in step [B] for the purpose of completely removing the solvent, promoting reorientation by heating, or, if necessary, thermally imidizing the amic acid structure present in the polymer. The treatment of heating the coating film is carried out after irradiation with radiation, at the same time as irradiation with polarized radiation, or both. From the viewpoint of cost reduction of the exposure apparatus and heat reorientation, it is preferable to perform heat treatment after irradiating polarized radiation in step [B].
In the step [C], the heat treatment may be performed in one step at a predetermined temperature, or may be performed in a plurality of steps at different heating temperatures. In the case of the one-step heat treatment, the heating temperature is not particularly limited, but it is preferably higher than the prebake temperature. Specifically, it is preferably 100 to 300 ° C, more preferably 120 to 250 ° C, and even more preferably 150 to 250 ° C. The heating time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes.

When the step [C] is a heat treatment in a plurality of stages, the step [C] includes a first heating step of heating at a first temperature and a second heating step of heating at a temperature higher than the first temperature. Is preferable. By performing the heat treatment in a plurality of stages, the reliability and afterimage characteristics of the liquid crystal display element can be further improved, which is preferable.
The heating temperature (first temperature) in the first heating step is a liquid crystal compound (liquid crystal compound (QR)) blended in the polymer composition in terms of the effect of improving the reliability and afterimage characteristics of the liquid crystal display element. The lower limit is Tm1, which is 20 ° C. lower than the lower limit temperature of the temperature range in which the liquid crystal compound (Q)) exhibits liquid crystallinity (hereinafter, also referred to as “liquid crystal temperature range Ra”), and the upper limit temperature of the liquid crystal temperature range Ra is higher. It is preferable that the temperature is within the range Rb (Tm1 ≦ Rb ≦ Tm2) up to a temperature Tm2 higher than 20 ° C. The lower limit of the range Rb is preferably a temperature 10 ° C. lower than the lower limit temperature of the liquid crystal temperature range Ra, and more preferably a temperature 5 ° C. lower than the lower limit temperature of the liquid crystal temperature range Ra. The upper limit of the range Rb is preferably a temperature 10 ° C. higher than the upper limit temperature of the liquid crystal temperature range Ra, and more preferably a temperature 5 ° C. higher than the upper limit temperature of the liquid crystal temperature range Ra. The heating time at the first temperature is preferably 1 to 60 minutes, more preferably 5 to 30 minutes.

The presence or absence of liquid crystallinity in the compound can be determined by, for example, a method of observing the endothermic and heat generation behavior of the compound using a differential scanning calorimetry device, or the presence or absence of birefringence and fluidity during heating of the compound using a polarizing microscope. It can be discriminated by the observation method or the like.

The heating temperature in the second heating step is not particularly limited as long as it is higher than the first temperature, but is preferably a temperature 10 ° C. or higher higher than the first temperature, and more preferably 10 to 50 ° C. higher. It is preferable, and the temperature is more preferably 20 to 40 ° C. higher. The heating time in the second heating step is preferably 1 to 150 minutes, more preferably 5 to 100 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

[Step [D]: Irradiation of unpolarized radiation]
In the method for producing a liquid crystal alignment film according to the present invention, in addition to the above steps [A] to [C], unpolarized light is further applied to at least one of before, during, and after heating by the second heating step. The step [D] of irradiating the ultraviolet rays of the above may be included. By performing the process of this step [D], the liquid crystal orientation of the coating film is further improved, and the reliability of the obtained liquid crystal display element and the effect of improving the afterimage characteristics can be enhanced, which is preferable.

Irradiation of unpolarized radiation in step [D] may be performed at least one of before, during, and after heating by the second heating step of step [C]. Specifically, for example, the irradiation timing is performed between the first heating step and the second heating step of the step [C], after the second heating step and before the construction of the liquid crystal cell, and second. Examples thereof include a mode performed during heating by a heating step. Among these, from the viewpoint of improving the liquid crystal orientation, it is preferable that the mode is performed between the first heating step and the second heating step.
As the radiation to irradiate the coating film, for example, ultraviolet rays including light having a wavelength of 150 to 800 nm and visible light can be used. The description of the above step [B] can be applied to the description of the type, wavelength and light source of the radiation to be irradiated. Dose of radiation to be irradiated is preferably 1,000~500,000J / ^{m 2,} more preferably from 5,000~200,000J / ^{m 2.} Light irradiation of the coating film is usually carried out at a temperature of 0 to 120 ° C., preferably 5 to 100 ° C., and more preferably 10 to 80 ° C.

