CN105518521A - Polymer composition and liquid crystal alignment film for in-plane-switching-type liquid crystal display element - Google Patents

Abstract

The present invention addresses the problem of providing a novel polymer composition for obtaining a liquid crystal alignment film for an in-plane-switching-type liquid crystal display element, the polymer composition having excellent image persistence characteristics and imparting alignment control performance with high efficiency, and a liquid crystal alignment film for an in-plane-switching-type liquid crystal display element that uses the polymer composition. The present invention solves the abovementioned problem by a polymer composition containing (A) a photosensitive side-chain macromolecule exhibiting liquid crystal properties in a predetermined temperature range, (B) polyurea, and (C) an organic solvent.

Description

Polymer composition and liquid crystal alignment film for lateral electric field driven liquid crystal display element

technical field

The present invention relates to a novel polymer composition, a liquid crystal alignment film for a transverse electric field-driven liquid crystal display element using the same, and a method for manufacturing a substrate having the alignment film. More specifically, it relates to a new method for producing a liquid crystal display element excellent in image sticking characteristics.

Background technique

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

That is, the liquid crystal aligning film is a constituent part of the liquid crystal display element, and is formed on the surfaces of the substrates sandwiching the liquid crystal that are in contact with the liquid crystal, and plays a role of orienting the liquid crystal in a specific direction between the substrates. Furthermore, in addition to the function of orienting the liquid crystal in a specific direction such as a direction parallel to the substrate, the liquid crystal aligning film may also require the function of controlling the pretilt angle of the liquid crystal. The ability (henceforth orientation control ability) of such a liquid crystal aligning film to control the liquid crystal orientation is provided by performing an orientation process to the organic film which comprises a liquid crystal aligning film.

Conventionally, a brush rubbing method is known as an orientation treatment method for a liquid crystal aligning film for providing an orientation control ability. The brushing method refers to a method of rubbing (brushing) the surface of an organic film such as polyvinyl alcohol, polyamide, polyimide, etc. on a substrate in a constant direction with a cloth such as cotton, nylon, or polyester. , so that the liquid crystal is aligned along the rubbing direction (brushing direction). This brushing method can easily realize a relatively stable liquid crystal alignment state, so it can be utilized in the conventional manufacturing process of liquid crystal display elements. Moreover, as an organic film used for a liquid crystal aligning film, the polyimide-type organic film excellent in reliability, such as heat resistance, and electric characteristic is mainly selected.

However, the rubbing method of rubbing the surface of the liquid crystal aligning film containing polyimide etc. has the problem of dust generation and static electricity generation. In addition, due to the high-definition of liquid crystal display elements in recent years, the unevenness caused by the electrodes on the corresponding substrate or the switching active elements for liquid crystal driving, it is impossible to rub the surface of the liquid crystal alignment film uniformly with a cloth, and it is impossible to achieve a uniform liquid crystal. orientation.

Therefore, as another orientation treatment method of the liquid crystal aligning film which does not perform brush rubbing, the photo-alignment method is actively studied.

There are various photo-alignment methods. Linearly polarized light or collimated light forms anisotropy in an organic film constituting a liquid crystal alignment film, and aligns liquid crystals based on the anisotropy.

As a main photo-alignment method, a decomposition-type photo-alignment method is known. In this method, for example, a polyimide film is irradiated with polarized ultraviolet rays and anisotropically decomposed by utilizing the polarization direction dependence of ultraviolet absorption of the molecular structure. And the liquid crystal is aligned by the polyimide which remained without decomposing (for example, refer patent document 1.).

In addition, photo-crosslinking-type and photo-isomerization-type photo-alignment methods are also known as other photo-alignment methods. In the photo-crosslinking photo-alignment method, for example, polyvinyl cinnamate is used to irradiate polarized ultraviolet rays to cause a dimerization reaction (crosslinking reaction) of double bond portions of two side chains parallel to the polarized light. And, the liquid crystal is aligned in a direction perpendicular to the polarization direction (for example, refer to Non-Patent Document 1). In the photoisomerization-type photo-alignment method, when a side chain-type polymer having azobenzene is used in the side chain, polarized ultraviolet rays are irradiated to cause an isomerization reaction of the azobenzene moiety in the side chain parallel to the polarized light, The liquid crystal is aligned in a direction perpendicular to the polarization direction (for example, refer to Non-Patent Document 2).

As in the above example, in the method of aligning the liquid crystal aligning film by the photo-alignment method, there is no need to perform brushing, and there is no need to worry about dust and static electricity. In addition, alignment treatment can be performed even on a substrate of a liquid crystal display element having irregularities on the surface, thus becoming an alignment treatment method for a liquid crystal alignment film suitable for an industrial production process.

prior art literature

patent documents

Patent Document 1: Japanese Patent No. 3893659

non-patent literature

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

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

Contents of the invention

The problem to be solved by the invention

As described above, compared with the brushing method that has been used industrially as an alignment treatment method for liquid crystal display elements, the photo-alignment method has a significant advantage because it does not require a brushing step. In addition, compared with the brushing method in which the orientation control ability by brushing is basically fixed, the photo-alignment method can control the orientation control ability by changing the irradiation amount of polarized light. However, when the photo-alignment method is intended to achieve the same degree of alignment control ability as that achieved by the brush rubbing 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 with ultraviolet light emitted from a high-pressure mercury lamp with a power of 500 W for 60 minutes, and a long time and a large amount of ultraviolet irradiation are required. In addition, in the case of a dimerization type or a photoisomerization type photoalignment method, a large amount of ultraviolet irradiation of about several J (joules) to several tens of J may be required. Furthermore, in the case of photo-crosslinking type or photo-isomerization type photo-alignment methods, the orientation thermal stability and photostability of the liquid crystal are poor, so when it is made into a liquid crystal display element, there is a concern that poor alignment and display sticking may occur. In particular, in a transverse electric field drive type liquid crystal display element, liquid crystal molecules are switched in-plane, so liquid crystal orientation shift after liquid crystal driving is likely to occur, and display sticking due to AC driving is regarded as a significant problem.

