CN105392866B - Method for manufacturing substrate having liquid crystal alignment film for in-plane switching liquid crystal display element - Google Patents

Abstract

The present invention provides a lateral electric field-driven liquid crystal display element which is imparted with high efficiency in alignment control capability and is excellent in image sticking characteristics. The present invention solves the above-mentioned problems by means of a polymer composition containing (A) a photosensitive side-chain type polymer that exhibits liquid crystallinity in a specific temperature range; (B) a molecule having An amine compound in which one primary amino group and a nitrogen-containing aromatic heterocycle are bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; and (C) an organic solvent. In particular, the above-mentioned problems are solved by a method for producing a substrate having a liquid crystal aligning film that obtains a liquid crystal aligning film for a transverse electric field-driven liquid crystal display element provided with an alignment control ability by including the following steps: [ I] a step of applying the composition on a substrate having a conductive film for lateral electric field driving to form a coating film; [II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] applying [ The step of heating the coating film obtained in II].

Description

Production of a substrate having a liquid crystal aligning film for a transverse electric field-driven liquid crystal display element method of making

technical field

This invention relates to the manufacturing method of the board|substrate which has the liquid crystal aligning film for transverse electric field drive type liquid crystal display elements. More specifically, it relates to a new method for producing a liquid crystal display element having excellent image sticking properties.

Background technique

Liquid crystal display elements are known as display devices that are light in weight, thin in cross-section, and low in power consumption, and in recent years, they have been used for large-scale television applications and the like, and have achieved remarkable development. The liquid crystal display element is configured by sandwiching a liquid crystal layer between, for example, a pair of transparent substrates provided with electrodes. And in a liquid crystal display element, the organic film containing an organic material is used as a liquid crystal aligning film, and a liquid crystal exhibits a desired alignment state between substrates.

That is, the liquid crystal aligning film is a constituent member of the liquid crystal display element, is formed on the surface in contact with the liquid crystal of the substrates sandwiching the liquid crystal, and plays a role of aligning the liquid crystal in a specific direction between the substrates. Moreover, in addition to the function of aligning liquid crystals in a specific direction such as a direction parallel to the substrate, the liquid crystal aligning film may be required to control the pretilt angle of the liquid crystal. The ability to control the liquid crystal orientation of such a liquid crystal aligning film (hereinafter referred to as orientation control ability.) is imparted by subjecting the organic film constituting the liquid crystal aligning film to an orientation treatment.

As an alignment treatment method for a liquid crystal aligning film for imparting alignment control ability, a brushing method has been conventionally known. The brushing method refers to a method of rubbing (brushing) the surface of an organic film such as polyvinyl alcohol, polyamide, and polyimide on a substrate with a cloth such as cotton, nylon, and polyester in a certain direction. , so that the liquid crystal is oriented along the rubbing direction (brushing direction). Since this brushing method can easily realize a relatively stable liquid crystal alignment state, it is used in the manufacturing process of a conventional liquid crystal display element. In addition, as the organic film used for the liquid crystal aligning film, a polyimide-based organic film excellent in reliability such as heat resistance and electrical properties is mainly selected.

However, the brushing method which rubs the surface of the liquid crystal aligning film containing polyimide etc. has the problem of generation|occurrence|production of dust and static electricity. In addition, due to the recent high-definition liquid crystal display elements and unevenness caused by electrodes on the corresponding substrates or switching active elements for liquid crystal driving, the surface of the liquid crystal aligning film cannot be uniformly rubbed with a cloth, and a uniform liquid crystal cannot be realized. orientation.

Therefore, the photo-alignment method has been actively studied as another method of aligning the liquid crystal aligning film without brushing.

There are various methods for the photo-alignment method, and anisotropy is formed in the organic film constituting the liquid crystal aligning film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy.

As a main photo-alignment method, a decomposition-type photo-alignment method is known. For example, when a polyimide film is irradiated with polarized ultraviolet rays, anisotropic decomposition occurs by utilizing the polarization direction dependence of the ultraviolet absorption of the molecular structure. And a liquid crystal is orientated by the polyimide which remained without decomposition|disassembly (for example, refer patent document 1.).

In addition, photo-crosslinking type and photo-isomerization type photo-alignment methods are also known. For example, using polyvinyl cinnamate, and irradiating polarized ultraviolet rays, the double bond moieties of the two side chains parallel to the polarized light undergo a dimerization reaction (crosslinking reaction). Then, the liquid crystal is aligned in a direction perpendicular to the polarization direction (for example, refer to Non-Patent Document 1). In addition, when a side chain type polymer having azobenzene in its side chain is used, polarized ultraviolet rays are irradiated to cause an isomerization reaction of the azobenzene moiety of the side chain parallel to the polarized light, and the liquid crystal is caused to move along the direction perpendicular to the polarization direction. orientation (for example, refer to Non-Patent Document 2.).

As in the above-mentioned example, in the method of aligning a liquid crystal aligning film by the photo-alignment method, there is no need to perform brushing, and there is no need to worry about the generation of dust and static electricity. Moreover, even if it is a board|substrate of the liquid crystal display element which has unevenness|corrugation on the surface, an orientation process can be performed, and it becomes the orientation process method of the liquid crystal aligning film suitable for an industrial production process.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent No. 3893659

Non-patent literature

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

Non-patent document 2: K.Ichimura et al., Chem. Rev. 100, 1847 (2000).

SUMMARY OF THE INVENTION

Invention to solve problem

As described above, compared with the brushing method which has been industrially used as an alignment treatment method of a liquid crystal display element, the photo-alignment method does not require a step such as a brushing step, and thus has a significant advantage. Moreover, compared with the brushing method in which the orientation control ability by brushing is substantially constant, the photo-alignment method can control the orientation control ability by changing the irradiation amount of polarized light. However, when the photo-alignment method intends to achieve the same level of alignment control ability as that obtained by the brushing method, a large amount of polarized light irradiation may be required, or stable liquid crystal alignment may not be achieved.

For example, in the decomposition-type photo-alignment method described in the above-mentioned Patent Document 1, it is necessary to irradiate the polyimide film for 60 minutes with ultraviolet light from a high-pressure mercury lamp with a power of 500 W, etc., and a large amount of ultraviolet light for a long time is required. In addition, in the case of a dimerization-type and photoisomerization-type photoalignment method, a large amount of ultraviolet irradiation of several J (Joules) to several tens of J may be required. Furthermore, in the case of the photo-crosslinking type and the photo-isomerization type photo-alignment method, since the thermal stability and photostability of liquid crystal alignment are poor, when a liquid crystal display element is used, there are problems of poor alignment and display afterimage. In particular, in a lateral electric field driven liquid crystal display element, since liquid crystal molecules are switched in-plane, liquid crystal orientation shift after liquid crystal driving is likely to occur, and display afterimages caused by AC driving are regarded as a significant problem.

Therefore, the photo-alignment method is required to realize the high efficiency of the alignment treatment and stable liquid crystal alignment, and the liquid crystal aligning film and the liquid crystal aligning agent which can efficiently impart high alignment control ability to the liquid crystal aligning film are required.

An object of the present invention is to provide a substrate having a liquid crystal aligning film for a lateral electric field driven liquid crystal display element, which is imparted with high efficiency in alignment control capability and excellent in image sticking properties, and a lateral electric field driven liquid crystal display element having the same.

In addition, an object of the present invention is to provide a transverse electric field-driven liquid crystal element having an improved voltage holding ratio by adsorbing ionic impurities in liquid crystal at the interface of a liquid crystal aligning film, and a liquid crystal alignment device used for the element, in addition to the above object. membrane.

solution to the problem

The inventors of the present invention have made intensive studies in order to achieve the above-mentioned problems, and as a result, have found the following invention.

<1> A polymer composition containing:

(A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a specific temperature range;

(B) An amine compound having one primary amino group and a nitrogen-containing aromatic heterocycle in the molecule, and wherein the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; and

(C) Organic solvent.

<2> In the above <1>, the component (A) may have a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photoFries rearrangement.

<3> In the above <1> or <2>, the component (B) may be the following formula A-[1] (wherein Y ₁₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group group, Y ₁₂ is an amine compound represented by a nitrogen-containing aromatic heterocycle).

<4> In any one of said <1>-<3>, (A) component may have any photosensitive side chain chosen from the group which consists of following formula (1)-(6).

In the formula, A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O - or -O-CO-CH=CH-;

S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them is optionally substituted by a halogen group;

T is a single bond or an alkylene group with 1 to 12 carbon atoms, and the hydrogen atom bonded to them is optionally substituted by a halogen group;

Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different substituents selected from these The 2 to 6 rings are bonded by the bonding group B, and the hydrogen atoms bonded to them are independently optionally -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or a carbon number of 1- 5 alkyl), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl having 1 to 5 carbons, or alkane having 1 to 5 carbons Oxygen substitution;

Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and is bonded to them The hydrogen atoms of each are independently optionally replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. 5 alkoxy substitution;

R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ ;

X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O- or -O-CO-CH=CH- , when the number of X reaches 2, X is optionally the same or different from each other;

Cou represents coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bound to them are each independently optionally -NO ₂ , -CN, -CH=C(CN) ₂ , -CH= CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms, or alkoxy group with 1 to 5 carbon atoms;

One of q1 and q2 is 1, and the other is 0;

q3 is 0 or 1;

P and Q are each independently a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof; Wherein, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side where -CH=CH- is bonded is an aromatic ring, and the number of P is 2 or more When , P is optionally the same or different from each other, and when the number of Q reaches 2 or more, Q is optionally the same or different from each other;

l1 is 0 or 1;

l2 is an integer from 0 to 2;

When both l1 and l2 are 0, when T is a single bond, A also means a single bond;

When l1 is 1, when T is a single bond, B also means a single bond;

H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof.

<5> In any one of said <1>-<3>, (A) component may have any photosensitive side chain chosen from the group which consists of following formula (7)-(10).

In the formula, A, B, D, Y ₁ , X, Y ₂ and R have the same definitions as above;

l represents an integer from 1 to 12;

m represents an integer from 0 to 2, and m1 and m2 represent an integer from 1 to 3;

n represents an integer of 0 to 12 (wherein, when n=0, B is a single bond).

<6> In any one of said <1>-<3>, (A) component may have any photosensitive side chain chosen from the group which consists of following formula (11)-(13).

In the formula, A, X, l, m, m1 and R have the same definitions as above.

<7> In any one of said <1>-<3>, (A) component may have the photosensitive side chain represented by following formula (14) or (15).

In the formula, A, Y ₁ , l, m1 and m2 have the same definitions as above.

<8> In any one of said <1>-<3>, (A) component may have the photosensitive side chain represented by following formula (16) or (17).

In the formula, A, X, l and m have the same definitions as above.

<9> In any one of said <1>-<3>, (A) component may have the photosensitive side chain represented by following formula (18) or (19).

In the formula, A, B, Y ₁ , q1 , q2 , m1 and m2 have the same definitions as above.

R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkane having 1 to 5 carbon atoms. Oxygen.

<10> In any one of said <1>-<3>, (A) component may have the photosensitive side chain represented by following formula (20).

In the formula, A, Y ₁ , X, l and m have the same definitions as above.

<11> In any one of the above <1> to <10>, the component (A) may have any one liquid crystal side chain selected from the group consisting of the following formulae (21) to (31).

In the formula, A, B, q1 and q2 have the same definitions as above;

Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and a bond Each of their hydrogen atoms is independently optionally substituted by -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

R ₃ represents hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, containing nitrogen heterocycle, alicyclic hydrocarbon with 5-8 carbons, alkyl with 1-12 carbons, or alkoxy with 1-12 carbons;

l represents an integer from 1 to 12, m represents an integer from 0 to 2, where, in formulas (23) to (24), the sum of all m is 2 or more, and in formulas (25) to (26), all m The sum of is 1 or more, and m1, m2 and m3 each independently represent an integer from 1 to 3;

R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and alkyl or alkoxy;

Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, and -CF ₂ -.

<12> A method for producing a substrate having a liquid crystal aligning film for a transverse electric field-driven liquid crystal display element, comprising the following steps to obtain the liquid crystal aligning film to which an orientation control ability is imparted:

[I] A step of applying the composition according to any one of the above <1> to <11> on a substrate having a conductive film for lateral electric field driving to form a coating film;

[II] A step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and

[III] A step of heating the coating film obtained in [II].

<13> A board|substrate which has a liquid crystal aligning film for transverse electric field drive type liquid crystal display elements manufactured by the method of said <12>.

<14> A lateral electric field driven liquid crystal display element having the substrate of the above <13>.

<15> A method for manufacturing a transverse electric field driven liquid crystal display element, which obtains the liquid crystal display element by including the following steps:

The process of preparing the substrate (first substrate) of the above <13>;

The process of obtaining the 2nd board|substrate which has the said liquid crystal aligning film, and the liquid crystal aligning film provided with the orientation control ability is obtained by having the following processes [I'], [II'] and [III'];

[IV] A process for obtaining a liquid crystal display element by arranging the first substrate and the second substrate so as to face each other so that the liquid crystal aligning films of the first substrate and the second substrate face each other with the liquid crystal interposed therebetween,

The steps [I'], [II'] and [III'] are:

[I'] A step of forming a coating film by applying a polymer composition containing: (A) a photosensitive side chain type high-density liquid crystal exhibiting liquid crystallinity on a second substrate to form a coating film Molecules, (B) 1 molecule has 2 or more selected from the group consisting of hydroxyl group, hydroxyalkyl group, alkoxy group, alkoxyalkyl group, oxiranyl group, epoxy group, isocyanate group, oxetanyl group , a crosslinkable compound of at least one substituent in a cyclocarbonate group, a trialkoxysilyl group and a polymerizable unsaturated bond group, and (C) an organic solvent;

[II'] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I']; and

[III'] A step of heating the coating film obtained in [II'].