≪Liquid crystal element≫
The liquid crystal element according to the present invention includes a liquid crystal alignment film formed by using the above polymer composition. The operation mode of the liquid crystal element is not particularly limited, and for example, TN type, STN type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, optical compensation bend type (OCB). It can be applied to various operation modes such as type).

The liquid crystal element according to the present invention can be manufactured, for example, by a process including the following step [E].
[Step [E]: Construction of liquid crystal cell]
(E-1) A liquid crystal cell is manufactured by preparing two substrates on which a liquid crystal alignment film is formed as described above and arranging liquid crystals between the two substrates arranged opposite to each other. For example, the following two methods can be mentioned for manufacturing a liquid crystal cell. The first method is a conventionally known method. First, two substrates are arranged facing each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealant to form the substrate surface and the sealant. A liquid crystal cell is manufactured by injecting and filling the cell gap partitioned by the above and then sealing the injection hole. The second method is a method called the ODF (One Drop Fill) method. For example, an ultraviolet photocurable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and the liquid crystal is further dropped on a predetermined number of places on the liquid crystal alignment film surface. After that, the other substrate is attached so that the liquid crystal alignment films face each other, the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant to produce a liquid crystal cell. .. Regardless of which method is used, the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used is isotropic, and then slowly cooled to room temperature to obtain a flow orientation at the time of filling the liquid crystal. It is desirable to remove it.

As the sealing agent, for example, an epoxy resin containing an aluminum oxide sphere as a curing agent and a spacer can be used.
Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal, and among them, nematic liquid crystal is preferable. A cyclohexane-based liquid crystal, a pyrimidine-based liquid crystal, a dioxane-based liquid crystal, a bicyclooctane-based liquid crystal, a Cuban-based liquid crystal, or the like can be used. Further, to these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate, and cholesteryl carbonate; chiral agents such as those sold under the trade names "C-15" and "CB-15" (manufactured by Merck). A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate may be added and used.

After that, the liquid crystal cell constructed in the above (E-1) may be subjected to a process of irradiating the liquid crystal cell with unpolarized radiation. Such irradiation treatment is preferable in that the orientation of the liquid crystal alignment film can be further improved, and the reliability and afterimage characteristics of the obtained liquid crystal display element can be improved. The radiation irradiation at this time may be performed in a state where no voltage is applied between the conductive films of the pair of substrates, or may be performed in a state where a voltage is applied. When a voltage is applied between the conductive films, the voltage can be, for example, a direct current of 0 to 50 V or an alternating current. The description of the above step [D] can be applied to various conditions such as the wavelength of the radiation to be irradiated, the light source, and the irradiation amount.

Then, the liquid crystal display element according to the present invention can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell. As the polarizing plate attached to the outer surface of the liquid crystal cell, a polarizing plate called "H film" in which polyvinyl alcohol is stretched and oriented to absorb iodine is sandwiched between cellulose acetate protective films or the H film itself. A polarizing plate made of the above can be mentioned.

The liquid crystal element according to the present invention can be effectively applied to various devices, for example, a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, a smartphone, and the like. It can be used for various display devices such as various monitors, LCD TVs and information displays, and dimming films. Further, the liquid crystal element formed by using the liquid crystal alignment agent of the present disclosure can also be applied to a retardation film.

In the following examples, the weight average molecular weight Mw of the polymer, the imidization ratio, the epoxy equivalent, and the solution viscosity of the polymer solution were measured by the following methods.
[Weight average molecular weight Mw of polymer]
Mw is a polystyrene-equivalent value measured by GPC under the following conditions.
Column: Made by Tosoh Corporation, TSKgelGRCXLII
Solvent: tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
[Imidization rate of polymer]
A solution containing polyimide is put into pure water, the obtained precipitate is sufficiently dried under reduced pressure at room temperature, dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR is measured at room temperature using tetramethylsilane as a reference substance. did. From the obtained ¹ H-NMR spectrum, the imidization ratio was determined using the following mathematical formula (EX-1).
Imidization rate (%) = (1-A ¹ / A ² x α) x 100 ... (EX-1)
(In formula (1), A ¹ is the peak area derived from the proton of the NH group appearing near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the precursor of the polymer (polyamic acid). ) Is the ratio of the number of other protons to one proton of the NH group.)
[Epoxy equivalent]
The epoxy equivalent was measured by the hydrochloric acid-methylethylketone method described in JIS C 2105.
[Solution viscosity of polymer solution]
The solution viscosity (mPa · s) of the polymer solution was measured at 25 ° C. using an E-type rotational viscometer.