Therefore, in the photo-alignment method, high efficiency of alignment treatment and stable liquid crystal alignment are required, and a liquid crystal aligning film and a liquid crystal aligning agent capable of efficiently imparting high alignment control ability to a liquid crystal aligning film are required.

The object of the present invention is to provide a novel polymer composition, a liquid crystal alignment film for a transverse electric field driven liquid crystal display element using the same, a substrate having the alignment film, and a transverse electric field driven liquid crystal display element having the substrate The said polymer composition can provide the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements which was provided with orientation control ability with high efficiency, and was excellent in image sticking characteristics. Another object of this invention is to provide the manufacturing method of the liquid crystal aligning film which has an improved voltage retention rate, and the board|substrate which has this liquid crystal aligning film even by low-temperature baking.

solutions to problems

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

<1> a polymer composition, especially a polymer composition for the manufacture of a liquid crystal alignment film for a transverse electric field driven type liquid crystal display element, which contains:

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

(B) polyurea, and

(C) Organic solvents.

<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 polyurea as the (B) component may be obtained by polymerizing a diisocyanate component and a diamine component.

<4> In the above <1> or <2>, the polyurea as the (B) component can be obtained by making a diisocyanate component, a carboxylic acid derivative having two or more carboxylic acid moieties and/or its anhydride, and a diamine The components are obtained by polymerization reaction.

<5> In the above <3> or <4>, the diisocyanate component may be an aromatic diisocyanate and/or an aliphatic diisocyanate.

<6> In any one of said <1>-<5>, (A) component may have any one photosensitive side chain selected 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 with 1 to 12 carbon atoms, and the hydrogen atoms bonded to them are optionally substituted by halogen groups;

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

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

_Y2 is a group selected from the group consisting of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and is bonded to them The hydrogen atoms in are independently optionally replaced by -NO ₂ , -CN, -CH═C(CN) ₂ , -CH═CH-CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkyl group with 1 to 5 carbons Alkoxy substitution;

R represents a hydroxyl group, an alkoxy group with 1 to 6 carbons, or the same definition as _Y1 ;

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 bonded to them are each independently optionally replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH= Substituted by CH-CN, halogen group, alkyl group with 1 to 5 carbons or alkoxy group with 1 to 5 carbons;

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 divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons with 5 to 8 carbon atoms, and combinations thereof; Among them, 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 represents a single bond;

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

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

<7> In any one of said <1>-<5>, (A) component may have any one photosensitive side chain selected 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, 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).

<8> In any one of said <1>-<5>, (A) component may have any one photosensitive side chain selected 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.

<9> In any one of said <1>-<5>, (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.

<10> In any one of said <1>-<5>, (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.

<11> In any one of said <1>-<5>, (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 with 1 to 5 carbons, or an alkoxy group with 1 to 5 carbons base.

<12> In any one of said <1>-<5>, (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.

<13> In any one of the above <1> to <12>, the component (A) may have any liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).

In the formula, A and B have the same definition as above;

_Y3 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 heterocycle, and an alicyclic hydrocarbon with a carbon number of 5 to 8, and combinations thereof, the bond The hydrogen atoms associated with them are each independently optionally substituted by -NO ₂ , -CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkoxy group with 1 to 5 carbons;

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 Azacyclic rings, alicyclic hydrocarbons with 5 to 8 carbons, alkyl groups with 1 to 12 carbons or alkoxy groups with 1 to 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, wherein, in formulas (23) to (24), the sum of all m is 2 or more; in formulas (25) to (26), all m The sum of is 1 or more, and m1, m2 and m3 each independently represent an integer of 1 to 3;

R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and an alicyclic hydrocarbon with 5 to 8 carbons, and Alkyl or alkoxy;

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

<14> a kind of manufacture method that has the substrate of transverse electric field driven type liquid crystal display element liquid crystal aligning film, it obtains the aforementioned liquid crystal aligning film that has been endowed with alignment control ability by possessing following procedure:

[I] coating any composition of the above <1> to <13> 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].

<15> The board|substrate which has the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements manufactured by the method of said <14>.

<16> A lateral electric field driven liquid crystal display element comprising the substrate of <15> above.

<17> A method of manufacturing a transverse electric field driven liquid crystal display element, which obtains the liquid crystal display element by having the following steps:

A step of preparing the substrate (first substrate) of <15> above;

A step of obtaining a second substrate having a liquid crystal aligning film that is provided with the following steps [I'], [II'], and [III'] to obtain a liquid crystal aligning film endowed with orientation control ability; and

[IV] The process of arranging the first substrate and the second substrate opposite to each other so that the liquid crystal alignment films of the first substrate and the second substrate face each other through the liquid crystal to obtain a liquid crystal display element;

Described operation [I '], [II '] and [III '] are:

[I'] A step of forming a coating film by coating a polymer composition containing: (A) a photosensitive side chain-type polymer exhibiting liquid crystallinity in a specific temperature range; molecule, (B) polyurea and (C) 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'].

<18> A lateral electric field driven liquid crystal display element manufactured by the above-mentioned <17>.

Moreover, the following invention was found as another aspect.

<P1> A method of manufacturing a substrate having a liquid crystal alignment film for a transverse electric field-driven type liquid crystal display element, which obtains the aforementioned liquid crystal alignment film endowed with orientation control ability by possessing the following steps:

[I] A process of coating a polymer composition on a substrate having a conductive film for driving a transverse electric field to form a coating film, the polymer composition containing: (A) exhibiting liquid crystallinity in a specific temperature range Photosensitive side chain polymer, (B) polyurea and (C) 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].

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

<P3> In said <P1> or <P2>, the polyurea which is (B) component can be obtained by polymerizing a diisocyanate component and a diamine component.

<P4> In <P3> above, the diisocyanate component may be an aromatic diisocyanate and/or an aliphatic diisocyanate.