<16> A lateral electric field driven liquid crystal display element manufactured by the method of the above <15>.

In addition, as another aspect, the following inventions have been found.

<P1> The manufacturing method of the board|substrate which has the liquid crystal aligning film for transverse electric field drive type liquid crystal display elements which obtains the said liquid crystal aligning film provided with the orientation control ability by including the following steps,

[I] A step of forming a coating film by applying a polymer composition containing: (A) a liquid crystal exhibiting liquid crystallinity in a specific temperature range on a substrate having a conductive film for driving a transverse electric field to form a coating film Photosensitive side chain type polymer, (B) an amine compound having one primary amino group and a nitrogen-containing aromatic heterocycle in the molecule, and the aforementioned primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, (C) Organic solvents;

[II] A step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and

[III] A step of heating the coating film obtained in [II].

<P2> In the above <P1>, the component (A) may have a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photoFries rearrangement.

<P3> In the above <P1> or <P2>, the component (B) may be the following formula A-[1] (wherein Y ₁₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group group, Y ₁₂ is an amine compound represented by a nitrogen-containing aromatic heterocycle).

<P4> In any one of said <P1>-<P3>, (A) component may have any photosensitive side chain chosen from the group which consists of following formula (1)-(6).

In the formula, A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O - or -O-CO-CH=CH-;

S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them is optionally substituted by a halogen group;

T is a single bond or an alkylene group with 1 to 12 carbon atoms, and the hydrogen atom bonded to them is optionally substituted by a halogen group;

Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different substituents selected from these The 2 to 6 rings are bonded by the bonding group B, and the hydrogen atoms bonded to them are independently optionally -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or a carbon number of 1- 5 alkyl), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl having 1 to 5 carbons, or alkane having 1 to 5 carbons Oxygen substitution;

Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and is bonded to them The hydrogen atoms of each are independently optionally replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. 5 alkoxy substitution;

R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ ;

X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O- or -O-CO-CH=CH- ;

Cou represents coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bound to them are each independently optionally -NO ₂ , -CN, -CH=C(CN) ₂ , -CH= CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms, or alkoxy group with 1 to 5 carbon atoms;

One of q1 and q2 is 1, and the other is 0;

q3 is 0 or 1;

P and Q are each independently selected from the group consisting of a single bond, a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof group. Wherein, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side where -CH=CH- is bonded is an aromatic ring;

H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof.

<P5> In any one of said <P1>-<P3>, (A) component may have any photosensitive side chain chosen from the group which consists of following formula (7)-(10).

In the formula, A, B, D, Y ₁ , X, Y ₂ and R have the same definitions as above;

l represents an integer from 1 to 12;

m represents an integer from 0 to 2, and m1 and m2 represent an integer from 1 to 3;

n represents an integer of 0 to 12 (wherein, when n=0, B is a single bond).

<P6> In any one of said <P1>-<P3>, (A) component may have any photosensitive side chain chosen from the group which consists of following formula (11)-(13).

In the formula, A, X, l, m and R have the same definitions as above.

<P7> In any one of said <P1>-<P3>, (A) component may have the photosensitive side chain represented by following formula (14) or (15).

In the formula, A, Y ₁ , X, l, m1 and m2 have the same definitions as above.

<P8> In any one of said <P1>-<P3>, (A) component may have the photosensitive side chain represented by following formula (16) or (17).

In the formula, A, X, l and m have the same definitions as above.

<P9> In any one of said <P1>-<P3>, (A) component may have the photosensitive side chain represented by following formula (18) or (19).

In the formula, A, B, Y ₁ , q1 , q2 , m1 and m2 have the same definitions as above.

R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkane having 1 to 5 carbon atoms. Oxygen.

<P10> In any one of said <P1>-<P3>, (A) component may have the photosensitive side chain represented by following formula (20).

In the formula, A, Y ₁ , X, l and m have the same definitions as above.

<P11> In any one of said <P1>-<P10>, (A) component may have any one liquid crystalline side chain selected from the group which consists of following formula (21)-(31).

In the formula, A, B, q1 and q2 have the same definitions as above;

Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and a bond Each of their hydrogen atoms is independently optionally substituted by -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

R ₃ represents hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, containing nitrogen heterocycle, alicyclic hydrocarbon with 5-8 carbons, alkyl with 1-12 carbons, or alkoxy with 1-12 carbons;

l represents an integer from 1 to 12, m represents an integer from 0 to 2, where, in formulas (25) to (26), the sum of all m is 2 or more, and in formulas (27) to (28), all m The sum of is 1 or more, and m1, m2 and m3 each independently represent an integer from 1 to 3;

R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and alkyl or alkoxy;

Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, and -CF ₂ -.

<P12> A board|substrate which has a liquid crystal aligning film for transverse electric field drive type liquid crystal display elements manufactured by any one of said <P1>-<P11>.

<P13> A lateral electric field driven liquid crystal display element having the substrate of the above <P12>.

<P14> A method for manufacturing a transverse electric field driven liquid crystal display element, which obtains the liquid crystal display element by including the following steps:

The process of preparing the substrate (first substrate) of the above <P12>;

The process of obtaining the 2nd board|substrate which has the following process [I'], [II'] and [III'], and the said liquid crystal aligning film provided with the orientation control ability is obtained by having the following process [I'], [II'] and [III'];

[IV] A step of obtaining a liquid crystal display element by arranging the first substrate and the second substrate so as to face each other so that the liquid crystal aligning films of the first substrate and the second substrate face each other with the liquid crystal interposed therebetween,

The steps [I'], [II'] and [III'] are:

[I'] A step of forming a coating film by applying a polymer composition containing: (A) a photosensitive side chain type high-density liquid crystal exhibiting liquid crystallinity on a second substrate to form a coating film molecule, (B) an amine compound having a primary amino group and a nitrogen-containing aromatic heterocycle in the molecule, and the aforementioned primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, (C) an organic solvent;

[II'] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I']; and

[III'] A step of heating the coating film obtained in [II'].

<P15> A lateral electric field driven liquid crystal display element manufactured by the above-mentioned <P14>.

<P16> A composition for producing a liquid crystal aligning film for a transverse electric field-driven liquid crystal display element, comprising: (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a specific temperature range; (B) a molecule An amine compound having one primary amino group and a nitrogen-containing aromatic heterocycle therein, and wherein the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; and (C) an organic solvent.

<P17> In the above <P16>, the component (B) may be the above formula A-[1] (wherein Y ₁₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y ₁₂ is Amine compound represented by nitrogen-containing aromatic heterocycle).

effect of invention

According to the present invention, it is possible to provide a substrate having a liquid crystal aligning film for a transverse electric field driven liquid crystal display element, which is efficiently imparted with alignment control ability and excellent in image sticking properties, and a transverse electric field driven liquid crystal display element having the same.

Since the lateral electric field driven liquid crystal display element manufactured by the method of the present invention is efficiently provided with the orientation control ability, the display properties are not impaired even if it is continuously driven for a long time.

Furthermore, according to the present invention, in addition to the above-mentioned effects, it is possible to provide a transverse electric field driven liquid crystal element having an improved voltage holding ratio by adsorbing ionic impurities in a liquid crystal at the interface of a liquid crystal aligning film, and a liquid crystal alignment for the element. membrane.

Description of drawings

FIG. 1 is a diagram schematically illustrating an example of anisotropy introduction treatment in the method for producing a liquid crystal aligning film used in the present invention, in which a crosslinkable organic group is used for a photosensitive side chain and anisotropy introduced hour chart.

2 is a diagram schematically illustrating an example of an anisotropy introduction treatment in the method for producing a liquid crystal aligning film used in the present invention, in which a crosslinkable organic group is used in a photosensitive side chain and anisotropy introduced Big picture.

FIG. 3 is a diagram schematically illustrating an example of anisotropy introduction treatment in the method for producing a liquid crystal aligning film used in the present invention, in which a photosensitive side chain uses an organic material that undergoes Fries rearrangement or isomerization. groups and the introduced anisotropy is small.

FIG. 4 is a diagram schematically illustrating an example of anisotropy introduction treatment in the method for producing a liquid crystal aligning film used in the present invention, in which a photosensitive side chain uses an organic material that undergoes Fries rearrangement or isomerization. group and the introduced anisotropy is large.

Detailed ways

The inventors of the present invention have completed the present invention as a result of earnest research and as a result of obtaining the following findings.

The polymer composition used in the production method of the present invention has a photosensitive side chain type polymer (hereinafter also simply referred to as a side chain type polymer) that can express liquid crystallinity, and the coating film obtained using the polymer composition has Film of photosensitive side chain type polymer which can express liquid crystallinity. This coating film does not need to be brushed, and is oriented by polarized light irradiation. And it becomes the coating film (henceforth also called a liquid crystal aligning film) provided with orientation control ability through the process of heating this side chain type polymer film after polarized light irradiation. At this time, the minute anisotropy expressed by polarized light irradiation becomes a driving force, and the liquid crystalline side chain type polymer itself is effectively realigned by self-assembly. As a result, efficient alignment treatment can be realized as a liquid crystal aligning film, and a liquid crystal aligning film provided with high alignment control ability can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.

<The manufacturing method of the board|substrate which has a liquid crystal aligning film> and the <the manufacturing method of the liquid crystal display element>

The manufacturing method of the board|substrate with a liquid crystal aligning film of this invention is equipped with the following process:

[I] A step of forming a coating film by applying a polymer composition containing: (A) a liquid crystal exhibiting liquid crystallinity in a specific temperature range on a substrate having a conductive film for driving a transverse electric field to form a coating film A photosensitive side chain type polymer, (B) an amine compound having one primary amino group and a nitrogen-containing aromatic heterocycle in the molecule, and the aforementioned primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and (C) )Organic solvents;

[II] A step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and

[III] A step of heating the coating film obtained in [II].

By the said process, the liquid crystal aligning film for transverse electric field drive type liquid crystal display elements provided with the orientation control ability can be obtained, and the board|substrate which has this liquid crystal aligning film can be obtained.

Moreover, by preparing a second substrate in addition to the substrate (first substrate) obtained above, a lateral electric field-driven liquid crystal display element can be obtained.

The second substrate uses the above-mentioned steps [I] to [III] (due to the use of the conductive film without the transverse electric field driving) by using the substrate without the transverse electric field driving conductive film instead of the substrate with the transverse electric field driving conductive film. Therefore, in this application, it may be abbreviated as process [I'] - [III']) for convenience, and the 2nd board|substrate which has the liquid crystal aligning film provided with the orientation control ability can be obtained.

The manufacturing method of the lateral electric field driven liquid crystal display element includes the following steps:

[IV] The process of obtaining a liquid crystal display element by arranging the 1st board|substrate and 2nd board|substrate obtained above so that the liquid crystal aligning film of a 1st board|substrate and a 2nd board|substrate may oppose via a liquid crystal. Thereby, a lateral electric field driven liquid crystal display element can be obtained.

Hereinafter, each step of [I] to [III] and [IV] included in the production method of the present invention will be described.

<Process [I]>

In step [I], a polymer composition containing a photosensitive side that exhibits liquid crystallinity in a specific temperature range is coated on the substrate having the conductive film for lateral electric field driving to form a coating film A chain polymer; an amine compound having one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; and an organic solvent.

<substrate>

The substrate is not particularly limited, but when the liquid crystal display element to be manufactured is a transmissive type, it is preferable to use a substrate with high transparency. In this case, it is not particularly limited, and a glass substrate, an acrylic substrate, a plastic substrate such as a polycarbonate substrate, or the like can be used.

In addition, in consideration of application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer may be used.

<Conductive Film for Lateral Electric Field Driving>

The substrate has a conductive film for lateral electric field driving.

As this conductive film, when the liquid crystal display element is a transmission type, ITO (Indium Tin Oxide: Indium Tin Oxide), IZO (Indium Zinc Oxide: Indium Zinc Oxide), etc. are mentioned, but it is not limited to these.

In addition, in the case of a reflection-type liquid crystal display element, as a conductive film, materials that reflect light, such as aluminum, are mentioned, and the invention is not limited to these.

A conventionally known method can be used for the method of forming the conductive film on the substrate.

<Polymer composition>

The polymer composition is coated on the substrate having the conductive film for lateral electric field driving, especially the polymer composition is coated on the conductive film.

The polymer composition used in the production method of the present invention contains: (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a specific temperature range; (B) has one primary amino group and a nitrogen-containing molecule in the molecule. An aromatic heterocyclic ring and an amine compound in which the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; and (C) an organic solvent.

<<(A) Side chain type polymer>>

(A) component is a photosensitive side chain type polymer|macromolecule which expresses liquid crystallinity in a specific temperature range.

(A) Side chain type polymer|macromolecule should just show liquid crystallinity in the temperature range of 100-300 degreeC by reacting under the light of the wavelength range of 250nm - 400nm.

(A) It is preferable that a side chain type polymer has a photosensitive side chain which reacts with the light of the wavelength range of 250 nm - 400 nm.