<Synthesis of polymer>
[Synthesis Example 1]
100 parts of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 80 parts of 2,2'-dimethyl-4,4'-diaminobiphenyl as diamine, and 3,5- 20 mol of diaminobenzoic acid was dissolved in N-methyl-2-pyrrolidone (NMP) and reacted at 40 ° C. for 3 hours to obtain a solution containing 10% by weight of polyamic acid (PAA-1). A small amount of the obtained polyamic acid solution was taken and measured, and the solution viscosity was 120 mPa · s.

[Synthesis Examples 2-4]
Polyamic acids (PAA-2) to (PAA-4) were synthesized in the same manner as in Synthesis Example 1 except that the types and amounts of tetracarboxylic dianhydride and diamine used were changed as shown in Table 1 below.

In Table 1, the numerical values in parentheses of the tetracarboxylic dianhydride and the diamine represent the ratio [molar part] of each compound to 100 parts in total of the tetracarboxylic dianhydride used for the synthesis of the polymer. The abbreviations of the compounds in Table 1 have the following meanings.
<Tetracarboxylic dianhydride>
t-1: 2,3,5-tricarboxycyclopentyl acetate dianhydride t-2: 1,2,4,5-cyclopentanetetracarboxylic dianhydride t-3: 1R, 2S, 4S, 5R-1 , 2,4,5-Cyclohexanetetracarboxylic dianhydride (PMDA-HS)
<Diamine>
d-1: 2,2'-dimethyl-4,4'-diaminobiphenyl d-2: 4,4'-diaminodiphenyl ether d-3: 3,5-diaminobenzoic acid d-4: The above formula (D-2) Compound represented by -6) d-5: Compound represented by the above formula (D-2-2)

[Synthesis Example 5]
100 parts of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 20 parts of 4,4'-diaminodiphenyl ether as diamine, 70 parts of 3,5-diaminobenzoic acid, and the above. A solution containing 10 mol parts of the compound represented by the formula (D-2-6) dissolved in N-methyl-2-pyrrolidone (NMP), reacted at 60 ° C. for 6 hours, and containing 20% by weight of polyamic acid. Got A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 60 mPa · s.
Next, NMP was added to the obtained polyamic acid solution to prepare a solution having a polyamic acid concentration of 7% by weight, and pyridine and acetic anhydride were each 1.3 times the total amount of the tetracarboxylic dianhydride used. Mole-by-mol was added, and a dehydration ring-closing reaction was carried out at 110 ° C. for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new NMP (the pyridine and acetic anhydride used in the dehydration ring closure reaction were removed from the system by this operation. The same applies hereinafter), so that the imidization rate was about 70. A solution containing 16% by weight of polyimide (PI-1) was obtained.

[Synthesis Example 6]
As a tetracarboxylic dianhydride, 30 g of 1R, 2S, 4S, 5R-1,2,4,5-cyclohexanetetracarboxylic dianhydride was added to 500 mL of ethanol. The obtained precipitate was separated by filtration, washed with ethanol, and then dried under reduced pressure to obtain a compound (t-3E) as a tetracarboxylic dianester in powder form. Next, 100 mol parts of compound (t-3E) was dissolved in NMP, and then 50 mol parts of 2,2'-dimethyl-4,4'-diaminobiphenyl and 40 mol of 3,5-diaminobenzoic acid were used as diamines. Parts and 10 mol parts of the compound represented by the above formula (D-2-6) were added and dissolved. 300 mol parts of 4- (4,6-dimethoxy-1,3,5-triazine-2-yl) -4-methylmorpholinium chloride (DMT-MM, 15 ± 2 wt% hydrate) in this solution. Was added and the reaction was carried out at room temperature for 4 hours to obtain a solution containing 10% by weight of polyamic acid ester (PAE-1). The weight average molecular weight Mw of the obtained polymer (PAE-1) was 64,000, and the polymer viscosity was 90 mPa · s.