<P5> In any one of <P1> to <P4> above, the component (A) may have any one photosensitive side chain selected from the group consisting of the following formulas (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 with 1 to 12 carbon atoms, and the hydrogen atoms bonded to them are optionally substituted by halogen groups;

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

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

_Y2 is a group selected from the group consisting of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and is bonded to them The hydrogen atoms in are independently optionally replaced by -NO ₂ , -CN, -CH═C(CN) ₂ , -CH═CH-CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkyl group with 1 to 5 carbons Alkoxy substitution;

R represents a hydroxyl group, an alkoxy group with 1 to 6 carbons, or the same definition as _Y1 ;

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 bonded to them are each independently optionally replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH= Substituted by CH-CN, halogen group, alkyl group with 1 to 5 carbons or alkoxy group with 1 to 5 carbons;

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

q3 is 0 or 1;

P and Q are each independently a single bond, 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 group. Wherein, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side where -CH=CH- is bonded to is an aromatic ring;

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

<P6> In any one of <P1> to <P4> above, the component (A) may have any one photosensitive side chain selected from the group consisting of the following formulas (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, 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).

<P7> In any one of said <P1>-<P4>, (A) component may have any one photosensitive side chain selected from the group which consists of following formula (11)-(13).

In the formula, A, X, l, m, m2 and R have the same definitions as above.

<P8> In any one of said <P1>-<P4>, (A) component may have the photosensitive side chain represented by following formula (14) or (15).

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

<P9> In any one of said <P1>-<P4>, (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.

<P10> In any one of said <P1>-<P4>, (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 with 1 to 5 carbons, or an alkoxy group with 1 to 5 carbons base.

<P11> In any one of said <P1>-<P4>, (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.

<P12> In any one of <P1> to <P11> above, the component (A) may have any liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).

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

_Y3 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 heterocycle, and an alicyclic hydrocarbon with a carbon number of 5 to 8, and combinations thereof, the bond The hydrogen atoms associated with them are each independently optionally substituted by -NO ₂ , -CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkoxy group with 1 to 5 carbons;

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 Azacyclic rings, alicyclic hydrocarbons with 5 to 8 carbons, alkyl groups with 1 to 12 carbons or alkoxy groups with 1 to 12 carbons;

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

R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and an alicyclic hydrocarbon with 5 to 8 carbons, and Alkyl or alkoxy;

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

<P13> The board|substrate which has the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements manufactured by any one of said <P1>-<P12>.

<P14> A lateral electric field driven liquid crystal display element having the substrate of the above-mentioned <P13>.

<P15> A method for manufacturing a transverse electric field driven liquid crystal display element, which obtains the liquid crystal display element by having the following steps:

The process of preparing the substrate (first substrate) of <P13> above;

A step of obtaining a second substrate having a liquid crystal aligning film that is provided with the following steps [I'], [II'], and [III'] to obtain a liquid crystal aligning film endowed with orientation control ability; and

[IV] The process of arranging the first substrate and the second substrate facing each other in such a way that the liquid crystal alignment films of the first substrate and the second substrate face each other through the liquid crystal, thereby obtaining a liquid crystal display element,

Described operation [I '], [II '] and [III '] are:

[I'] A step of forming a coating film by coating a polymer composition containing: (A) a photosensitive side chain-type polymer exhibiting liquid crystallinity in a specific temperature range to form a coating film; molecule, (B) polyurea and (C) 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'].

<P16> A transverse electric field driven liquid crystal display element manufactured by the above <P15>.

<P17> A composition for producing a liquid crystal alignment film for a transverse electric field driven liquid crystal display element, which contains: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, (B) a polymer Urea and (C) an organic solvent.

<P18> In said <P17>, the polyurea which is (B) component can be obtained by polymerizing a diisocyanate component and a diamine component.

<P19> In the above <P18>, the diisocyanate component may be an aromatic diisocyanate and/or an aliphatic diisocyanate.

The effect of the invention

According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film for a lateral electric field-driven liquid crystal display element, which is provided with orientation control ability at high efficiency and excellent in image sticking characteristics, and a lateral electric field driven liquid crystal display element having the substrate.

The lateral electric field driven liquid crystal display element manufactured by the method of the present invention is efficiently provided with orientation control capability, and therefore, the display characteristics will not be impaired even if it is driven continuously for a long time.

In addition, in the present invention, by making the polymer composition contain polyurea as the component (B), it is possible to provide a transverse electric field-driven liquid crystal element having an excellent voltage retention even when fired at a low temperature, and a liquid crystal used for the element. Alignment film. That is, according to the present invention, even if residual solvents (N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, etc. belonging to high-boiling point solvents) remain in low-temperature firing, it is possible to obtain The higher voltage retention rate of the alignment film.

Description of drawings

Fig. 1 is a diagram schematically illustrating an example of the anisotropy introducing treatment in the manufacturing method of the liquid crystal aligning film used in the present invention, and the photosensitive side chain uses a crosslinkable organic group and introduces anisotropy hour graph.

Fig. 2 is a diagram schematically illustrating an example of anisotropy introducing treatment in a method for producing a liquid crystal alignment film used in the present invention, and is an anisotropy introduced by using a crosslinkable organic group as a photosensitive side chain. big picture.

Fig. 3 is a diagram schematically illustrating an example of anisotropy introducing treatment in the method for producing a liquid crystal alignment film used in the present invention, and the photosensitive side chain uses an organic compound that undergoes Fries rearrangement or isomerization. group and the graph of the introduced anisotropy hours.

Fig. 4 is a diagram schematically illustrating an example of the anisotropy introducing treatment in the manufacturing method of the liquid crystal aligning film used in the present invention, and the photosensitive side chain uses an organic compound that undergoes Fries rearrangement or isomerization. group and the introduced anisotropy is large.

detailed description

As a result of intensive studies, the inventors of the present invention obtained the following knowledge and completed the present invention.