(A) The side chain type polymer exhibits liquid crystallinity in the temperature range of 100°C to 300°C, and therefore preferably has a mesogenic group.

(A) The main chain of the side chain type polymer has a photosensitive side chain bonded thereto, and can undergo a crosslinking reaction, an isomerization reaction, or a photoFries rearrangement in response to light. The side chain structure having photosensitivity is not particularly limited, and a structure in which a crosslinking reaction or photoFries rearrangement occurs in response to light is desirable, and a structure in which a crosslinking reaction occurs is more desirable. In this case, the achieved orientation control ability can be stably maintained for a long period of time even when exposed to external stress such as heat. The structure of the photosensitive side chain type polymer film that can express liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a rigid mesogen component in the side chain structure. At this time, when this side chain type polymer is used as a liquid crystal aligning film, stable liquid crystal orientation can be obtained.

The structure of the polymer can be, for example, a structure having a main chain and a side chain bonded thereto, and the side chain has a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenyl benzoate group, an azobenzene group Mesogen components such as radicals, and photosensitive groups that undergo cross-linking and isomerization reactions due to induced light bound to the front end; have a main chain and a side chain bound to it, and the side chain has both a mesogen The composition also undergoes a photofries rearrangement of the phenyl benzoate group.

As a more specific example of the structure of the photosensitive side chain type polymer film capable of expressing liquid crystallinity, a structure having a main chain and a side chain selected from the group consisting of hydrocarbons and (meth)acrylates is preferable. , itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other radical polymerizable groups and at least one of the group consisting of siloxane, and the side chain contains at least one of the following formulae (1) to (6).

In the formula, A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O - or -O-CO-CH=CH-;

S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them is optionally substituted by a halogen group;

T is a single bond or an alkylene group with 1 to 12 carbon atoms, and the hydrogen atom bonded to them is optionally substituted by a halogen group;

Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different substituents selected from these The 2 to 6 rings are bonded by the bonding group B, and the hydrogen atoms bonded to them are independently optionally -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or a carbon number of 1- 5 alkyl), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl having 1 to 5 carbons, or alkane having 1 to 5 carbons Oxygen substitution;

Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and is bonded to them The hydrogen atoms of each are independently optionally replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. 5 alkoxy substitution;

R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ ;

X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O- or -O-CO-CH=CH- , when the number of X reaches 2, X is optionally the same or different from each other;

Cou represents coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bound to them are each independently optionally -NO ₂ , -CN, -CH=C(CN) ₂ , -CH= CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms, or alkoxy group with 1 to 5 carbon atoms;

One of q1 and q2 is 1, and the other is 0;

q3 is 0 or 1;

P and Q are each independently a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof; Wherein, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side where -CH=CH- is bonded is an aromatic ring, and the number of P is 2 or more When , P is optionally the same or different from each other, and when the number of Q reaches 2 or more, Q is optionally the same or different from each other;

l1 is 0 or 1;

l2 is an integer from 0 to 2;

When both l1 and l2 are 0, when T is a single bond, A also means a single bond;

When l1 is 1, when T is a single bond, B also means a single bond;

H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof.

The side chain may be any photosensitive side chain selected from the group consisting of the following formulae (7) to (10).

In the formula, A, B, D, Y ₁ , X, Y ₂ and R have the same definitions as above;

l represents an integer from 1 to 12;

m represents an integer from 0 to 2, and m1 and m2 represent an integer from 1 to 3;

n represents an integer of 0 to 12 (wherein, when n=0, B is a single bond).

The side chain may be any photosensitive side chain selected from the group consisting of the following formulae (11) to (13).

In the formula, A, X, l, m, m1 and R have the same definitions as above.

The side chain may be a photosensitive side chain represented by the following formula (14) or (15).

In the formula, A, Y ₁ , l, m1 and m2 have the same definitions as above.

The side chain may be a photosensitive side chain represented by the following formula (16) or (17).

In the formula, A, X, l and m have the same definitions as above.

In addition, the side chain may be a photosensitive side chain represented by the following formula (18) or (19).

In the formula, A, B, Y ₁ , q1 , q2 , m1 and m2 have the same definitions as above.

R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkane having 1 to 5 carbon atoms. Oxygen.

The side chain may be a photosensitive side chain represented by the following formula (20).

In the formula, A, Y ₁ , X, l and m have the same definitions as above.

In addition, the (A) side chain type polymer may have any one liquid crystalline side chain selected from the group consisting of the following formulae (21) to (31).

In the formula, A, B, q1 and q2 have the same definitions as above;

Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and a bond Each of their hydrogen atoms is independently optionally substituted by -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

R ₃ represents hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, containing nitrogen heterocycle, alicyclic hydrocarbon with 5-8 carbons, alkyl with 1-12 carbons, or alkoxy with 1-12 carbons;

l represents an integer from 1 to 12, m represents an integer from 0 to 2, where, in formulas (23) to (24), the sum of all m is 2 or more, and in formulas (25) to (26), all m The sum of is 1 or more, and m1, m2 and m3 each independently represent an integer from 1 to 3;

R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and alkyl or alkoxy;

Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, and -CF ₂ -.

<<Preparation method of photosensitive side chain type polymer>>

The photosensitive side chain type polymer|macromolecule which can express the said liquid crystallinity can be obtained by polymerizing the photoreactive side chain monomer which has the said photosensitive side chain, and a liquid crystal side chain monomer.

[Photoreactive side chain monomer]

The photoreactive side chain monomer refers to a monomer capable of forming a polymer having a photosensitive side chain in a side chain portion of the polymer when forming a polymer.

As a photoreactive group which a side chain has, the following structures and derivatives thereof are preferable.

As a more specific example of the photoreactive side chain monomer, a structure having a polymerizable group selected from hydrocarbons, (meth)acrylates, and itaconate esters and a photosensitive side chain is preferable , Fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other radical polymerizable groups and siloxane composition The photosensitive side chain is a photosensitive side chain containing at least one of the above-mentioned formulae (1) to (6), preferably, for example, the photosensitive side chain contains the above-mentioned formulae (7) to (10) at least one of the photosensitive side chains, the photosensitive side chains containing at least one of the above formulae (11) to (13), the photosensitive side chains represented by the above formulas (14) or (15), the above A photosensitive side chain represented by formula (16) or (17), a photosensitive side chain represented by said formula (18) or (19), and a photosensitive side chain represented by said formula (20).

In the present application, as photoreactive and/or liquid crystal side chain monomers, novel compounds (1) to (11) represented by the following formulae (1) to (11); and the following formulae (12) to Compounds (12) to (17) represented by (17).

In the formula, R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; R ¹⁰ represents Br or CN; S represents an alkylene group having 2 to 10 carbon atoms; u represents 0 or 1; and Py Represents 2-pyridyl, 3-pyridyl or 4-pyridyl. In addition, v represents 1 or 2.

[Liquid crystal side chain monomer]

The liquid crystalline side chain monomer refers to a monomer derived from a polymer that exhibits liquid crystallinity and that can form a mesogen group at a side chain site of the polymer.

The mesogen group in the side chain may be a group that independently forms a mesogen structure, such as biphenyl and phenyl benzoate, or a group such as benzoic acid or the like that hydrogen bonds between side chains to form a mesogen structure. the group. As a mesogen group which a side chain has, the following structures are preferable.

As a more specific example of the liquid crystal side chain monomer, a structure having a polymerizable group selected from the group consisting of a hydrocarbon, a (meth)acrylate, an itaconate, and a side chain is preferable. Composed of free radical polymerizable groups such as fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and siloxane At least one of the group is constituted, and the side chain includes at least one of the above-mentioned formulae (21) to (31).

(A) The side chain type polymer|macromolecule can be obtained by the polymerization reaction of the photoreactive side chain monomer which expresses the liquid crystallinity mentioned above. In addition, it can be obtained by the copolymerization of a photoreactive side chain monomer that does not express liquid crystallinity and a liquid crystal side chain monomer, or the copolymerization of a photoreactive side chain monomer expressing liquid crystallinity and a liquid crystal side chain monomer. Furthermore, in the range which does not impair the liquid crystallinity expressing ability, it can copolymerize with another monomer.

Examples of the other monomers include commercially available monomers capable of radical polymerization.

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

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and the like.

Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracenyl methyl acrylate, phenyl acrylate, and 2,2,2 acrylate. -Trifluoroethyl, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, acrylic acid Tetrahydrofurfuryl, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclic acrylate Decyl ester, and 8-ethyl-8-tricyclodecyl acrylate, etc.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, methyl methacrylate, and methyl methacrylate. Anthracenyl methyl acrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methacrylic acid 2-methoxyethyl ester, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-Methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-methacrylate -Ethyl-8-tricyclodecyl ester, etc. Glycidyl (meth)acrylate, (3-methyl-3-oxetanyl)methyl (meth)acrylate and (3-ethyl-3-oxetanyl) (meth)acrylate can also be used A (meth)acrylate compound having a cyclic ether group such as cyclobutanyl) methyl ester.

As a vinyl compound, vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether, etc. are mentioned, for example.

As a styrene compound, styrene, methylstyrene, chlorostyrene, bromostyrene, etc. are mentioned, for example.

As a maleimide compound, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc. are mentioned, for example.

The production method of the side chain type polymer of the present embodiment is not particularly limited, and a general industrially applied method can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization of vinyl groups using a liquid crystalline side chain monomer and a photoreactive side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control and the like.

As the polymerization initiator for radical polymerization, known compounds such as a radical polymerization initiator and a reversible addition-cleavage type chain transfer (RAFT) polymerization agent can be used.

The radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.) , Hydrogen peroxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilaurin Acyl peroxides, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peroxyesters (tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, 2-ethylcyclohexane acid tert-amyl oxide, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2 '-bis(2-hydroxyethyl)azobisisobutyronitrile, etc.). Such a radical thermal polymerization initiator may be used individually by 1 type, or may be used in combination of 2 or more types.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that starts radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, Isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2- Methyl-4'-isopropyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2 ,2-Dimethoxy-2-phenylacetophenone, camphorquinone, benzoanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane- 1-keto, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid iso Amyl ester, 4,4'-bis(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(tert-butylperoxycarbonyl)benzophenone, 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)s-triazine, 2-(3',4' -Dimethoxystyryl)-4,6-bis(trichloromethyl)s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(triazine) Chloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl) -4,6-bis(trichloromethyl)s-triazine, 4-[p-N,N-bis(ethoxycarbonylmethyl)]-2,6-bis(trichloromethyl)s-triazine , 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl) ) s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2 -Chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorobenzene) base)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'bis(2,4-dibromophenyl)-4,4',5,5' -Tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2' - Biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecyl Carbazole, 1-hydroxycyclohexyl phenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl) -Phenyl) titanium, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxy) carbonyl) benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(tert-butylperoxycarbonyl)benzophenone, 3,4'-bis(methoxycarbonyl) Carbonyl)-4,3'-bis(tert-butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-bis(tert-butylperoxycarbonyl) ) benzophenone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, or 2-(3-methyl-1,3- Benzothiazole-2(3H)-ylidene)-1-(2-benzoyl)ethanone and the like. These compounds may be used alone or in combination of two or more.

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

The organic solvent used in the polymerization reaction of the photosensitive side chain type polymer which can express liquid crystallinity is not particularly limited as long as it is an organic solvent in which the produced polymer dissolves. Specific examples thereof are listed below.

Examples include: N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolactone, isopropanol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, Methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate Esters, Butyl Carbitol, Ethyl Carbitol, Ethylene Glycol, Ethylene Glycol Monoacetate, Ethylene Glycol Monoisopropyl Ether, Ethylene Glycol Monobutyl Ether, Propylene Glycol, Propylene Glycol Monoacetate, Propylene Glycol Monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether Methyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol Propylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl Cyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate , methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate , ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diethylene glycol Dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-Butoxy-N,N-dimethylpropionamide, etc.

These organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the produced polymer, as long as the produced polymer does not precipitate, it can be mixed with the above-mentioned organic solvent and used.

In addition, in the radical polymerization, oxygen in the organic solvent may inhibit the polymerization reaction, so the organic solvent is preferably used after degassing as much as possible.

The polymerization temperature at the time of radical polymerization can select the arbitrary temperature of 30 degreeC - 150 degreeC, Preferably it is the range of 50 degreeC - 100 degreeC. The reaction can be carried out at any concentration. When the concentration is too low, it is difficult to obtain a polymer with a high molecular weight. When the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and an organic solvent may be added thereafter.

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

[Recycling of polymers]

When recovering the produced polymer from the reaction solution of the photosensitive side chain type polymer that can express liquid crystallinity obtained by the above reaction, the reaction solution may be put into a poor solvent to precipitate these polymers. Examples of poor solvents for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. . The polymer which is thrown into the poor solvent and precipitated can be collected by filtration, and then dried at normal temperature or by heating under normal pressure or reduced pressure. In addition, when the operation of redissolving the polymer recovered by precipitation in an organic solvent and reprecipitating recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent in this case include alcohols, ketones, and hydrocarbons. When three or more poor solvents selected from these are used, the purification efficiency is further improved, which is preferable.

Regarding the molecular weight of the (A) side chain type polymer of the present invention, GPC (Gel Permeation Chromatography, Gel Permeation Chromatography) was used in consideration of the strength of the obtained coating film, the workability when forming the coating film, and the uniformity of the coating film. The weight average molecular weight measured by the ) method is preferably 2,000 to 1,000,000, and more preferably 5,000 to 100,000.