[Synthesis Example 7]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux cooling tube, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as a hydrolyzable silane compound and 500 g of methylisobutylketone as a solvent. And 10.0 g of triethylamine was charged as a catalyst and mixed at room temperature. 100 g of deionized water was added dropwise thereto from a dropping funnel over 30 minutes, and then the reaction was carried out at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out, washed with a 0.2 wt% ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain polyorganosiloxane (polyorganosiloxane). EPS-1) was obtained as a viscous transparent liquid. ^{When 1} H-NMR analysis was performed on this polyorganosiloxane, a peak based on an epoxy group was obtained near chemical shift (δ) = 3.2 ppm according to the theoretical intensity, and a side reaction of the epoxy group occurred during the reaction. It was confirmed that it was not. The epoxy equivalent of this polyorganosiloxane was measured and found to be 186 g / equivalent. The weight average molecular weight Mw of the obtained polymer (EPS-1) was 5,500.

[Synthesis Example 8]
In a reaction vessel equipped with a stirrer, a thermometer and a reflux cooling tube, methacrylic acid (45 mol parts with respect to 100 mol parts of the total amount of monomers used for polymerization) and styrene (10 mol parts) as polymerizable unsaturated compounds. ) And the compound represented by the following formula (e-3) (45 mol parts) were charged, and diethylene glycol ethyl methyl ether was added and dissolved so that the total of the polymerizable unsaturated compounds was 50% by weight.
Here, 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator is added in an amount of 3 mol% based on the total number of moles of the polymerizable unsaturated compound, and α-methylstyrene dimer is added as a chain transfer agent. 0.5 times the weight of the polymerization initiator was added. Then, after bubbling in a nitrogen stream for 10 minutes to replace nitrogen in the system, a polymerization reaction was carried out at 70 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol and then dried under reduced pressure at 40 ° C. for 15 hours to obtain polymethacrylate (PMAA-1). The weight average molecular weight Mw of the obtained polymer (PMAA-1) was 11,000.

[Synthesis Example 9]
The polymerizable unsaturated compound used is represented by methacrylic acid (30 mol parts with respect to 100 mol parts of the total amount of monomers used for polymerization), styrene (10 mol parts), and the above formula (e-3). Polymethacrylate (PMAA-2) was obtained by the same procedure as in Synthesis Example 8 above, except that the compound (30 mol parts) and glycidyl methacrylate (30 mol parts) were changed. The weight average molecular weight Mw of the obtained polymer (PMAA-2) was 12,000.
[Synthesis Example 10]
Polymethacrylate (PMAA-3) was prepared by the same operation as in Synthesis Example 8 above, except that the polymerizable unsaturated compound used was changed to the compound represented by the following formula (e-4) (100 mol parts). Obtained. The weight average molecular weight Mw of the obtained polymer (PMAA-3) was 10,000.

[Example 1]
(1) Preparation of Polymer Composition The compound (Q) is represented by the above formula (Q-1) in the solution containing the polyamic acid (PAA-1) obtained in Synthesis Example 1 as the polymer (P). The compound is 10 parts by weight with respect to 100 parts by weight of the polyamic acid (PAA-1), and the compound represented by the above formula (R-1) as the compound (R) is 100 parts by weight of the polyamic acid (PAA-1). 5 parts by weight was added to the solution to prepare a solution having a mixed solvent composed of NMP and butyl cellosolve (BCS) having a composition of NMP: BCS = 50: 50 (weight ratio) and a solid content concentration of 6.0% by weight. The polymer composition (S-1) was prepared by filtering this solution using a filter having a pore size of 1 μm.

(2) Manufacture of liquid crystal display element It has two metal electrodes (electrode A and electrode B) made of chrome patterned in a comb-tooth shape, and voltage can be applied independently to these electrodes A and B. A glass substrate was prepared. The polymer composition (S-1) prepared above is applied to a pair of the glass substrate and the opposing glass substrate on which no electrode is provided, and the surface of the glass substrate having the electrodes and one surface of the opposing glass substrate are covered with the polymer composition (S-1) prepared above. Each was applied using a spin coater. Then, prebaking was performed for 1 minute on a hot plate at 80 ° C. This operation was repeated to obtain a pair (two) of glass substrates having a coating film on the transparent conductive film. The coating film obtained above was subjected to photoalignment treatment by irradiating the coating film obtained above with polarized ultraviolet rays of 2,000 J / m ^{2 containing a bright line of 313 nm from the normal direction of the substrate using an Hg-Xe lamp and a Gran Tailor prism.} It should be noted that this irradiation amount is a value measured using a photometer measured based on a wavelength of 313 nm.
Next, it was confirmed that the compound represented by the above formula (Q-1) exhibited liquid crystallinity at 80 ° C., and subsequently, the glass substrate after irradiation with polarized ultraviolet rays was placed on a hot plate at 80 ° C. for 15 minutes. It was heated. Further, the inside of the refrigerator was heated (post-baked) for 1 hour in a nitrogen-substituted oven at 200 ° C. to form a coating film (liquid crystal alignment film) having an average film thickness of 0.08 μm.
Next, for one of the pair of substrates, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer edge of the surface having the liquid crystal alignment film, and then the pair of substrates is coated with the liquid crystal alignment film surface. The adhesives were cured by overlapping and crimping them so that they face each other. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck Co., Ltd.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive. Further, the polarizing plates were attached to both outer surfaces of the substrate so that the changing directions of the two polarizing plates were orthogonal to each other to produce a liquid crystal display element.