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) capable of exhibiting liquid crystallinity, and the coating film obtained by using the above polymer composition is A film with a photosensitive side chain type polymer capable of exhibiting liquid crystallinity. The coating film does not need to be brushed and rubbed, but is oriented by polarized light irradiation. And after polarized light irradiation, it becomes the coating film (henceforth a liquid crystal aligning film) provided with orientation control ability through the process of heating this side chain type polymer film. At this time, the minute anisotropy expressed by the irradiation of polarized light becomes a driving force, and the liquid crystalline side chain polymer itself is efficiently reoriented by self-assembly. As a result, efficient orientation process can be realizable as a liquid crystal aligning film, and the liquid crystal aligning film provided with high orientation control ability is obtained.

Moreover, in the polymer composition of this invention, polyurea is used as (B) component in addition to the side chain type polymer which is (A) component, and the organic solvent which is (C) component. Thereby, even if it bakes at low temperature, it is unexpected that the voltage retention rate of a liquid crystal aligning film improves significantly. In particular, the above effects are increased by using a specific substance as polyurea. The inventors of the present invention consider that these phenomena are caused by adding the (B) component. In addition, the (A) component and the (B) component exert interaction, thus dramatically improving the desired effect (notes to be explained) Yes, these include the inventor's knowledge of the mechanism of the present invention and do not limit the present invention).

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

<Manufacturing Method of Substrate Having Liquid Crystal Alignment Film> and <Manufacturing Method of Liquid Crystal Display Element>

The manufacturing method of the substrate with liquid crystal alignment film of the present invention has following steps:

[I] A process of coating a polymer composition on a substrate having a conductive film for driving a transverse electric field to form a coating film, the polymer composition containing: (A) exhibiting liquid crystallinity in a specific temperature range Photosensitive side chain polymer, (B) polyurea and (C) 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].

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

Also, by preparing a second substrate in addition to the substrate (first substrate) obtained above, a transverse electric field drive type liquid crystal display element can be obtained.

For the second substrate, in addition to using a substrate without a transverse electric field driving conductive film instead of a substrate with a transverse electric field driving conductive film, by using the above steps [I] to [III] (due to using no transverse electric field driving For the sake of convenience, it may be simply referred to as steps [I'] to [III'] in this application), and a second substrate having a liquid crystal aligning film endowed with orientation control ability can be obtained.

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

[IV] A step of arranging the first substrate and the second substrate obtained above so that the liquid crystal aligning films of the first substrate and the second substrate face each other with the liquid crystal interposed therebetween, to obtain a liquid crystal display element. Thereby, a transverse electric field drive type 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 is coated on a substrate having a conductive film for driving a transverse electric field to form a coating film. The polymer composition contains: a photosensitive side that exhibits liquid crystallinity in a specific temperature range Chain polymers, polyureas and organic solvents.

<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 highly transparent substrate. In this case, it is not particularly limited, and plastic substrates such as glass substrates, acrylic substrates, and polycarbonate substrates can be used.

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

<Conductive film for lateral electric field drive>

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

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

Moreover, in the case of a reflective liquid crystal display element, although the material etc. which reflect light, such as aluminum, are mentioned as a conductive film, it is not limited to these.

As a method of forming a conductive film on a substrate, conventionally known methods can be used.

<Polymer composition>

Coating a polymer composition on a substrate having a conductive film for driving a transverse electric field, especially coating a polymer composition on a conductive film.

The polymer composition used in the production method of the present invention contains: (A) a photosensitive side-chain polymer exhibiting liquid crystallinity in a specific temperature range; (B) polyurea; and (C) an organic solvent.

<<(A) Side chain polymer>>

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

(A) It is sufficient that the side chain type polymer reacts with light in the wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in the temperature range of 100°C to 300°C.

(A) The side chain type polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm.

(A) The side chain type polymer preferably has a mesogen group in order to exhibit liquid crystallinity in the temperature range of 100°C to 300°C.

(A) A photosensitive side chain is bonded to the main chain of the side chain type polymer, and can undergo crosslinking reaction, isomerization reaction, or photofries rearrangement in response to light. The photosensitive side chain structure is not particularly limited, but is preferably a structure that undergoes a crosslinking reaction or photo-Friesian rearrangement in response to light, more preferably a structure that undergoes a crosslinking reaction. In this case, even when exposed to external stress such as heat, the achieved orientation control ability can be stably maintained for a long period of time. The structure of the photosensitive side chain type polymer capable of expressing 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 the side chain type polymer is used as a liquid crystal aligning film, stable liquid crystal orientation can be obtained.

The structure of this polymer can be made into the following structure, for example: it has a main chain and a side chain bonded thereto, and the side chain has a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, an azobenzene Mesogen components such as bases and photosensitive groups that are bonded to the front end in response to light and undergo crosslinking reactions and isomerization reactions; have a main chain and side chains bonded to it. The original component also undergoes a photofries rearrangement of the phenylbenzoate group.

As a more specific example of the structure of a photosensitive side chain type polymer capable of exhibiting liquid crystallinity, it is preferably a structure having a main chain and a side chain consisting of a main chain selected from hydrocarbons, (meth)acrylates, Radical polymerizable groups such as itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and At least one of the group consisting of siloxanes, wherein the side chain contains at least one of the following formulas (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 with 1 to 12 carbon atoms, and the hydrogen atoms bonded to them are optionally substituted by halogen groups;

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

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

_Y2 is a group selected from the group consisting of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and is bonded to them The hydrogen atoms in are independently optionally replaced by -NO ₂ , -CN, -CH═C(CN) ₂ , -CH═CH-CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkyl group with 1 to 5 carbons Alkoxy substitution;

R represents a hydroxyl group, an alkoxy group with 1 to 6 carbons, or the same definition as _Y1 ;

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 bonded to them are each independently optionally replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH= Substituted by CH-CN, halogen group, alkyl group with 1 to 5 carbons or alkoxy group with 1 to 5 carbons;

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 divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons with 5 to 8 carbon atoms, and combinations thereof; Among them, 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 represents a single bond;

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

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

The side chain may be any photosensitive side chain selected from the group consisting of the following formulas (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, 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 formulas (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, Y1, 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 with 1 to 5 carbons, or an alkoxy group with 1 to 5 carbons base.