[Preparation of polymer composition]

The polymer composition used in the present invention is preferably prepared in the form of a coating liquid for suitable formation of a liquid crystal aligning film. That is, the polymer composition used in the present invention is preferably prepared as a solution in which a resin component for forming a resin coating film is dissolved in an organic solvent. Here, this resin component means the resin component containing the photosensitive side chain type polymer|macromolecule which can express liquid crystallinity demonstrated above. In this case, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

In the polymer composition of the present embodiment, all of the resin components may be the above-mentioned photosensitive side-chain type polymers capable of expressing liquid crystallinity, and may be mixed to remove liquid crystals within a range that does not impair the liquid crystal expressing ability and photosensitivity. other polymers. At this time, content of the other polymer in a resin component is 0.5 mass % - 80 mass %, Preferably it is 1 mass % - 50 mass %.

Such other polymers include, for example, poly(meth)acrylates, polyamic acids, polyimides, and the like, and examples thereof include polymers that are not photosensitive side-chain type polymers capable of expressing liquid crystallinity.

<Amine compound>

The polymer composition used in the present invention has a specific amine compound, specifically, has one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic ring Amine compound of formula hydrocarbyl.

The specific amine compound is not particularly limited as long as it exhibits the following effects i) and/or ii) when the polymer composition used in the present invention forms a liquid crystal aligning film. i) adsorption of ionic impurities in the liquid crystal at the interface of the liquid crystal aligning film, and/or, ii) improvement of the voltage holding ratio is achieved.

The amount of the specific amine compound is not particularly limited as long as the above-mentioned effects are exhibited, and may be 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass in 100 parts by mass of the polymer composition used in the present invention.

Specific examples of the aliphatic hydrocarbon group include a linear alkylene group, an alkylene group having a branched structure, a divalent hydrocarbon group having an unsaturated bond, and the like. 1-20 are preferable, as for carbon number of aliphatic hydrocarbon group, 1-15 are more preferable, and 1-10 are still more preferable.

Specific examples of the divalent non-aromatic cyclic hydrocarbon group include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, and a cyclononane ring , cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclodecane ring Octane ring, cyclononadecane ring, cycloeicosane ring, tricycloeicosane ring, tricyclodocosane ring, bicycloheptane ring, decalin ring, norbornene ring, adamantane Ring etc. A non-aromatic cyclic hydrocarbon group is preferably a ring containing 3 to 20 carbons, more preferably a ring containing 3 to 15 carbons, and still more preferably a ring containing 3 to 10 carbons.

The nitrogen-containing aromatic heterocyclic ring contained in the amine compound may contain at least one, preferably one to four, selected from the following formulas [20a], [20b] and [20c] (wherein Z ₂ is Aromatic cyclic hydrocarbons having a structure in the group consisting of straight-chain or branched alkyl groups having 1 to 5 carbon atoms.

Specifically, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, and a purine ring can be mentioned. , thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoline ring, phenanthroline ring , indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, etc. Furthermore, carbon atoms of these nitrogen-containing aromatic heterocycles may have a substituent containing a heteroatom.

A more preferable amine compound may be the following formula A-[1] (in the formula, Y ₁₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y ₁₂ is a nitrogen-containing aromatic heterocycle) The amine compound shown. In formula A-[1], Y ₁₂ is not particularly limited as long as it is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

Preferable Y ₁₁ in Formula A-[1] may be a divalent organic group having one selected from the group consisting of aliphatic hydrocarbon groups having 1 to 20 carbon atoms and non-aromatic cyclic hydrocarbon groups having 3 to 20 carbon atoms. As a non-aromatic cyclic hydrocarbon group, the said structure is mentioned. More preferably, Y ₁₁ includes aliphatic hydrocarbon groups having 1 to 15 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring, etc. Y ₁₁ may be particularly preferably a straight-chain or branched alkylene group having 1 to 10 carbon atoms.

In addition, -CH ₂ - in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group that is not adjacent to the amino group contained in Y ₁₁ is optionally -O-, -NH-, -CO-O-, -O- CO-, -CO-NH-, -NH-CO-, -CO-, -S-, -S(O) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, divalent cyclic hydrocarbon or heterocyclic substitution. In addition, the hydrogen atom bonded to any carbon atom may be optionally replaced by a straight-chain or branched alkylene group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, Hydroxyl substitution.

Specific examples of the divalent cyclic hydrocarbon group include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a camomile ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a phenacene ring, a cyclopropane ring, and a cyclobutane ring. ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, Cyclotetradecane, cyclopentadecane, cyclohexadecane, cycloheptadecane, cyclooctadecane, cyclononadecane, cycloeicosane, tricycloeicosane , tricyclic docosane ring, bicycloheptane ring, decalin ring, norbornene ring, adamantane ring, etc.

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

Y ₁₂ in formula A-[1] is a nitrogen-containing aromatic heterocyclic ring, and may be a structure containing at least one selected from the group consisting of formula [20a], formula [20b], and formula [20c] as described above of aromatic cyclic hydrocarbons. The above-mentioned structure is mentioned as the specific example. Among these, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a benzimidazole ring, and a quinoxaine ring are preferred oxoline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring, phthalazine ring.

In addition, Y ₁₁ is preferably bonded to a formula not contained in Y ₁₂ from the viewpoint of the ease of forming a salt with the carboxyl group in the specific polyimide and the easiness of electrostatic interaction called hydrogen bonding between the nitrogen-containing aromatic heterocyclic ring and the carboxyl group. Substituents adjacent to [20a], formula [20b] and formula [20c].

Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of formula A-[1] as Y ₁₂ may optionally have a halogen atom and/or a substituent of an organic group, and the organic group may optionally contain an oxygen atom, a sulfur atom, Hetero atoms such as nitrogen atoms.

The preferred combination of Y ₁₁ and Y ₁₂ in formula A-[1] is: Y ₁₁ is selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. One kind of divalent organic group, Y ₁₂ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, A benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring or phthalazine ring. It should be noted that the carbon atom of the nitrogen-containing aromatic heterocycle of Y ₁₂ may optionally have a halogen atom and/or a substituent of an organic group, and the organic group may contain heteroatoms such as oxygen atom, sulfur atom and nitrogen atom.

A more preferable amine compound is the following formula A-[2] (wherein Y ₁₃ is a divalent aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms, and Y ₁₄ is a single bond or - O-, -NH-, -S-, -SO ₂ - or a divalent organic group having 1 to 19 carbon atoms. In addition, Y ₁₃ and Y ₁₄ have total carbon atoms of 1 to 20. Y ₁₅ is a group containing amine compound represented by nitrogen aromatic heterocycle.

Y ₁₃ in the formula A-[2] is a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms. Specific examples thereof are straight-chain or branched alkylene groups having 1 to 10 carbon atoms, unsaturated alkylene groups having 1 to 10 carbon atoms, cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, ring pentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloeicosane ring, tricycloeicosane ring, tricyclodocosane ring, bicycloheptane ring, decalin ring, norbornene ring, adamantane ring, etc. More preferably, a linear or branched alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, Cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring. Particularly preferred is a straight-chain or branched alkylene group having 1 to 10 carbon atoms.

-CH ₂ - in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in Y ₁₃ is optionally replaced by -O-, -NH-, -CO-O-, -O-CO -, -CO-NH-, -NH-CO-, -CO-, -S-, -S(O) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, divalent Cyclic hydrocarbyl or heterocyclic substitution. In addition, the hydrogen atom bonded to any carbon atom may be optionally replaced by a straight-chain or branched alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, or a hydroxyl group. replace. The cyclic hydrocarbon groups and heterocycles mentioned here have the same meanings as the definitions described for Y ₁₁ in the formula A-[1].

Y ₁₄ in formula A-[2] is a single bond or -O-, -NH-, -S-, -SO ₂ - or a divalent organic group having 1 to 19 carbon atoms. The divalent organic group having 1 to 19 carbon atoms is a divalent organic group having 1 to 19 carbon atoms, and may optionally contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or the like. Specific examples of such Y ₁₄ are listed below.

For example, single bond, -O-, -NH-, -S-, -SO ₂ -, hydrocarbon group having 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -CF ₂ -, -C(CF ₃ ) ₂ -, -CH(OH)-, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, - O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane Alkane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane Alkane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloeicosane ring, tricycloeicosane ring, tricyclodocosane ring, Bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, chamomile ring, indene ring, fluorene ring, anthracycline, phenanthrene ring, phenarene ring, pyrrole Ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, oxazole ring, piperazine ring, piperidine ring, dioxane ring, morpholine ring, etc. As Y ₁₄ , two or more of these may be included.

Specific examples of the above-mentioned two or more types include -NH-CH ₂ -, -NH-C ₂ H ₄ -, -NH-C ₃ H ₆ -, -NH-C ₄ H ₈ -, and -S -CH ₂ -, -SC ₂ H ₄ -, -SC ₃ H ₆ -, -SC ₄ H ₈ -, -O-CH ₂ -, -OC ₂ H ₄ -, -OC ₃ H ₆ -, -OC ₄ H ₈ -, -NH-CO-CH ₂ -, -NH-CO-C ₂ H ₄ -, -NH-CO-C ₃ H ₆ -, -NH-CO-C ₄ H ₈ -, -CO-CH ₂ -, -CO-C ₂ H ₄ -, -CO-C ₃ H ₆ -, -CO-C ₄ H ₈ -, -CO-NH-CH ₂ -, -CO-NH-C ₂ H ₄ -, -CO-NH-C ₃ H ₆ -, -CO-NH-C ₄ H ₈ -, -NH-CH ₂ -CH(CH ₃ )-, -NH-C ₂ H ₄ -CH(CH ₃ )-, -NH- _{C3H6 -} CH( _CH3 )-, -NH- _C4H8 -CH( _CH3 )-, -S- _CH2 -CH( _CH3 )-, _{-SC2H4 - CH} (CH ₃ )-, -SC ₃ H ₆ -CH(CH ₃ )-, -SC ₄ H ₈ -CH(CH ₃ )-, -O-CH ₃ -CH(CH ₃ )-, -OC ₂ H ₄ -CH(CH ₃ )-, -OC ₃ H ₆ -CH(CH ₃ )-, -OC ₄ H ₈ -CH(CH ₃ )-, -NH-CO-CH ₂ -CH(CH ₃ )-, - NH-CO-C ₂ H ₄ -CH(CH ₃ )-, -NH-CO-C ₃ H ₆ -CH(CH ₃ )-, -NH-CO-C ₄ H ₈ -CH(CH ₃ )-, -CH(OH) _-CH2- , -CH(OH) _-C2H4- , _-CH (OH) _-C3H6- , _-CH (OH) _-C4H8- , -CH ₍ CH ₂ OH)-CH ₂ -, -CH(CH ₂ OH)-C ₂ H ₄ -, -CH(CH ₂ OH)-C ₃ H ₆ -, -CH(CH ₂ OH)-C ₄ H ₈ -, -NH-CH(CH2OH) _-CH2- , -CO-NH- _CH (CH2OH) _-CH2- , -NH-CO- _CH (CH2OH) _-CH2- , -CO- _CH (CH ₂ OH)-CH ₂ -, -S-CH(CH ₂ OH)-CH ₂ -, -O-CH (CH ₂ OH)-CH ₂ -, -CH(N(CH ₃ ) ₂ )-, -C ₆ H ₄ -O-, -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH- , -C ₆ H ₄ -NH-CO-, -C ₆ H ₄ -CO-, -C ₆ H ₄ -CH ₂ -, -C ₆ H ₄ -S- and the like.

Y ₁₅ in Formula A-[2] is a nitrogen-containing aromatic heterocycle, and has the same definition as Y ₁₂ in Formula A-[1]. Specific examples thereof include the same structures as those of Y ₁₂ described above. Among these, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a benzimidazole ring, and a quinoxaine ring are preferred oxoline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring, or phthalazine ring.

In addition, Y ₁₄ is preferably bonded to a formula not contained in Y ₁₅ from the viewpoint of the ease of forming a salt with the carboxyl group in the specific polyimide and the easiness of electrostatic interaction called hydrogen bonding between the nitrogen-containing aromatic heterocycle and the carboxyl group. [20a], the adjacent carbon atoms of the formula [20b] or the formula [20c].

Further, the carbon atom of the nitrogen-containing aromatic heterocycle of formula A-[2] as Y ₁₅ may optionally have a halogen atom and/or a substituent of an organic group, and the organic group may optionally contain an oxygen atom, a sulfur atom, Hetero atoms such as nitrogen atoms.