(3) Evaluation of reliability For the liquid crystal display element manufactured above, after applying a voltage of 5 V at 23 ° C. for an application time of 60 microseconds and a span of 167 milliseconds, the voltage is held 167 milliseconds after the application is released. The rate (VHR) was measured and the value was taken as the initial VHR (VHR _BF ). As the measuring device, VHR-1 manufactured by Toyo Corporation was used. Next, the liquid crystal display element after the initial VHR measurement was allowed to stand in an oven at 80 ° C. under irradiation with an LED lamp for 200 hours, and then allowed to stand at room temperature to be naturally cooled to room temperature. The voltage holding ratio of the cooled liquid crystal cell was measured again by the same method as described above. This value was defined as VHR (VHR _AFBL ) after stress was applied. The amount of decrease in voltage retention rate ΔVHR (%) was calculated from the following mathematical formula (EX-2), and the reliability was evaluated.
ΔVHR = ((VHR _{BF -VHR AFBL} ) ÷ VHR _BF ) × 100 ... (EX-2)
When ΔVHR is less than 1.0%, the reliability is “excellent” (◎), when it is 1.0% or more and less than 2.0%, the reliability is “good” (○), 2.0% or more. When it was less than 3.0%, it was judged as "OK" (Δ), and when it was 3.0% or more, it was judged as "Poor" (×). As a result, the ΔVHR of the liquid crystal display element of this example was 1.2%, and the reliability was evaluated as “good” (◯).

(4) Evaluation of afterimage characteristics (AC afterimage evaluation)
The liquid crystal display element manufactured above was left at room temperature for 300 hours with AC10V (60Hz) applied to the electrode A and AC0V (60Hz) applied to the electrode B, respectively. Then, the electrode A and the electrode B were simultaneously driven from AC to 10 V (60 Hz) every 0.1 V, and the transmittance difference ΔT at a transmittance of 50% was measured.
When ΔT is less than 1.0%, the AC afterimage characteristic is “excellent” (⊚), when it is 1.0% or more and less than 2.0%, it is “good” (○), and 2.0% or more 3 When it was less than 0.0%, it was judged as "OK" (Δ), and when it was 3.0% or more, it was judged as "Defective" (×). As a result, the ΔT of the liquid crystal display element of this example was 1.5%, and the afterimage characteristic was evaluated as “good” (◯).

[Example 2]
(1) Preparation of polymer composition The same as in Example 1 (1) above, except that the type of polymer used, the type and amount of additives, and the solvent composition were changed as shown in Table 2 below. The polymer composition (S-2) was prepared.
(2) Manufacture of liquid crystal display element The polymer composition used was changed to (S-2), and the irradiation amount of polarized ultraviolet rays including bright lines of 313 nm was changed to ^{3,000 J / m 2 for the coating film.} After heat treatment at 80 ° C. for 15 minutes and before post-baking, a metal halide lamp was used to apply 10,000 J / m ² of unpolarized ultraviolet light containing a 365 nm emission line to the coating film on the substrate. A liquid crystal display element was produced by the same method as in Example 1 (2) above except for the point of irradiation from the normal direction of the substrate.
(3) Evaluation of Reliability With respect to the liquid crystal display element manufactured above, the reliability of the liquid crystal display element was evaluated in the same manner as in (3) of Example 1 above. As a result, ΔVHR = 0.5% in this liquid crystal display element, and the reliability was evaluated as “excellent” (⊚).
(4) Evaluation of Afterimage Characteristics With respect to the liquid crystal display element manufactured above, the afterimage characteristics of the liquid crystal display element were evaluated in the same manner as in (4) of Example 1 above. As a result, ΔT = 0.6% in this liquid crystal display element, which was an evaluation of the afterimage characteristic “excellent” (⊚).