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 liquid crystal side chain selected from the group consisting of the following formulas (21) to (31).

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

_Y3 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 heterocycle, and an alicyclic hydrocarbon with a carbon number of 5 to 8, and combinations thereof, the bond The hydrogen atoms associated with them are each independently optionally substituted by -NO ₂ , -CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkoxy group with 1 to 5 carbons;

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 Azacyclic rings, alicyclic hydrocarbons with 5 to 8 carbons, alkyl groups with 1 to 12 carbons or alkoxy groups with 1 to 12 carbons;

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

R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and an alicyclic hydrocarbon with 5 to 8 carbons, and Alkyl or alkoxy;

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

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

The above-mentioned photosensitive side chain type polymer capable of expressing liquid crystallinity can be obtained by polymerizing a photoreactive side chain monomer having the above-mentioned photosensitive side chain and a liquid crystalline 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 at a side chain site 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 a photoreactive side chain monomer, it is preferably a structure having a polymerizable group and a photosensitive side chain: the polymerizable group is selected from hydrocarbons, (meth)acrylates, itacron Radical polymerizable groups such as ester, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and siloxane at least one of the group consisting of alkanes; and, the photosensitive side chain includes at least one of the above-mentioned formulas (1) to (6), preferably, for example, includes the above-mentioned formulas (7) to (10) At least one photosensitive side chain, a photosensitive side chain comprising at least one of the above formulas (11) to (13), a photosensitive side chain represented by the above formula (14) or (15), the above formula ( 16) or the photosensitive side chain represented by (17), the photosensitive side chain represented by said formula (18) or (19), the photosensitive side chain represented by said formula (20).

In the present application, novel compounds (1) to (11) represented by the following formulas (1) to (11) are provided as photoreactive and/or liquid crystalline side chain monomers.

In the formula, R represents a hydrogen atom or a methyl group; S represents an alkylene group with 2 to 10 carbons; R ¹⁰ represents Br or CN; S represents an alkylene group with 2 to 10 carbons; u represents 0 or 1; represents 2-pyridyl, 3-pyridyl or 4-pyridyl.

In addition, in the present application, novel compounds (12) to (17) represented by the following formulas (12) to (17) are provided as photoreactive and/or liquid crystalline side chain monomers.

In formulas (12) to (17), R represents a hydrogen atom or a methyl group; S represents an alkylene group with 2 to 10 carbons; v represents 1 or 2; u represents 0 or 1 (wherein, in formula (12), S represents an alkylene group having 2 to 9 carbon atoms, and in formula (14), S represents an alkylene group having 1 to 10 carbon atoms).

[Liquid crystal side chain monomer]

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

The mesogen group in the side chain may be a mesogen structure alone such as biphenyl or phenyl benzoate, or a mesogen structure formed by hydrogen bonding of side chains such as benzoic acid. group. As a mesogen group which a side chain has, it is preferable to have the following structure.

As a more specific example of a liquid crystal side chain monomer, it is preferably a structure having a polymerizable group selected from hydrocarbons, (meth)acrylates, itaconate esters, and side chains as follows: Fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other free radical polymerizable groups and siloxane At least one of the above-mentioned side chains comprises at least one of the above-mentioned formulas (21) to (31).

(A) The side chain type polymer can be obtained by the polymerization reaction of the photoreactive side chain monomer which expresses liquid crystallinity mentioned above. In addition, it can be obtained by copolymerization of a photoreactive side chain monomer not expressing liquid crystallinity and a liquid crystalline side chain monomer, or copolymerization of a photoreactive side chain monomer expressing liquid crystallinity and a liquid crystalline side chain monomer. Furthermore, it can be copolymerized with other monomers within the range which does not impair the ability to express liquid crystallinity.

Examples of other monomers include industrially 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, and vinyl compounds.

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

Examples of acrylate compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracenylmethyl acrylate, phenyl acrylate, acrylic acid 2,2,2 - 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-tricycloacrylate Decyl ester, and 8-ethyl-8-tricyclodecanyl acrylate, etc.

Examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, methyl 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-tricyclodecanyl methacrylate, and 8-methacrylic acid -Ethyl-8-tricyclodecanyl 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 butyl)methyl ester.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

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

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

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

As the polymerization initiator for radical polymerization, known compounds such as radical polymerization initiators and reversible addition-fragmentation chain transfer (RAFT) polymerization reagents can be used.

The thermal radical 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, dilaurate acyl peroxides, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peroxyesters (tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, peroxide Oxidation of tert-amyl 2-ethylcyclohexane, 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 use it in combination of 2 or more types.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, Isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2- Methyl-4'-isopropyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2 ,2-Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-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'-di(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(tri 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 )-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 '-Bimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecane ylcarbazole, 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'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetrakis(tert-hexylperoxy ylcarbonyl) benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(tert-butylperoxycarbonyl)benzophenone, 3,4'-bis(methoxy ylcarbonyl)-4,3'-bis(tert-butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-bis(tert-butylperoxy carbonyl)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 emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, solution polymerization, and the like can be used.

The organic solvent used in the polymerization reaction of the photosensitive side-chain type polymer capable of expressing liquid crystallinity is not particularly limited as long as it dissolves the produced polymer. 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, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylamylketone, Methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate Ester, 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 mono 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, three 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-ethoxypropionate, 3-methoxypropionate, 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-dimethylpropanamide, etc.

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

In addition, in the radical polymerization, oxygen in the organic solvent hinders 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 arbitrary temperature of 30 degreeC - 150 degreeC, Preferably it is the range of 50 degreeC - 100 degreeC. In addition, the reaction can be carried out at any concentration. When the concentration is too low, it is difficult to obtain a high-molecular-weight polymer. When the concentration is too high, the viscosity of the reaction solution becomes too high and it is difficult to stir uniformly. Therefore, the monomer concentration is preferably 1 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 becomes small, and when the ratio of the radical polymerization initiator to the monomer is small, the molecular weight of the obtained polymer becomes smaller. Therefore, the ratio of the radical initiator is preferably 0.1 mol% to 10 mol% with respect to the polymerizable monomer. In addition, various monomer components, solvents, initiators, etc. may be added during polymerization.