The preferred combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in formula A-[2] is: Y ₁₃ is a straight-chain or branched alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring Alkane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane Ring, norbornene ring or adamantane ring, Y ₁₄ is a single bond, a straight-chain or branched alkylene group having 1 to 10 carbon atoms, -O-, -NH-, -CO-O-, -O-CO -, -CO-NH-, -NH-CO-, -CO-, -S-, -SO ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, -CH(OH)-, -NH-CH ₂ -, - NH-C ₂ H ₄ -, -NH-C ₃ H ₆ -, -NH-C ₄ H ₈ -, -S-CH ₂ -, -SC ₂ H ₄ -, -SC ₃ H ₆ -, -SC ₄ H ₈ -, -O-CH ₂ -, -OC ₂ H ₄ -, -OC ₃ H ₆ -, -OC ₄ H ₈ -, -NH-CO-CH ₂ -, -NH-CO-C ₂ H ₄ -, -NH-CO-C ₃ H ₆ -, -NH-CO-C ₄ H ₈ -, -CO-CH ₂ -, -CO-C ₂ H ₄ -, -CO-C ₃ H ₆ -, - CO-C ₄ H ₈ -, -CO-NH-CH ₂ -, -CO-NH-C ₂ H ₄ -, -CO-NH-C ₃ H ₆ -, -CO-NH-C 4 H 8 -, -CO-NH-C ₄ H ₈ -, -NH-CH ₂ -CH(CH ₃ )-, -NH-C ₂ H ₄ -CH(CH ₃ )-, -NH-C ₃ H ₆ -CH(CH ₃ )-, -NH-C ₄ H ₈ -CH(CH ₃ )-, -S-CH ₂ -CH(CH ₃ )-, -SC ₂ H ₄ -CH(CH ₃ )-, -SC ₃ H ₆ -CH(CH ₃ )-, -SC ₄ H ₈ -CH(CH ₃ )-, -O-CH ₃ -CH(CH ₃ )-, -OC ₂ H ₄ -CH(CH ₃ )-, -OC ₃ H ₆ -CH(CH ₃ )-, - OC ₄ H ₈ -CH(CH ₃ )-, -NH-CO-CH ₂ -CH(CH ₃ )-, -NH-CO-C ₂ H ₄ -CH(CH ₃ )-, -NH-CO-C ₃ H ₆ -CH(CH ₃ )-, -NH-CO-C ₄ H ₈ -CH(CH ₃ )-, -CH(OH)-CH ₂ -, -CH(OH)-C ₂ H ₄ -, -CH(OH)-C ₃ H ₆ -, -CH(OH)-C ₄ H ₈ -, - CH(CH ₂ OH)-CH ₂ -, -CH(CH ₂ OH)-C ₂ H ₄ -, -CH(CH ₂ OH)-C ₃ H ₆ -, -CH(CH ₂ OH)-C ₄ H ₈ -, -NH-CH(CH ₂ OH)-CH ₂ -, -CO-NH-CH(CH ₂ OH)-CH ₂ -, -NH-CO-CH(CH ₂ OH)-CH ₂ -, - CO-CH(CH ₂ OH)-CH ₂ -, -S-CH(CH ₂ OH)-CH ₂ -, -O-CH(CH ₂ OH)-CH ₂ -, -CH(N(CH ₃ ) ₂ )-, -C ₆ H ₄ -O-, -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH-, -C ₆ H ₄ -NH-CO-, -C ₆ H ₄ -CO- -, -C ₆ H ₄ -CH ₂ -, -C ₆ H ₄ -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, Cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, chamomile ring, indene ring, fluorene ring, Anthracycline, phenanthrene ring, phenacene ring, Y ₁₅ is pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring , a benzimidazole ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring or a phthalazine ring. It should be noted that the carbon atom of the nitrogen-containing aromatic heterocycle of Y ₁₅ may optionally have a halogen atom and/or a substituent of an organic group, and the organic group may optionally contain heteroatoms such as oxygen atom, sulfur atom, nitrogen atom, etc. .

A more preferred combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in formula A-[2] is: Y ₁₃ is a straight-chain or branched alkylene group having 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring, a ring Pentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, or adamantane ring, Y ₁₄ is a single bond, a straight-chain or branched alkylene group having 1 to 5 carbon atoms, -O-, - NH-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -S-, -S(O) ₂ -, -CH(OH)-, -NH-CH2-, -S _- CH2-, _-O -CH2-, -OC2H4-, -NH _{- CO -} CH2-, -CO _- CH2-, -CO-NH- _{CH 2} -, -NH-CH ₂ -CH(CH ₃ )-, -S-CH ₂ -CH(CH ₃ )-, -O-CH ₃ -CH(CH ₃ )-, -NH-CO-CH ₂ - CH(CH ₃ )-, -CH(OH)-CH ₂ -, -CH(OH)-C ₂ H ₄ -, -CH(CH ₂ OH)-CH ₂ -, -NH-CH(CH ₂ OH) -CH ₂ -, -CO-NH-CH(CH ₂ OH)-CH ₂ -, -NH-CO-CH(CH ₂ OH)-CH ₂ -, -CO-CH(CH ₂ OH)-CH ₂ - , -S-CH(CH ₂ OH)-CH ₂ -, -O-CH(CH ₂ OH)-CH ₂ -, -CH(N(CH ₃ ) ₂ )-, -C ₆ H ₄ -O-, -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH-, -C ₆ H ₄ -NH-CO-, -C ₆ H ₄ -CO-, -C ₆ H ₄ -CH ₂ -, -C ₆ H ₄ -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydro naphthalene ring, camomile ring, indene ring, fluorene ring, anthracycline, phenanthrene ring, or phenacene ring, Y ₁₅ is pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, A triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring or phthalazine ring. It should be noted that the carbon atom of the nitrogen-containing aromatic heterocycle of Y ₁₅ may optionally have a halogen atom and/or a substituent of an organic group, and the organic group may optionally contain heteroatoms such as an oxygen atom, a sulfur atom, and a nitrogen atom. .

A further preferred combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in formula A-[2] is: Y ₁₃ is a straight-chain or branched alkylene group with 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring, Cyclopentane ring or cyclohexane ring, Y ₁₄ is a single bond, a straight-chain or branched alkylene group having 1 to 5 carbon atoms, -O-, -NH-, -CO-O-, -O-CO -, -CO-NH-, -NH-CO-, -CO-, -CH(OH)-, -NH-CH2-, -S _- CH2-, _-O -CH2-, -NH- _CO -CH ₂ -, -CO-CH ₂ -, -CO-NH-CH ₂ -, -NH-CH ₂ -CH(CH ₃ )-, -S-CH ₂ -CH(CH ₃ )-, -O- CH ₃ -CH(CH ₃ )-, -NH-CO-CH ₂ -CH(CH ₃ )-, -CH(OH)-CH ₂ -, -CH(OH)-C ₂ H ₄ -, -CH( CH ₂ OH)-CH ₂ -, -NH-CH(CH ₂ OH)-CH ₂ -, -CO-NH-CH(CH ₂ OH)-CH ₂ -, -NH-CO-CH(CH ₂ OH) -CH ₂ -, -CO-CH(CH ₂ OH)-CH ₂ -, -S-CH(CH ₂ OH)-CH ₂ -, -O-CH(CH ₂ OH)-CH ₂ -, -CH( N(CH ₃ ) ₂ )-, -C ₆ H ₄ -O-, -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH-, -C ₆ H ₄ -NH-CO-, - C ₆ H ₄ -CO-, -C ₆ H ₄ -CH ₂ -, -C ₆ H ₄ -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring , norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring or anthracene ring, Y ₁₅ is pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, A triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, or a benzimidazole ring. It should be noted that the carbon atom of the nitrogen-containing aromatic heterocycle of Y ₁₅ may optionally have a halogen atom and/or a substituent of an organic group, and the organic group may optionally contain heteroatoms such as an oxygen atom, a sulfur atom, and a nitrogen atom. .

A particularly preferred combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in formula A-[2] is: Y ₁₃ is a straight-chain or branched alkylene group having 1 to 5 carbon atoms, a cyclobutane ring, or a cyclohexane Ring, Y ₁₄ is a single bond, -O-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CH(OH)-, benzene ring, naphthalene ring, fluorene ring or anthracycline, Y ₁₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring. It should be noted that the carbon atom of the nitrogen-containing aromatic heterocycle of Y ₁₅ may optionally have a halogen atom and/or a substituent of an organic group, and the organic group may optionally contain heteroatoms such as an oxygen atom, a sulfur atom, and a nitrogen atom. .

As a specific example of the specific amine compound of (B) component of this invention, the compound of M1-M156 is mentioned.

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

<Organic solvent>

The organic solvent used in the polymer composition used in the present invention is not particularly limited as long as it can dissolve the resin component. Specific examples thereof are listed below.

Examples include: N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-ethylpyrrolidone -Vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, gamma-butyrolactone, 3-methoxy-N,N-dimethylpropionamide , 3-ethoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 1,3-dimethylimidazolidinone, ethyl amyl ketone, Methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl Alkyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether , dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl ether 3-methoxybutyl acetate, tripropylene glycol methyl ether, etc. They can be used alone or in combination.

The polymer composition used in the present invention may contain components other than the above-mentioned (A), (B) and (C) components. Examples thereof include, but are not limited to, solvents or compounds that improve the uniformity of film thickness and surface smoothness when applying the polymer composition, and compounds that improve the adhesion between the liquid crystal aligning film and the substrate.

Specific examples of the solvent (poor solvent) for improving the uniformity of the film thickness and the surface smoothness include the following solvents.

For example, isopropanol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, Butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, Dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl -3-Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyric acid Butyl ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate , methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate , ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methylpropionate Oxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diethyl acid ester, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy) propanol, methyl lactate Solvents with low surface tension, such as ester, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc.

These poor solvents may be used alone or in combination of two or more. When the above-mentioned solvent is used, in order not to significantly reduce the solubility of the entire solvent contained in the polymer composition, it is preferably 5% by mass to 80% by mass, and more preferably 20% by mass to 60% by mass of the entire solvent.

As a compound which improves the uniformity of a film thickness and surface smoothness, a fluorine-type surfactant, a silicone-type surfactant, a nonionic surfactant, etc. are mentioned.

More specifically, Eftop (registered trademark) 301, EF303, EF352 (manufactured by Tohkem products Corporation); Megafac (registered trademark) F171, F173, R-30 (manufactured by DIC CORPORATION); Fluorad FC430, FC431 (Sumitomo 3M Limited), for example AsahiGuard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.); Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC SEIMICHEMICAL CO., LTD.), etc. The usage ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, with respect to 100 parts by mass of the resin component contained in the polymer composition.

As a specific example of the compound which improves the adhesiveness of a liquid crystal aligning film and a board|substrate, the functional silane containing compound etc. which are shown below are mentioned.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2 -aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3 -Ureapropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilane Silylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-trimethoxysilyl Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl -3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl- 3-Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis( oxyethylene)-3-aminopropyltriethoxysilane, etc.

Furthermore, in order to improve the adhesiveness of a board|substrate and a liquid crystal aligning film, and to prevent the reduction of electric characteristics by backlight when a liquid crystal display element is constituted, etc., the following phenolic plastics, epoxy group-containing compounds can be contained in the polymer composition. Compound additives. Specific phenolic plastic additives are shown below, but are not limited to this structure.

Specific examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6- Tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidylm-xylylenediamine, 1,3-bis(N,N-diglycidylcarbamate group) cyclohexane, N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, etc.

When using the compound for improving the adhesiveness of a liquid crystal aligning film and a board|substrate, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of resin components contained in the polymer composition, and its usage-amount is more preferably 1-30 mass parts 20 parts by mass. When the usage-amount is less than 0.1 mass part, the effect of improving adhesiveness cannot be anticipated, and when it exceeds 30 mass parts, the orientation of a liquid crystal may deteriorate.

As additives, photosensitizers can also be used. Preferred are leuco sensitizers and triplet sensitizers.

As photosensitizers, there are aromatic nitro compounds, coumarin (7-diethylamino-4-methyl coumarin, 7-hydroxy 4-methyl coumarin), coumarin ketone, carbonyl dicoumarin ketones, aromatic 2-hydroxy ketones, and amino-substituted aromatic 2-hydroxy ketones (2-hydroxybenzophenone, mono-p-(dimethylamino)-2-hydroxybenzophenone, or di-p-(dimethylamino)-2-hydroxybenzophenone amino)-2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzoxanthone, thiazoline (2-benzoylmethylene-3- Methyl-β-naphthothiazoline, 2-(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3-methylbenzothiazole 2-(4-biphenylmethylene)-3-methylbenzothiazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2- (4-biphenylmethylene)-3-methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline), oxa oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2-(β-naphthoylmethylene)-3-methylbenzoxazoline, 2-( α-Naphthoylmethylene)-3-methylbenzoxazoline, 2-(4-biphenylmethylene)-3-methylbenzoxazoline, 2-(β-naphthoylidene Methyl)-3-methyl-β-naphthoxazoline, 2-(4-biphenylmethylene)-3-methyl-β-naphthoxazoline, 2-(p-fluorobenzyl) Acylmethylene)-3-methyl-β-naphthoxazoline), benzothiazole, nitroaniline (m-nitroaniline or p-nitroaniline, 2,4,6-trinitroaniline) or Nitroacenaphthylene (5-nitroacenaphthene), (2-[(m-hydroxy-p-methoxy)styryl]benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone acetal Ketone (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthylcarbinol, 2-naphthalenecarboxylate, 9-anthracenecarboxylate and 9-anthracenecarboxylate), benzopyran, azo Indene, Merlot Coumarin, etc.

Preferred are aromatic 2-hydroxy ketones (benzophenones), coumarin, coumarin ketones, carbonyl dicoumarins, acetophenones, anthraquinones, xanthones, thioxanthones and benzene Acetone ketal.

In addition to the above substances, in the polymer composition, as long as the effects of the present invention are not impaired, for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal aligning film, dielectrics and conductive substances may be added, Furthermore, a crosslinkable compound can be added for the purpose of improving the hardness and density of the film when it is used as a liquid crystal aligning film.