[Reference Examples 3 and 4, Examples 6 and 7 and Comparative Examples 1 to 3]
A polymer composition was prepared in the same manner as in (1) of Example 1 above, except that the type of polymer used, the type and amount of additives, and the solvent composition were changed as shown in Table 2 below. .. Further, using the obtained polymer composition, the irradiation amount of polarized ultraviolet rays and the irradiation amount of unpolarized ultraviolet rays were changed as shown in Table 3 below in (2) of Example 2 above, and the point that Reference Example 4 was polarized. The same as (2) of Example 2 above except that the wavelength of ultraviolet rays was changed from 313 nm to 365 nm (the same wavelengths as in Example 2 for Reference Examples 3, Examples 6 and 7 and Comparative Examples 1 to 3). A liquid crystal display element was manufactured. The irradiation amount of polarized ultraviolet rays in Reference Example 4 is a value measured using a photometer measured based on a wavelength of 365 nm. Further, the reliability and afterimage characteristics of the obtained liquid crystal display element were evaluated in the same manner as in Example 1 above. The results are shown in Table 3 below.

In Table 2, the numerical values in the compounding amount column of the polymer (P) and the additive are the compounding ratio [parts by weight] of each compound with respect to the total 100 parts by weight of the polymer (P) used for preparing the polymer composition. show. The abbreviation X of the additive indicates that it is a compound represented by the above formula X, respectively. The abbreviations for solvents have the following meanings.
(solvent)
NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone BCS: Butyl cellosolve PG: 1-butoxy-2-propanol DMI: 1,3-dimethyl-2-imidazolidinone PGDAc: Propylene glycol diacetate DAA : Diacetone alcohol DEDG: Diethylene glycol diethyl ether

In Table 3, "-" indicates that the corresponding column was not irradiated with ultraviolet rays.

[Reference example 5]
(1) Preparation of polymer composition With the above-mentioned Example 1 (1) except that the type and amount of the polymer used, the type and amount of the additive, and the solvent composition were changed as described in Table 2 above. A polymer composition (S-5) was prepared in the same manner.
(2) Manufacture of liquid crystal display element It has two metal electrodes (electrode A and electrode B) made of chrome patterned in a comb-tooth shape, and voltage can be applied independently to these electrodes A and B. A glass substrate was prepared. The polymer composition (S-5) prepared above is applied to a pair of the glass substrate and the opposing glass substrate on which no electrode is provided, and the surface of the glass substrate having the electrodes and one surface of the opposing glass substrate. Each was applied using a spin coater. Then, prebaking was performed for 1 minute on a hot plate at 80 ° C. This operation was repeated to obtain a pair (two) of glass substrates having a coating film (liquid crystal alignment film) on the transparent conductive film. The coating film obtained above was subjected to photoalignment treatment by irradiating ^{the coating film obtained above with 10,000 J / m 2} polarized ultraviolet rays containing a bright line of 365 nm from the normal direction of the substrate using an Hg-Xe lamp and a Gran Tailor prism. It should be noted that this irradiation amount is a value measured using a photometer measured based on a wavelength of 365 nm.
Then, the glass substrate after irradiation with polarized ultraviolet rays was heated on a hot plate at 80 ° C. for 15 minutes. Next, the heated coating film was irradiated with unpolarized ultraviolet rays of 50,000 J / m ² from the normal direction of the substrate by using an ultraviolet irradiation device using a metal halide lamp as a light source. It should be noted that this irradiation amount is a value measured using a photometer measured based on a wavelength of 365 nm. Further, the inside of the chamber was heated (post-baked) in an oven at 200 ° C. with nitrogen substitution for 1 hour to form a coating film having an average film thickness of 0.08 μm.
Next, for one of the pair of substrates, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer edge of the surface having the liquid crystal alignment film, and then the pair of substrates is coated with the liquid crystal alignment film surface. The adhesives were cured by overlapping and crimping them so that they face each other. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck Co., Ltd.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive.
For the obtained liquid crystal cell, AC0V (60Hz) is applied between the electrodes, and in a state where the liquid crystal is not driven, an ultraviolet irradiation device using a metal halide lamp as a light source is used, and unpolarized ultraviolet light 30 including a emission line of 365 nm is used. 000 J / m ² was irradiated from the normal direction of the substrate plate. It should be noted that this irradiation amount is a value measured using a photometer measured based on a wavelength of 365 nm. Further, the polarizing plates were attached to both outer surfaces of the substrate so that the changing directions of the two polarizing plates were orthogonal to each other to produce a liquid crystal display element.