[Recycling of polymers]

When recovering the produced polymer from the reaction solution of the photosensitive side chain type polymer capable of expressing liquid crystallinity obtained by the above reaction, the reaction solution may be poured into a poor solvent to precipitate the polymer. Examples of poor solvents used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, etc. . The polymer deposited in the poor solvent and precipitated can be collected by filtration and then dried at normal temperature or under reduced pressure at normal temperature or with heat. In addition, when the operation of redissolving the precipitated polymer in an organic solvent and reprecipitating it 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, when considering the strength of the obtained coating film, the workability when forming the coating film, and the uniformity of the coating film, the GPC (GelPermeationChromatography, gel permeation chromatography) method is used. The measured weight average molecular weight is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000.

[Preparation of polymer composition]

It is preferable to prepare the polymer composition used for this invention in the form of a coating liquid, and to suitably form a liquid crystal aligning film. That is, the polymer composition used in the present invention is preferably prepared in the form of a solution in which a resin component for forming a resin coating is dissolved in an organic solvent. Here, the resin component refers to a resin component containing the above-mentioned photosensitive side chain type polymer capable of expressing liquid crystallinity. 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, particularly preferably 3% by mass to 10% by mass.

In the polymer composition of this embodiment, the above-mentioned resin components may all be the above-mentioned photosensitive side-chain polymers capable of exhibiting liquid crystallinity, and may be mixed with other polymers within the range that does not impair liquid crystal expressiveness and photosensitivity. other polymers. In this case, the content of other polymers in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.

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

<<(B)Ingredient>>

The polymer composition used in the present invention contains polyurea as the (B) component. (B) The component is preferably a polymer obtained by polymerizing a diisocyanate component and a diamine component.

<<<Diisocyanate component>>>

As a diisocyanate component which is a raw material of (B) component, an aromatic diisocyanate, an aliphatic diisocyanate, etc. are mentioned, for example. The diisocyanate component is preferably an aromatic diisocyanate or an aliphatic diisocyanate.

Here, the aromatic diisocyanate means that the R group of the diisocyanate structure (O=C=N-R-N=C=O) includes an aromatic ring-containing structure. In addition, the aliphatic diisocyanate means that the R group of the aforementioned isocyanate structure contains a cyclic or acyclic aliphatic structure.

Specific examples of aromatic diisocyanate include ortho-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate (for example, 2,4-toluene diisocyanate), 1,4-diisocyanate Isocyanate-2-methoxybenzene, 2,5-diisocyanate xylenes, 2,2'-bis(4-diisocyanatophenyl)propane, 4,4'-diisocyanate Diphenylmethane, 4,4'-diisocyanate diphenyl ether, 4,4'-diisocyanate diphenyl sulfone, 3,3'-diisocyanate diphenyl sulfone, 2,2' - Benzophenone diisocyanate and the like. As an aromatic diisocyanate, 2, 4- toluene diisocyanate is mentioned preferably. Specific examples of aliphatic diisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, tetramethylethylene diisocyanate, and the like. As aliphatic diisocyanate, Preferably, isophorone diisocyanate is mentioned. Among them, isophorone diisocyanate and toluene 2,4-diisocyanate are preferable from the viewpoint of polymerization reactivity and voltage retention, and furthermore, from the viewpoint of availability, polymerization reactivity, and voltage retention, Preferred is isophorone diisocyanate.

<<<Diamine composition>>>

As a diamine component which is a raw material of (B) component, the following alicyclic diamine, aromatic diamine, heterocyclic diamine, aliphatic diamine, and the diamine containing a urea bond are mentioned, for example.

Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminocyclohexane, Amino-3,3'-dimethyldicyclohexylamine, isophoronediamine, etc.

Examples of aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-di Amino-2,5-dichlorobenzene, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4 '-Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldi Phenylmethane, 2,2'-diaminostilbene, 4,4'-diaminostilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,5-bis (4-aminophenoxy)benzoic acid, 4,4'-bis(4-aminophenoxy)bibenzyl, 2,2-bis[(4-aminophenoxy)methyl]propane, 2,2 -Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl] Oxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, 1,1-bis(4-aminophenyl)cyclohexane, α,α'-bis(4- Aminophenyl)-1,4-diisopropylbenzene, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis (4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrene, 1,6-diaminopyrene, 1,8-diaminopyrene, 2,7-diaminofluorene, 1,3-bis(4-amino Phenyl)tetramethyldisiloxane, benzidine, 2,2'-dimethylbenzidine, 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminobenzene base) propane, 1,4-bis(4-aminophenyl)butane, 1,5-bis(4-aminophenyl)pentane, 1,6-bis(4-aminophenyl)hexane, 1 ,7-bis(4-aminophenyl)heptane, 1,8-bis(4-aminophenyl)octane, 1,9-bis(4-aminophenyl)nonane, 1,10-bis( 4-aminophenyl)decane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy) Oxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy) ) octane, 1,9-bis(4- Aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, bis(4-aminophenyl)propane-1,3-dioate, bis(4-aminophenyl) Butane-1,4-dioate, bis(4-aminophenyl)pentane-1,5-dioate, bis(4-aminophenyl)hexane-1,6-dioate, di (4-aminophenyl)heptane-1,7-dioate, bis(4-aminophenyl)octane-1,8-dioate, bis(4-aminophenyl)nonane-1, 9-diacid ester, bis(4-aminophenyl)decane-1,10-diacid ester, 1,3-bis[4-(4-aminophenoxy)phenoxy]propane, 1,4 -Bis[4-(4-aminophenoxy)phenoxy]butane, 1,5-bis[4-(4-aminophenoxy)phenoxy]pentane, 1,6-bis[4 -(4-aminophenoxy)phenoxy]hexane, 1,7-bis[4-(4-aminophenoxy)phenoxy]heptane, 1,8-bis[4-(4- Aminophenoxy)phenoxy]octane, 1,9-bis[4-(4-aminophenoxy)phenoxy]nonane, 1,10-bis[4-(4-aminophenoxy ) phenoxy] decane, etc.