The method of coating the above-mentioned polymer composition on the substrate having the conductive film for lateral electric field driving is not particularly limited.

Regarding the coating method, industrially, it is generally a method performed by screen printing, offset printing, flexographic printing, or inkjet method. As another coating method, there are a dipping method, a roll coating method, a slit coating method, a spin coating method (spin coating method), a spray coating method, and the like, and these can be used according to the purpose.

After the polymer composition is applied on the substrate having the conductive film for lateral electric field driving, it is heated at 50 to 200° C., preferably 50 to 150° C., by heating means such as a hot plate, a thermal cycle type oven, or an IR (infrared) type oven. The solvent evaporates, whereby a coating film can be obtained. The drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain type polymer.

When the thickness of the coating film is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and when the thickness of the coating film is too thin, the reliability of the liquid crystal display element may decrease, so it is preferably 5 nm to 300 nm, more preferably 10 nm to 10 nm. 150nm.

Moreover, you may provide the process of cooling the board|substrate on which the coating film was formed to room temperature after the [I] process and before the next [II] process.

<Process [II]>

In step [II], polarized ultraviolet rays are irradiated to the coating film obtained in step [I]. When irradiating polarized ultraviolet rays to the film surface of the coating film, polarized ultraviolet rays are irradiated to the substrate through a polarizing plate from a specific direction. As the ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. It is preferable to select the optimum wavelength by means of a filter or the like according to the kind of coating film to be used. In addition, for example, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selectively used so that the photocrosslinking reaction can be selectively induced. As the ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The amount of exposure to polarized ultraviolet rays depends on the coating film to be used. The irradiation amount is preferably within a range of 1% to 70% of the amount of polarized ultraviolet rays that achieves the maximum value of ΔA (hereinafter also referred to as ΔAmax), and more preferably within a range of 1% to 50%. It is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays of the coating film.

<Process [III]>

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

For the heating, heating means such as a hot plate, a thermal cycle type oven, or an IR (infrared) type oven can be used. The heating temperature can be determined in consideration of the temperature at which the coating film used expresses liquid crystallinity.

The heating temperature is preferably within a temperature range at which the side chain type polymer expresses liquid crystallinity (hereinafter referred to as liquid crystal expression temperature). In the case of a thin film surface such as a coating film, the liquid crystal expression temperature on the coating film surface is expected to be lower than the liquid crystal expression temperature when the photosensitive side chain type polymer exhibiting liquid crystallinity is observed as a whole. Therefore, the heating temperature is more preferably within the temperature range of the temperature of the liquid crystal on the surface of the coating film. That is, the temperature range of the heating temperature after irradiating polarized ultraviolet rays is preferably a temperature 10°C lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain type polymer used as the lower limit, and 10°C lower than the upper limit of the liquid crystal temperature range. The temperature in °C is the temperature in the range of the upper limit. When the heating temperature is lower than the above temperature range, the effect of increasing the anisotropy in the coating film by heat tends to be insufficient, and when the heating temperature is too high compared with the above temperature range, the coating film state tends to be close to anisotropy. The tendency of an isotropic liquid state (isotropic phase), in this case, may be difficult to reorient in one direction due to self-assembly.

It should be noted that the liquid crystal expression temperature refers to the glass transition temperature (Tg) at which the surface of the side chain type polymer or the coating film undergoes phase transition from the solid phase to the liquid crystal phase, and from the liquid crystal phase to the homogeneous phase (isotropic phase). ) below the homogeneous phase transition temperature (Tiso) at which phase transition occurs.

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

By having the above steps, in the production method of the present invention, it is possible to efficiently introduce anisotropy into the coating film. And the board|substrate with a liquid crystal aligning film can be manufactured efficiently.

<Process [IV]>

The step [IV] is to make the substrate (first substrate) having a liquid crystal aligning film on the conductive film for lateral electric field drive obtained in [III] similarly to those obtained in the above [I'] to [III'] without having a liquid crystal aligning film. The process of producing a liquid crystal display element of a lateral electric field driven type by producing a liquid crystal cell by a known method and arranging the substrates (second substrate) with a liquid crystal aligning film of the conductive film so as to face each other with both liquid crystal aligning films facing each other with the liquid crystal interposed therebetween. . It should be noted that, in the steps [I'] to [III'], in the step [I], a substrate without the conductive film for lateral electric field driving is used instead of the substrate having the conductive film for lateral electric field driving, It can be carried out in the same manner as the steps [I] to [III]. The steps [I] to [III] differ from the steps [I'] to [III'] only in the presence or absence of the above-mentioned conductive film, so the description of the steps [I'] to [III'] is omitted.

One example of production of a liquid crystal cell or a liquid crystal display element will be exemplified by a method of preparing the above-mentioned first substrate and second substrate, spreading spacers on the liquid crystal aligning film of one substrate, and making the liquid crystal aligning film surface The method of attaching to another board|substrate by the inner side, injecting a liquid crystal under reduced pressure, and sealing; Or, the method of attaching a board|substrate and sealing after dripping a liquid crystal on the liquid crystal aligning film surface with a spacer scattered. In this case, it is preferable to use a substrate having an electrode having a comb-like structure for driving a transverse electric field as one of the substrates. The spacer diameter at this time is preferably 1 μm to 30 μm, and more preferably 2 μm to 10 μm. The spacer diameter determines the distance between the pair of substrates for sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.

In the manufacturing method of the board|substrate with a coating film of this invention, after apply|coating a polymer composition on a board|substrate and forming a coating film, polarized ultraviolet rays are irradiated. Next, the anisotropy is efficiently introduced into the side chain type polymer film by heating, and the board|substrate with a liquid crystal aligning film which has a liquid crystal orientation control ability is manufactured.

In the coating film used in the present invention, anisotropy can be efficiently introduced into the coating film by utilizing the principle of molecular reorientation induced by the photoreaction of the side chain and the self-assembly based on liquid crystallinity. In the production method of the present invention, when the side chain type polymer has a structure in which a photocrosslinkable group is a photoreactive group, after forming a coating film on the substrate using the side chain type polymer, polarized ultraviolet rays are irradiated, followed by heating Then, a liquid crystal display element was produced.

Hereinafter, an embodiment using a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group will be referred to as a first embodiment, and an embodiment using a side chain polymer having a photoFries rearrangement group or a photoreactive group will be referred to as a first embodiment. The embodiment of the side chain type polymer in which the structured group is the structure of the photoreactive group is referred to as the second embodiment, and will be described.

FIG. 1 is a schematic diagram illustrating a method for producing a liquid crystal aligning film in which a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group is used in the first aspect of the present invention. A diagram of an example of anisotropic introduction processing. FIG. 1( a ) is a diagram schematically illustrating the state of the side chain type polymer film before polarized light irradiation, and FIG. 1( b ) is a diagram schematically illustrating a side chain type polymer film after polarized light irradiation. Figure 1(c) is a diagram schematically illustrating the state of the side chain type polymer film after heating, especially when the introduced anisotropy is small, that is, in the first aspect of the present invention, [ II] A schematic diagram when the amount of ultraviolet irradiation in the step makes ΔA within the range of 1% to 15% of the maximum ultraviolet irradiation amount.

2 schematically illustrates a method for producing a liquid crystal aligning film in which a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group is used in the first aspect of the present invention A diagram of an example of anisotropic introduction processing. FIG. 2( a ) is a diagram schematically illustrating the state of the side chain type polymer film before polarized light irradiation, and FIG. 2( b ) is a diagram schematically illustrating a side chain type polymer film after polarized light irradiation. 2(c) is a diagram schematically illustrating the state of the side chain type polymer film after heating, especially when the introduced anisotropy is large, that is, in the first aspect of the present invention, [II] A schematic diagram when the ultraviolet irradiation amount in the step is within a range of 15% to 70% of the maximum ultraviolet irradiation amount for ΔA.

3 schematically illustrates a structure using a photo-isomerizable group or a photo-Fries rearrangement group represented by the above formula (18) as a photo-reactive group in the second aspect of the present invention The figure of an example of the anisotropy introduction process in the manufacturing method of a liquid crystal aligning film with the side chain type polymer of . FIG. 3( a ) is a diagram schematically illustrating the state of the side chain type polymer film before polarized light irradiation, and FIG. 3( b ) is a diagram schematically illustrating a side chain type polymer film after polarized light irradiation. Fig. 3(c) is a diagram schematically illustrating the state of the side chain type polymer film after heating, especially when the introduced anisotropy is small, that is, in the second aspect of the present invention, [ II] A schematic diagram when the ultraviolet irradiation dose in the step is within a range of 1% to 70% of the maximum ultraviolet irradiation dose for ΔA.

FIG. 4 schematically illustrates the use of a side chain type polymer having a structure having a photofries rearrangement group represented by the above formula (19) as a photoreactive group in the second aspect of the present invention. The figure of an example of the anisotropy introduction process in the manufacturing method of a liquid crystal aligning film. FIG. 4( a ) is a diagram schematically illustrating the state of the side chain type polymer film before polarized light irradiation, and FIG. 4( b ) is a diagram schematically illustrating a side chain type polymer film after polarized light irradiation. 4(c) is a diagram schematically illustrating the state of the side chain type polymer film after heating, especially when the introduced anisotropy is large, that is, in the second aspect of the present invention, [II] A schematic diagram when the ultraviolet irradiation amount in the step is within a range of 1% to 70% of the maximum ultraviolet irradiation amount for ΔA.

In the first aspect of the present invention, by the treatment of introducing anisotropy to the coating film, when the ultraviolet irradiation amount in the step [II] is within a range of 1% to 15% of the maximum ultraviolet irradiation amount for ΔA, first, the The coating film 1 is formed on the substrate. As shown in FIG. 1( a ), the coating film 1 formed on the substrate has a structure in which side chains 2 are randomly arranged. According to the random arrangement of the side chains 2 of the coating film 1, the mesogen components and the photosensitive groups of the side chains 2 are also randomly aligned, and the coating film 1 is isotropic.

In the first aspect of the present invention, by the treatment of introducing anisotropy into the coating film, when the ultraviolet irradiation amount in the step [II] is within a range of 15% to 70% of the maximum ultraviolet irradiation amount for ΔA, first, The coating film 3 is formed on the substrate. As shown in FIG. 2( a ), the coating film 3 formed on the substrate has a structure in which side chains 4 are randomly arranged. According to the random arrangement of the side chains 4 of the coating film 3, the mesogen components and the photosensitive groups of the side chains 4 are also randomly aligned, and the coating film 2 is isotropic.

In the second aspect of the present invention, by the treatment of introducing anisotropy to the coating film, a film using a structure having a photoisomerizable group or a photoFries rearrangement group represented by the above formula (18) is applied. In the case of a liquid crystal aligning film of a side chain type polymer, when the ultraviolet irradiation dose in the [II] step is within a range of 1% to 70% of the maximum ultraviolet irradiation dose for ΔA, first, the coating film 5 is formed on the substrate. As shown in FIG. 3( a ), the coating film 5 formed on the substrate has a structure in which side chains 6 are randomly arranged. According to the random arrangement of the side chains 6 of the coating film 5, the mesogen components and photosensitive groups of the side chains 6 are also randomly aligned, and the side chain type polymer film 5 is isotropic.

In the second aspect of the present invention, the liquid crystal orientation using the side chain type polymer having the structure of the photofries rearrangement group represented by the above formula (19) is applied by the treatment of introducing anisotropy to the coating film In the case of the film, the coating film 7 is first formed on the substrate when the ultraviolet irradiation amount in the step [II] is within a range of 1% to 70% of the maximum ultraviolet irradiation amount for ΔA. As shown in FIG. 4( a ), the coating film 7 formed on the substrate has a structure in which side chains 8 are randomly arranged. According to the random arrangement of the side chains 8 of the coating film 7, the mesogen components and the photosensitive groups of the side chains 8 are also randomly aligned, and the coating film 7 is isotropic.

In the first aspect of the present embodiment, the isotropic coating film 1 is irradiated with polarized ultraviolet rays when the amount of ultraviolet irradiation in the step [II] is within the range of 1% to 15% of the maximum ultraviolet irradiation amount for ΔA. As a result, as shown in FIG. 1( b ), among the side chains 2 arranged in the direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 2 a having a photosensitive group is preferentially generated Photoreactions such as dimerization. As a result, the density of the photoreacted side chains 2 a slightly increases in the polarization direction of the irradiated ultraviolet rays, and as a result, very small anisotropy is imparted to the coating film 1 .

In the first aspect of the present embodiment, the isotropic coating film 3 is irradiated with polarized ultraviolet rays when the amount of ultraviolet irradiation in the step [II] is within a range of 15% to 70% of the maximum ultraviolet irradiation amount for ΔA. As a result, as shown in FIG. 2( b ), among the side chains 4 arranged in the direction parallel to the polarization direction of the ultraviolet rays, the photosensitive group of the side chain 4 a having a photosensitive group is preferentially generated. Photoreactions such as dimerization. As a result, the density of the photoreacted side chains 4 a increases in the polarization direction of the irradiated ultraviolet rays, and as a result, small anisotropy is imparted to the coating film 3 .