(3) Evaluation of Reliability With respect to the liquid crystal display element manufactured above, the reliability of the liquid crystal display element was evaluated in the same manner as in (3) of Example 1 above. As a result, ΔVHR = 0.3% in this liquid crystal display element, and the reliability was evaluated as “excellent” (⊚).
(4) Evaluation of Afterimage Characteristics With respect to the liquid crystal display element manufactured above, the afterimage characteristics of the liquid crystal display element were evaluated in the same manner as in (4) of Example 1 above. As a result, ΔT = 0.4% in this liquid crystal display element, which was an evaluation of the afterimage characteristic “excellent” (⊚).

[Example 8]
The polymer composition (S-) is the same as in Example 1 (1) above, except that the type of polymer used, the type and amount of additives, and the solvent composition are changed as shown in Table 2 above. 8) was prepared. Further, except that the obtained polymer composition (S-8) was used and the irradiation amount of polarized ultraviolet rays and the irradiation amount of unpolarized ultraviolet rays were changed as shown in Table 3 above in (2) of Example 2 above. A liquid crystal display element was manufactured in the same manner as in (2) of Reference Example 5 above. Further, the reliability and afterimage characteristics of the obtained liquid crystal display element were evaluated in the same manner as in Example 1 above. As a result, in this example, ΔVHR = 2.7% and the reliability was “possible” (Δ), and ΔT = 2.5% and the afterimage characteristic was “possible” (Δ).

As shown in Table 3, in Examples 1, 2, 6 to 8 and Reference Examples 3 to 5, the reliability and afterimage characteristics of the liquid crystal display element were all evaluated as "excellent", "good" or "acceptable". there were. On the other hand, among the comparative examples containing the liquid crystal compound (Q) but not the small molecule compound (R), the afterimage characteristic was evaluated as "poor" in Comparative Example 1, and the reliability and afterimage in Comparative Example 3. All of the characteristics were evaluated as "defective". Further, in Comparative Example 2 containing the small molecule compound (R) but not the liquid crystal compound (Q), both the reliability and the afterimage characteristics were evaluated as “poor”. From the above results, it was found that a liquid crystal alignment film having good reliability and afterimage characteristics can be formed by combining the polymer composition of the example with the step [C] of heating the coating film after irradiation with polarized ultraviolet rays. ..

Claims (10)