As an example of an aromatic-aliphatic diamine, the diamine etc. which are represented by following formula [DAM] are mentioned.

(where,

Ar represents a benzene ring or a naphthalene ring,

R ₁ is an alkylene group with 1 to 5 carbon atoms, and

R ₂ is a hydrogen atom or a methyl group. )

Specific examples of aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminobenzylamine, -Aminophenethylamine, 4-aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3-(3-aminopropyl)aniline, 4- (3-aminopropyl)aniline, 3-(3-methylaminopropyl)aniline, 4-(3-methylaminopropyl)aniline, 3-(4-aminobutyl)aniline, 4-(4-amino Butyl)aniline, 3-(4-methylaminobutyl)aniline, 4-(4-methylaminobutyl)aniline, 3-(5-aminopentyl)aniline, 4-(5-aminopentyl)aniline , 3-(5-methylaminopentyl)aniline, 4-(5-methylaminopentyl)aniline, 2-(6-aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2 -(6-aminonaphthyl)ethylamine, 3-(6-aminonaphthyl)ethylamine, etc.

Examples of heterocyclic diamines include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diamino Dibenzofuran, 3,6-diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis(4-aminophenyl)-1 , 3,4-Oxadiazole and so on.

Examples of aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6- Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2, 2-Dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4, 4-Dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylnonane, 1,12-diaminododecane, 1,18- Diaminooctadecane, 1,2-bis(3-aminopropoxy)ethane, etc.

Examples of urea bond-containing diamines include N,N'-bis(4-aminophenethyl)urea and the like.

Furthermore, in (B) component, as a diamine component which polymerizes with a diisocyanate component, the diamine which has a side chain for vertical alignment can be contained in the range which does not impair the effect of this invention.

Moreover, the diamine component in (B) component may contain the following diamine.

(In the formula, m and n are respectively an integer of 1 to 11, m+n is an integer of 2 to 12, h is an integer of 1 to 3, and j is an integer of 0 to 3.)

Introduction of these diamines is advantageous for further improving the voltage retention (it is also called VHR) of the liquid crystal display element using the liquid crystal aligning film formed from the liquid crystal aligning agent of this invention. These diamines are preferable from the viewpoint of being excellent in the effect of reducing the accumulated charge of such a liquid crystal display element.

Moreover, as a diamine component in (B) component, the diaminosiloxane etc. which are represented by the following formula are also mentioned.

(In the formula, m is an integer of 1 to 10.)

The diamine components in these (B) components can be used individually by 1 type or in combination of 2 or more types according to characteristics, such as the liquid crystal orientation at the time of making a liquid crystal aligning film, a voltage retention characteristic, and accumulated electric charge. The mixing ratio at this time is not limited.

In addition, regarding the molecular weight of the polyurea as the (B) component, when considering the strength of the obtained liquid crystal aligning film, the workability when forming the liquid crystal aligning film, and the uniformity of the liquid crystal aligning film, GPC (GelPermeationChromatography, gel permeation chromatography) The weight average molecular weight measured by the method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

When obtaining the polymer of the said (B) component by the polymerization reaction of the diisocyanate component of each raw material, and a diamine component, a well-known synthesis method can be used. Generally, it is a method of making a diisocyanate component and a diamine component react in an organic solvent. The reaction of a diisocyanate component and a diamine component is advantageous in that it is relatively easy to perform in an organic solvent and does not generate a by-product.

The organic solvent used for the reaction of the diisocyanate component and the diamine component is not particularly limited as long as it dissolves the polyurea produced.

Specific examples thereof are listed below.

Examples of organic solvents usable here include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, gamma-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentyl Ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve Acetate, Butyl Carbitol, Ethyl Carbitol, Ethylene Glycol, Ethylene Glycol Monoacetate, Ethylene Glycol Monoisopropyl Ether, 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, di Propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate , tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, Methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, lactic acid Ethyl acetate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate Ethyl ester, ethyl 3-methoxypropionate, 3-ethoxypropionate, 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, di Glyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropane Amide, 3-butoxy-N,N-dimethylpropionamide, etc. They can be used alone or in combination. Furthermore, even if it is a solvent that does not dissolve polyurea, it can be used in admixture with the above-mentioned solvents within the range where the produced polyurea does not precipitate.

In addition, since the moisture in the organic solvent will hinder the polymerization reaction, it is preferable to use the organic solvent after being dehydrated and dried as much as possible.

When the diisocyanate component and the diamine component are reacted in an organic solvent, the following methods are mentioned: stirring a solution obtained by dispersing or dissolving the diamine component in an organic solvent, directly adding the diisocyanate component, or dispersing the diisocyanate component or a method of adding by dissolving in an organic solvent; conversely, a method of adding a diamine component to a solution obtained by dispersing or dissolving a diisocyanate component in an organic solvent; a method of alternately adding a diisocyanate component and a diamine component, etc., can Use any of these methods. In addition, when the diisocyanate component or the diamine component contains a plurality of compounds, they may be reacted in a pre-mixed state, or they may be separately reacted sequentially, and further, low-molecular-weight bodies reacted separately may be mixed and reacted to produce into high molecular weight bodies.

The polymerization temperature at this time can be selected from -20°C to 150°C, preferably in the range of -5°C to 100°C. In addition, the reaction can be carried out at any concentration. When the concentration is too low, it is difficult to obtain a high-molecular-weight polymer. When the concentration is too high, the viscosity of the reaction solution becomes too high and it is difficult to stir uniformly. The total concentration in the solution is preferably 1 to 50% by mass, more preferably 5 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 polymerization reaction of polyurea, the ratio of the total number of moles of diisocyanate components to the total number of moles of diamine components is preferably 0.8 to 1.2. As in a normal polycondensation reaction, the closer this molar ratio is to 1.0, the larger the molecular weight of polyurea to be produced.