In the second aspect of the present embodiment, a liquid crystal aligning film using a side chain type polymer having a structure of a photoisomerizable group or a photofries rearrangement group represented by the above formula (18) is applied, The isotropic coating film 5 is irradiated with polarized ultraviolet rays when the amount of ultraviolet irradiation in the step [II] is within a range of 1% to 15% of the maximum ultraviolet irradiation amount for ΔA. As a result, as shown in FIG. 3( b ), among the side chains 6 arranged in the direction parallel to the polarization direction of the ultraviolet rays, the photosensitive group of the side chain 6 a having a photosensitive group is preferentially generated Photoreactions such as photofries rearrangement. As a result, the density of the photoreacted side chains 6 a slightly increases in the polarization direction of the irradiated ultraviolet rays, and as a result, very small anisotropy is imparted to the coating film 5 .

In the second aspect of the present embodiment, a coating film using a side chain type polymer having a structure of a photofries rearrangement group represented by the above formula (19) is applied, and the amount of ultraviolet irradiation in the step [II] is The isotropic coating film 7 is irradiated with polarized ultraviolet rays when ΔA is within a range of 1% to 70% of the maximum ultraviolet irradiation amount. As a result, as shown in FIG. 4( b ), among the side chains 8 arranged in the direction parallel to the polarization direction of the ultraviolet rays, the photosensitive group of the side chain 8 a having a photosensitive group is preferentially generated Photoreactions such as photofries rearrangement. As a result, the density of the photoreacted side chains 8 a increases in the polarization direction of the irradiated ultraviolet rays, and as a result, small anisotropy is imparted to the coating film 7 .

Next, in the first aspect of the present embodiment, the coating film 1 irradiated with polarized light is heated and prepared when the amount of ultraviolet irradiation in the step [II] is within a range of 1% to 15% of the maximum ultraviolet irradiation amount for ΔA. into a liquid crystal state. As a result, as shown in FIG. 1( c ), in the coating film 1 , the amount of the crosslinking reaction generated is different between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular to the polarization direction of the irradiated ultraviolet rays . At this time, since the amount of the crosslinking reaction generated in the direction parallel to the polarization direction of the irradiated ultraviolet rays is very small, the crosslinking reaction site functions as a plasticizer. Therefore, the liquid crystallinity in the direction perpendicular to the polarization direction of the irradiated ultraviolet rays is higher than the liquid crystallinity in the direction parallel to the polarization direction of the irradiated ultraviolet rays, self-assembly occurs in the direction parallel to the polarization direction of the irradiated ultraviolet rays, and the side chains of the mesogen component are included. 2 Perform reorientation. As a result, the very small anisotropy of the coating film 1 induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 1 .

Similarly, in the first aspect of the present embodiment, when the ultraviolet irradiation amount in the step [II] is within a range of 15% to 70% of the maximum ultraviolet irradiation amount for ΔA, the coating film 3 irradiated with polarized light is heated to into a liquid crystal state. As a result, as shown in FIG. 2( c ), in the side chain type polymer film 3 , crosslinking occurs between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular to the polarization direction of the irradiated ultraviolet rays. The amount of reaction varies. Therefore, self-assembly occurs in a direction parallel to the polarization direction of the irradiated ultraviolet rays, and the side chains 4 including the mesogen component are realigned. As a result, the small anisotropy of the coating film 3 induced by the photocrosslinking reaction is amplified by heat, and the coating film 3 is given a larger anisotropy.

Similarly, in the second aspect of the present embodiment, a coating film using a side chain type polymer having a structure having a photoisomerizable group or a photofries rearrangement group represented by the above formula (18) is applied When the ultraviolet irradiation amount in the step [II] is within the range of 1% to 70% of the maximum ultraviolet irradiation amount of ΔA, the coating film 5 irradiated with polarized light is heated to be in a liquid crystal state. As a result, as shown in FIG. 3( c ), in the coating film 5 , the generated light Fries rearranges between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular to the polarization direction of the irradiated ultraviolet rays The amount of reaction varies. At this time, since the liquid crystal alignment force of the photofries rearrangement generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet rays is stronger than that of the side chains before the reaction, self-assembly occurs in the direction perpendicular to the polarization direction of the irradiated ultraviolet rays. , and the side chain 6 containing the mesogen component is reoriented. As a result, the very small anisotropy of the coating film 5 induced by the photo-Fries rearrangement reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 5 .

Similarly, in the second aspect of the present embodiment, a coating film using a side chain type polymer having a structure of a photofries rearrangement group represented by the above formula (19) is applied, and the ultraviolet irradiation in the step [II] is applied. When the amount is within the range of 1% to 70% of the maximum ultraviolet irradiation amount for ΔA, the coating film 7 irradiated with polarized light is heated to be in a liquid crystal state. As a result, as shown in FIG. 4( c ), in the side chain type polymer film 7 , light flux is generated between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular to the polarization direction of the irradiated ultraviolet rays. The amount of Liss rearrangement reaction varies. The photofries rearrangement 8(a) has a stronger anchoring force than the side chain 8 before the rearrangement. Therefore, when a certain amount or more of the photofries rearrangement is generated, the photo-Fries rearrangement occurs in a direction parallel to the polarization direction of the irradiated ultraviolet rays. After assembly, the side chain 8 containing the mesogen component is reoriented. As a result, the small anisotropy of the coating film 7 induced by the photo-Fries rearrangement reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 7 .

Therefore, anisotropy can be efficiently introduced into the coating film used in the method of the present invention by sequentially irradiating the coating film with polarized ultraviolet rays and heat treatment, and it can be used as a liquid crystal aligning film excellent in alignment control ability.

In addition, with respect to the coating film used in the method of the present invention, the irradiation amount of the polarized ultraviolet rays irradiated to the coating film and the heating temperature of the heat treatment are optimized. Thereby, anisotropy can be efficiently introduced into the coating film.

The optimal irradiation amount of polarized ultraviolet rays for efficiently introducing anisotropy into the coating film used in the present invention corresponds to photo-crosslinking reaction, photoisomerization reaction, or photosensitive group in the coating film. The amount of Fries rearrangement reaction reaches the optimum amount of polarized UV irradiation. As a result of irradiating polarized ultraviolet rays to the coating film used in the present invention, when there are few photosensitive groups in the side chains that undergo photocrosslinking reaction, photoisomerization reaction or photoFries rearrangement reaction, a sufficient photoreaction amount cannot be achieved. . In this case, sufficient self-assembly does not proceed even if it is heated thereafter. On the other hand, in the coating film used in the present invention, as a result of irradiating a structure having a photocrosslinkable group with polarized ultraviolet rays, when the photosensitive group of the side chain that undergoes the crosslinking reaction is excessive, the amount of the photosensitive group between the side chains is excessive. The cross-linking reaction will advance excessively. At this time, the obtained film may become rigid, which may hinder the subsequent advancement of self-assembly by heating. In addition, in the coating film used in the present invention, as a result of irradiating polarized ultraviolet rays to the structure having the photo-Fries rearrangement group, the photosensitive group of the side chain which undergoes the photo-Fries rearrangement reaction becomes excessive. , the liquid crystallinity of the coating film will decrease excessively. At this time, the liquid crystallinity of the obtained film is also lowered, and the subsequent progress of self-assembly by heating may be hindered. Furthermore, when polarized ultraviolet rays are irradiated to a structure having a photofries rearrangement group, if the irradiation amount of ultraviolet rays is too large, the side chain type polymer may be photodecomposed, which may hinder the subsequent advancement of self-assembly by heating. .

Therefore, in the coating film used in the present invention, the optimum amount of photo-crosslinking reaction, photo-isomerization reaction or photo-Fries rearrangement reaction of the photosensitive group of the side chain due to irradiation of polarized ultraviolet rays is preferably set. It is 0.1 mol % - 40 mol % of the photosensitive group which this side chain type polymer film has, More preferably, it is 0.1 mol % - 20 mol %. By making the quantity of the photosensitive group of the side chain which carry out a photoreaction into such a range, self-assembly in subsequent heat processing will advance efficiently, and high-efficiency anisotropy in a film can be formed.

In the coating film used in the method of the present invention, by optimizing the irradiation amount of polarized ultraviolet rays, the photocrosslinking reaction, the photoisomerization reaction, or the photosensitive group in the side chain of the side chain type polymer film is optimized. The amount of Fries rearrangement reaction. In addition, it is possible to efficiently introduce anisotropy into the coating film used in the present invention together with the subsequent heat treatment. At this time, the suitable amount of polarized ultraviolet rays can be performed based on the evaluation of the ultraviolet absorption of the coating film used in the present invention.

That is, for the coating film used in the present invention, the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorption in the direction perpendicular to the polarization direction of the polarized ultraviolet ray after irradiation of the polarized ultraviolet ray were measured, respectively. ΔA, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays in the coating film, was evaluated from the measurement results of ultraviolet absorption. Then, the maximum value (ΔAmax) of ΔA realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet rays realized therefrom were obtained. In the production method of the present invention, the amount of polarized ultraviolet light to be irradiated in the production of a liquid crystal aligning film can be specified based on the amount of polarized ultraviolet light that achieves ΔAmax.

In the production method of the present invention, the irradiation amount of the polarized ultraviolet rays irradiated to the coating film used in the present invention is preferably within a range of 1% to 70% of the amount of polarized ultraviolet rays that achieves ΔAmax, and more preferably 1% to 70%. 50% range. In the coating film used in the present invention, the irradiation amount of the polarized ultraviolet light in the range of 1% to 50% of the amount of the polarized ultraviolet light that achieves ΔAmax corresponds to the photosensitive group that the side chain type polymer film has. The amount of polarized ultraviolet rays in which the photocrosslinking reaction occurs in 0.1 mol % to 20 mol % of the whole.

As described above, in the production method of the present invention, in order to efficiently introduce anisotropy into the coating film, the above-mentioned suitable heating temperature may be determined based on the liquid crystal temperature range of the side chain type polymer. Therefore, for example, when the liquid crystal temperature range of the side chain type polymer used in the present invention is 100°C to 200°C, the heating temperature after polarized ultraviolet irradiation is desirably 90°C to 190°C. By setting in this way, larger anisotropy is imparted to the coating film used in the present invention.

By doing so, the liquid crystal display element provided by the present invention exhibits high reliability against external stress such as light and heat.

As described above, the substrate for a lateral electric field driven liquid crystal display element or a lateral electric field driven liquid crystal display element having the substrate produced by the method of the present invention is excellent in reliability, and can be suitably used for a large-screen and high-definition liquid crystal television Wait.

Hereinafter, the present invention will be described using examples, but the present invention is not limited to these examples.

Example

The methacrylic monomers MA1 and MA2, and the additives T1 and T2 used in the examples are shown below.

In addition, MA1 and M2 were synthesized as follows, respectively. That is, MA1 was synthesized by the synthesis method described in the patent document (WO2011-084546). MA2 was synthesized by the synthesis method described in the patent document (Japanese Patent Laid-Open No. 9-118717).

As the additives T1 (3-aminomethylpyridine) and T2 (1-(3-aminopropyl)imidazole), commercially available additives were used.

In addition, the abbreviation of the reagent used in this Example is shown below.

(Organic solvents)

THF: Tetrahydrofuran.

NMP: N-methyl-2-pyrrolidone.

BC: Butyl Cellosolve.

(polymerization initiator)

AIBN: 2,2'-azobisisobutyronitrile.

<Synthesis example 1>

MA1 (4.99 g, 15.0 mmol) and MA2 (4.60 g, 15.0 mmol) were dissolved in THF (88.5 g) and degassed with a diaphragm pump, and then AIBN (0.246 g, 1.5 mmol) was added and degassed again. Then, it was made to react at 50 degreeC for 30 hours, and the polymer solution of methacrylate was obtained. The polymer solution was added dropwise to diethyl ether (1000 ml), and the resulting precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40°C to obtain a methacrylate polymer powder.

NMP (54.0 g) was added to the obtained methacrylate polymer powder (6.0 g), and the mixture was stirred and dissolved at room temperature for 5 hours. To this solution, BC (40.0 g) was added and stirred to obtain a methacrylic polymer solution B1.

<Example 1>

To 5.0 g of the methacrylic polymer solution B1 obtained in Synthesis Example 1, 0.015 g of T1 was added, and the mixture was stirred at room temperature for 3 hours to obtain a polymer solution A1. This polymer solution is directly used as a liquid crystal aligning agent for forming a liquid crystal aligning film.

Using this liquid crystal aligning agent A1, production of a liquid crystal cell was performed according to the procedure shown below. The substrate was a glass substrate having a size of 30 mm×40 mm and a thickness of 0.7 mm, and a substrate in which a comb-shaped pixel electrode formed by patterning an ITO film was arranged was used.

The pixel electrode has a comb-like shape formed by arranging a plurality of "<"-shaped electrode elements having a curved center portion. The width of each electrode element in the width direction was 10 μm, and the interval between the electrode elements was 20 μm. The pixel electrode forming each pixel is formed by arranging a plurality of "<"-shaped electrode elements with a curved center portion, so that the shape of each pixel is not a rectangle, but has a curved center portion similar to the electrode element. Similar to the shape of the bold "<" word.