The step [A] of applying the polymer composition of the following [2] onto a substrate to form a coating film, and
In the step [B] of irradiating the coating film obtained in the step [A] with polarized radiation,
Look including the a step [C] for heating the coating film to at least one of the time after and the irradiation of the radiation in the step [B],
The step [C] is a method for producing a liquid crystal alignment film , which comprises a first heating step of heating at a first temperature and a second heating step of heating at a temperature higher than the first temperature.
[2] At least one polymer (P) selected from the group consisting of polyamic acids, polyamic acid esters, polyimides, polysiloxanes, and polymers obtained by addition polymerization, and radically polymerizable groups, cyclic ether groups, and cyclic thioether groups. , Oxazine ring-containing group, oxazoline group, isocyanate group, blocked isocyanate group, silanol group, methylol group, etherified methylol group and cyclic carbonate group. And a polymer composition containing a low molecular weight compound (R) having a photoorientation site and a molecular weight of 2,000 or less. The first temperature has a lower limit of 20 ° C. lower than the lower limit temperature of the temperature range in which the liquid crystal compound blended in the polymer composition exhibits liquid crystallinity, and is 20 ° C. higher than the upper limit temperature of the temperature range. a temperature within the range of the temperature upper limit, a method of manufacturing a liquid crystal alignment film according to claim 1. The production of the liquid crystal alignment film according to claim 1 or 2 , further comprising a step [D] of irradiating unpolarized radiation at least before, during, and after heating by the second heating step. Method. The polymer (P) has a first functional group, and the compound having the photooriented site has a second functional group.
One of the first functional group and the second functional group is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a phosphoric acid group and a sulfonic acid group, and the other group is a tertiary amino group. The method for producing a liquid crystal alignment film according to any one of claims 1 to 3 , which is at least one selected from the group consisting of a nitrogen-containing heterocyclic group. The step [A] of applying the polymer composition of the following [2] onto a substrate to form a coating film, and
In the step [B] of irradiating the coating film obtained in the step [A] with polarized radiation,
A method for producing a liquid crystal alignment film, which comprises a step [C] of heating the coating film after irradiation in the step [B] and at least during the irradiation.
[2] At least one polymer (P) selected from the group consisting of polyamic acids, polyamic acid esters, polyimides, polysiloxanes, and polymers obtained by addition polymerization, and radically polymerizable groups, cyclic ether groups, and cyclic thioether groups. , Oxazine ring-containing group, oxazoline group, isocyanate group, blocked isocyanate group, silanol group, methylol group, etherified methylol group and cyclic carbonate group. When the molecular weight of 2,000 or less for a low molecular compound having a photo-alignment moiety and (R), only contains,
The polymer (P) has a first functional group, and the compound having the photooriented site has a second functional group.
One of the first functional group and the second functional group is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a phosphoric acid group and a sulfonic acid group, and the other group is a tertiary amino group. And at least one polymer composition selected from the group consisting of nitrogen-containing heterocyclic groups. The liquid crystal alignment film according to claim 4 or 5, wherein the first functional group is a carboxyl group, and the second functional group is at least one selected from the group consisting of a tertiary amino group and a nitrogen-containing heterocyclic group. Manufacturing method. The polymer (P) has a nitrogen-containing heterocycle (excluding the imide ring of polyimide), and has at least one nitrogen-containing structure selected from the group consisting of a secondary amino group and a tertiary amino group. Item 8. The method for producing a liquid crystal alignment film according to any one of Items 1 to 6. The step [A] of applying the polymer composition of the following [2] onto a substrate to form a coating film, and
In the step [B] of irradiating the coating film obtained in the step [A] with polarized radiation,
A method for producing a liquid crystal alignment film, which comprises a step [C] of heating the coating film after irradiation in the step [B] and at least during the irradiation.
[2] At least one polymer (P) selected from the group consisting of polyamic acids, polyamic acid esters, polyimides, polysiloxanes, and polymers obtained by addition polymerization, and radically polymerizable groups, cyclic ether groups, and cyclic thioether groups. , Oxazine ring-containing group, oxazoline group, isocyanate group, blocked isocyanate group, silanol group, methylol group, etherified methylol group and cyclic carbonate group. When the molecular weight of 2,000 or less for a low molecular compound having a photo-alignment moiety and (R), only contains,
The polymer (P) is a polymer having at least one nitrogen-containing structure selected from the group consisting of a nitrogen-containing heterocycle (excluding the imide ring of polyimide) and a secondary amino group and a tertiary amino group. Composition. A liquid crystal cell is constructed by arranging a pair of substrates on which a liquid crystal alignment film is formed by the manufacturing method according to any one of claims 1 to 8 so as to face each other via a liquid crystal layer. Process and
A method for manufacturing a liquid crystal element, which comprises a step of irradiating the liquid crystal cell with unpolarized radiation. A step [A] of applying the polymer composition of the following [2] onto a substrate to form a coating film, and a step of irradiating the coating film obtained in the step [A] with polarized radiation [ B] and the a step [step of heating the coating film to at least one of the time after and the irradiation of the radiation in the B] [C], see containing the said step [C], the first temperature in a first heating step of heating, said second heating step of heating at a first temperature higher temperature than, a pair of substrates forming the liquid crystal alignment film by including manufacturing method, through the liquid crystal layer crystal The process of constructing a liquid crystal cell by arranging the alignment films so as to face each other,
A method for manufacturing a liquid crystal element, which comprises a step of irradiating the liquid crystal cell with unpolarized radiation.
[2] At least one polymer (P) selected from the group consisting of polyamic acids, polyamic acid esters, polyimides, polysiloxanes, and polymers obtained by addition polymerization, and radically polymerizable groups, cyclic ether groups, and cyclic thioether groups. , Oxazine ring-containing group, oxazoline group, isocyanate group, blocked isocyanate group, silanol group, methylol group, etherified methylol group and cyclic carbonate group. And a polymer composition containing a low molecular weight compound (R) having a photoorientation site and a molecular weight of 2,000 or less.