Each pixel is divided up and down with its central curved portion as a boundary, and has a first area on the upper side of the curved portion and a second area on the lower side. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements constituting the pixel electrodes thereof are different. That is, when the orientation treatment direction of the liquid crystal aligning film described later is used as a reference, in the first region of the pixel, the electrode element of the pixel electrode is formed at an angle of +15° (clockwise), and in the second region of the pixel, the electrode element of the pixel electrode is formed. Among them, the electrode elements of the pixel electrode are formed so as to present an angle of -15° (clockwise). That is, the first region and the second region of each pixel are configured such that the directions of the liquid crystal rotation in the substrate plane (plane switching) induced by applying a voltage between the pixel electrode and the counter electrode are opposite to each other.

<<Preparation of liquid crystal cell>>

The liquid crystal aligning agent A1 obtained in Example 1 was spin-coated on the prepared said board|substrate with an electrode. Next, it dried for 90 second with a 70 degreeC hotplate, and formed the liquid crystal aligning film with a film thickness of 100 nm. Next, after irradiating the ultraviolet-ray of 313 nm to the coating film surface at 20 mJ/cm< ² > via a polarizing plate, it heated with the hotplate of 150 degreeC for 10 minutes, and obtained the board|substrate with a liquid crystal aligning film. Moreover, as a counter substrate, a coating film was formed similarly to the glass substrate which did not form an electrode and has the columnar spacer of 4 micrometers in height, and the orientation process was performed. A sealant (manufactured by Kyoritsu Chemical Co., Ltd., XN-1500T) was printed on the liquid crystal aligning film of one substrate. Next, after affixing the other board|substrate so that a liquid crystal aligning film surface may oppose and an orientation direction may become 0 degree|times, a sealing compound is thermosetted, and the empty cell is produced. Liquid crystal MLC-2041 (manufactured by MERCK CORPORATION) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell including a liquid crystal display element having an IPS (In-Planes Switching) mode.

<<Evaluation of Voltage Holding Ratio (VHR)>>

Using the liquid crystal cell produced above, an AC voltage of 16 Vpp was applied at a frequency of 30 Hz for 168 hours in a constant temperature environment of 70°C. After that, the liquid crystal cell was left in a short-circuit state between the pixel electrode and the counter electrode, and left as it was at room temperature for 1 hour. A voltage of 5 V for 60 μs was applied to the obtained cell at a temperature of 70° C., the voltage after 16.67 ms was measured, and the degree to which the voltage could be maintained was calculated as a voltage retention ratio (VHR). In addition, the voltage holding ratio measuring apparatus VHR-1 by TOYO Corporation was used for the measurement of the voltage holding ratio.

The composition of the liquid crystal aligning agent of Example 1 is shown in Table 1 together with the result of VHR.

<Example 2>

A polymer solution A2 of Example 2 was obtained in the same manner as in Example 1 except that T2 was used instead of T1 in Example 1, a liquid crystal cell was prepared in the same manner as in Example 1, and the voltage holding ratio was measured. The results are shown in Table 1.

<Control 1>

In Control 1, a liquid crystal cell was prepared in the same manner as in Example 1, except that the polymer solution B1 obtained in Synthesis Example 1 was used as a liquid crystal aligning agent, and the voltage retention was measured. The results are shown in Table 1.

[Table 1]

Table 1. Composition and Voltage Holding Ratio VHR of Example 1 and Example 2 and Comparative Example

As can be seen from Table 1, the voltage holding ratio (VHR) was improved by using the additive in Examples 1 and 2 as compared with the control 1 in which the additive was not used.

<Afterimage evaluation>

The liquid crystal cell for IPS mode prepared in Example 1 was placed between two polarizing plates arranged so that the polarization axis was perpendicular, the backlight was turned on in a state where no voltage was applied, and the arrangement angle of the liquid crystal cell was adjusted so that light was transmitted. brightness is minimized. Then, the rotation angle when the liquid crystal cell is rotated from the darkest angle in the second region of the pixel to the darkest angle in the first region is calculated as the initial alignment azimuth angle. Next, an alternating voltage of 16 V _PP was applied at a frequency of 30 Hz for 168 hours in an oven at 60°C. After that, the liquid crystal cell was left in a short-circuit state between the pixel electrode and the counter electrode, and left as it was at room temperature for 1 hour. After being left to stand, the orientation azimuth angle was measured in the same manner, and the difference between the orientation azimuth angles before and after AC driving was calculated as an angle Δ (degree, deg.). The same measurement was performed in other Examples. As a result, in all the examples, the angle Δ was 0.1 or less. By irradiating the side chain type polymer film exhibiting liquid crystallinity with ultraviolet rays and heating within the temperature range of liquid crystal expression, liquid crystal alignment ability can be efficiently imparted to the entire polymer due to self-assembly, or even after long-term AC driving Shifts in orientation orientation are also hardly observable.

Description of reference numerals

figure 1

1 Side chain type polymer membrane

2. 2a side chain

figure 2

3 Side chain type polymer membrane

4. 4a side chain

image 3

5 Side chain type polymer membrane

6. 6a side chain

Figure 4

7 Side chain type polymer membrane

8. 8a side chain

Claims (12)

1. A polymer composition comprising: (A) a photosensitive side-chain polymer exhibiting liquid crystallinity in a temperature range of 100°C to 300°C; (B) an amine compound having one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; and (C) organic solvent, The component (A) has a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photoFries rearrangement, The (A) component has any one photosensitive side chain selected from the group consisting of the following formulae (1) to (6),

In the formula, A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O - or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them is optionally substituted by a halogen group; T is a single bond or an alkylene group with 1 to 12 carbon atoms, and the hydrogen atom bonded to them is optionally substituted by a halogen group; Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different substituents selected from these The 2 to 6 rings of the group are bonded through the bonding group B, and the hydrogen atoms bonded to them are independently optionally -COOR ₀ , -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms, or alkoxy group with 1 to 5 carbon atoms, in the formula, R ₀ represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms alkyl; Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and is bonded to them The hydrogen atoms of each are independently optionally replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. 5 alkoxy substitution; R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ ; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O- or -O-CO-CH=CH- , when the number of X reaches 2, X is optionally the same or different from each other; Cou represents coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bound to them are each independently optionally -NO ₂ , -CN, -CH=C(CN) ₂ , -CH= CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms, or alkoxy group with 1 to 5 carbon atoms; One of q1 and q2 is 1, and the other is 0; q3 is 0 or 1; P and Q are each independently a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof; Wherein, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side where -CH=CH- is bonded is an aromatic ring, and the number of P is 2 or more When , P is optionally the same or different from each other, and when the number of Q reaches 2 or more, Q is optionally the same or different from each other; l1 is 0 or 1; l2 is an integer from 0 to 2; When both l1 and l2 are 0, when T is a single bond, A also means a single bond; When l1 is 1, when T is a single bond, B also means a single bond; H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof, The (A) component has a compound selected from the group consisting of hydrocarbons, (meth)acrylates, itaconic acid esters, fumaric acid esters, maleic acid esters, α-methylene-γ-butyrolactone, styrene, ethylene A main chain composed of at least one of the group consisting of a base, maleimide, norbornene and siloxane, The component (A) has any one liquid crystalline side chain selected from the group consisting of the following formulae (21) to (31),

In the formula, A and B have the same definitions as above; Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and a bond Each of their hydrogen atoms is independently optionally substituted by -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; R ₃ represents hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, containing nitrogen heterocycle, alicyclic hydrocarbon with 5-8 carbons, alkyl with 1-12 carbons, or alkoxy with 1-12 carbons; One of q1 and q2 is 1, and the other is 0; l represents an integer from 1 to 12, m represents an integer from 0 to 2, where, in formulas (23) to (24), the sum of all m is 2 or more, and in formulas (25) to (26), all m The sum of is 1 or more, and m1, m2 and m3 each independently represent an integer from 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and alkyl or alkoxy; Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -, The component (B) is an amine compound represented by the following formula A-[1],

Y ₁₁ is a divalent organic group having one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms, and Y ₁₂ is a pyrrole ring, an imidazole ring , pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine a ring, a naphthyridine ring, a phenazine ring or a phthalazine ring, and the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₂ optionally has a halogen atom, The said (B) component is 0.01-10 mass parts in 100 mass parts of said polymer compositions. The composition according to claim 1, wherein the component (A) has any one photosensitive side chain selected from the group consisting of the following formulae (7) to (10),

In the formula, A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O - or -O-CO-CH=CH-; Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different substituents selected from these The 2 to 6 rings of the group are bonded through the bonding group B, and the hydrogen atoms bonded to them are independently optionally -COOR ₀ , -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms, or alkoxy group with 1 to 5 carbon atoms, in the formula, R ₀ represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms alkyl; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O- or -O-CO-CH=CH- , when the number of X reaches 2, X is optionally the same or different from each other; l represents an integer from 1 to 12; m represents an integer from 0 to 2, and m1 and m2 represent an integer from 1 to 3; n represents an integer from 0 to 12, wherein, when n=0, B is a single bond; Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and is bonded to them The hydrogen atoms of each are independently optionally replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. 5 alkoxy substitution; R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ . The composition according to claim 1, wherein the component (A) has any one photosensitive side chain selected from the group consisting of the following formulae (11) to (13),

In the formula, A each independently represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- or -O -CO-CH=CH-; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O- or -O-CO-CH=CH- , when the number of X reaches 2, X is optionally the same or different from each other; l represents an integer from 1 to 12, m represents an integer from 0 to 2, and m1 represents an integer from 1 to 3; R represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different substituents selected from these groups. A group in which 2 to 6 rings are bonded via a bonding group B, and the hydrogen atoms bonded to them are each independently optionally -COOR ₀ , -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1-5 carbons, or alkoxy group with 1-5 carbons, in the formula, R ₀ represents a hydrogen atom or an alkane with 1-5 carbons group, or R represents a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms. 4. The composition according to claim 1 or 2, wherein the component (A) has a photosensitive side chain represented by the following formula (14) or (15),

In the formula, A each independently represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- or -O -CO-CH=CH-; Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different substituents selected from these The 2 to 6 rings of the group are bonded through the bonding group B, and the hydrogen atoms bonded to them are independently optionally -COOR ₀ , -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms, or alkoxy group with 1 to 5 carbon atoms, in the formula, R ₀ represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms alkyl; l represents an integer from 1 to 12, and m1 and m2 represent an integer from 1 to 3. 5. The composition according to claim 1 or 2, wherein the component (A) has a photosensitive side chain represented by the following formula (16) or (17),

In the formula, A represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- or -O-CO- CH=CH-; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O- or -O-CO-CH=CH- , when the number of X reaches 2, X is optionally the same or different from each other; l represents an integer from 1 to 12, and m represents an integer from 0 to 2. 6. The composition according to claim 1 or 2, wherein the component (A) has any photosensitive side chain selected from the group consisting of the following formula (18) or (19),

In the formula, A and B each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- or -O-CO-CH=CH-; Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different substituents selected from these The 2 to 6 rings of the group are bonded through the bonding group B, and the hydrogen atoms bonded to them are independently optionally -COOR ₀ , -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms, or alkoxy group with 1 to 5 carbon atoms, in the formula, R ₀ represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms alkyl; One of q1 and q2 is 1, and the other is 0; l represents an integer from 1 to 12, and m1 and m2 represent an integer from 1 to 3; R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkane having 1 to 5 carbon atoms. Oxygen. 7. The composition according to claim 1 or 2, wherein the component (A) has a photosensitive side chain represented by the following formula (20),

In the formula, A represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- or -O-CO- CH=CH-; Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different substituents selected from these The 2 to 6 rings of the group are bonded through the bonding group B, and the hydrogen atoms bonded to them are independently optionally -COOR ₀ , -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms, or alkoxy group with 1 to 5 carbon atoms, in the formula, R ₀ represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms alkyl; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O- or -O-CO-CH=CH- , when the number of X reaches 2, X is optionally the same or different from each other; l represents an integer from 1 to 12, and m represents an integer from 0 to 2. 8. A method for producing a substrate having a liquid crystal aligning film for a transverse electric field-driven liquid crystal display element, comprising the steps of: [I] a step of applying the composition according to any one of claims 1 to 7 on a substrate having a conductive film for driving a transverse electric field to form a coating film; [II] A step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and [III] A step of heating the coating film obtained in [II]. 9 . A substrate having a liquid crystal aligning film for a transverse electric field-driven liquid crystal display element produced by the method of claim 8 . 10 . 10 . A lateral electric field driven liquid crystal display element comprising the substrate according to claim 9 . 11. A method for producing a transverse electric field driven liquid crystal display element, comprising the following steps to obtain the liquid crystal display element: the process of preparing the substrate according to claim 9, that is, the first substrate; The process of obtaining the 2nd board|substrate which has the following process [I'], [II'] and [III'] by having the following process [I'], [II'] and [III'] to obtain the liquid crystal aligning film to which the orientation control ability is provided; and [IV] A process for obtaining a liquid crystal display element by arranging the first substrate and the second substrate so as to face each other so that the liquid crystal aligning films of the first substrate and the second substrate face each other with the liquid crystal interposed therebetween; The steps [I'], [II'] and [III'] are: [I'] A step of coating a second substrate with a polymer composition containing: (A) photosensitivity that exhibits liquid crystallinity in a temperature range of 100°C to 300°C to form a coating film A side chain type polymer, (B) an amine compound having a primary amino group and a nitrogen-containing aromatic heterocycle in the molecule, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; and (C) Organic solvents; [II'] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I']; and [III'] A step of heating the coating film obtained in [II']. 12 . A lateral electric field driven liquid crystal display element manufactured by the method of claim 11 .

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