When recovering the polyurea produced|generated from the reaction solution of polyurea, what is necessary is just to throw in a reaction solution into a poor solvent, and to make it precipitate. Methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water etc. are mentioned as a poor solvent used for precipitation. After the polymer thrown into a poor solvent and precipitated is collected by filtration, it can be dried at normal temperature or under reduced pressure at normal or reduced pressure. In addition, when the operation of redissolving the precipitated polymer in an organic solvent and reprecipitating it 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.

Such a polyurea is, for example, a polymer having a repeating unit represented by the following formula [1].

(In formula [1], A ₁ is a divalent organic group, A ₂ is a divalent organic group, C ₁ and C ₂ are hydrogen atoms or alkyl groups with 1 to 3 carbons, and may be the same or different from each other. )

In the above formula [1], A ₁ and A ₂ may each be one type of polymer having the same repeating unit, or may be a polymer in which A ₁ and A ₂ are plural types of repeating units having different structures.

In the above formula [1], A ₁ is a group derived from the diisocyanate component of the raw material. _In addition, A2 is a group derived from a raw material diamine component.

According to a preferred aspect of the present invention, A ₁ is preferably a group derived from the preferred diisocyanate components listed above. Moreover, as _A2 , it is preferable that it is a group derived from the preferable diamine component listed above.

In addition, the polyurea used in the present invention is preferably obtained from diamine and diisocyanate, and a small amount of tetracarboxylic dianhydride, tetracarboxylic acid derivative, tricarboxylic acid derivative, dicarboxylic acid A polyurea obtained from a compound having two or more reaction sites for reacting with amino groups of a diamine component, such as a derivative, is also included in the present invention as long as the effect of the present invention is not impaired.

Here, the compound having two or more reaction sites that react with the amino group of the diamine component preferably refers to a carboxylic acid derivative having two or more carboxylic acid moieties capable of forming a carboxyl group that can react with an amine group and / or its anhydrides include, for example, tetracarboxylic acid derivatives and/or their anhydrides, tricarboxylic acid derivatives and/or their anhydrides, dicarboxylic acid derivatives and/or their anhydrides. In addition, such carboxylic acid derivatives and/or anhydrides thereof having two or more carboxylic acid moieties include those in which the carboxylic acid moieties form carboxylate, carboxylic anhydride, carboxylate, etc., for example, tetracarboxylic acid Dianhydride, dialkyl tetracarboxylate, dialkyl tetracarboxylate dichloride, and the like. Here, when using the compound which has two or more reaction sites which react with the amino group of a diamine component, it is preferable that the ratio of this compound and diisocyanate is 99:1-0:100 by molar ratio.

With regard to the amount of the "compound having two or more reactive sites reacting with the amino group of the diamine component" used, the total moles of the compound having two or more reactive sites reacting with the amino group of the diamine component and diisocyanate The ratio of the number of moles to the number of moles of diamine is about 0.8 to 1.2, preferably about 0.9 to 1.1. As in a normal polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polymer to be produced.

As a tetracarboxylic-acid derivative and/or its acid anhydride, the following tetracarboxylic dianhydrides are mentioned, for example.

Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3 ,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1 ,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1, 2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2 ,4,5-pentanetetracarboxylic dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyl tetra Carboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride, cis-3,7-dibutylcyclooct-1,5-diene-1,2,5,6-tetracarboxylic dicarboxylic acid Anhydride, tricyclo[4.2.1.0 ^2,5 ]nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dianhydride, hexacyclo[6.6.0.1 ^2,7 .0 ^{3 ,6} .1 ^9,14 .0 ^10,13 ]hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dianhydride, 3,4-dicarboxy-1,2 , 3,4-tetrahydro-1-naphthalene succinic dianhydride, etc.

Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, Carboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,2,5,6 -naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, and the like.

The said tetracarboxylic dianhydride can be used by 1 type or in combination of 2 or more types according to characteristics, such as the liquid crystal orientation of the liquid crystal aligning film to be formed, voltage retention characteristics, and accumulated electric charge.

Moreover, tetracarboxylic-acid dialkyl ester and tetracarboxylic-acid dialkyl diester dichloride can be used as a tetracarboxylic-acid component which is a raw material of (B) component. In addition, when a tetracarboxylic-acid component contains such tetracarboxylic-acid dialkyl ester and tetracarboxylic-acid dialkyl ester dichloride, a polymer becomes the polyamic acid ester which belongs to a polyimide precursor. Usable tetracarboxylic-acid dialkyl ester is not specifically limited, For example, aliphatic tetracarboxylic-acid diester, aromatic tetracarboxylic-acid dialkyl ester, etc. are mentioned.

Specific examples thereof are listed below.

Specific examples of aliphatic tetracarboxylic acid diesters include dialkyl 1,2,3,4-cyclobutane tetracarboxylate, 1,2-dimethyl-1,2,3,4- Dialkyl cyclobutane tetracarboxylate, 1,3-dimethyl-1,2,3,4-dialkyl cyclobutane tetracarboxylate, 1,2,3,4-tetramethyl- 1,2,3,4-Cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentane tetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid Dialkyl esters, dialkyl 1,2,4,5-cyclohexanetetracarboxylate, dialkyl 3,4-dicarboxy-1-cyclohexylsuccinate, 3,4-dicarboxy-1 ,Dialkyl 2,3,4-tetrahydro-1-naphthalene succinate, dialkyl 1,2,3,4-butane tetracarboxylate, 1,2,4,5-pentane tetracarboxylate dialkyl bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylate, dialkyl 3,3',4,4'-dicyclohexyltetracarboxylate Esters, Dialkyl 2,3,5-tricarboxycyclopentyl acetate, cis-3,7-dibutylcyclooct-1,5-diene-1,2,5,6-tetracarboxylic dioxane tricyclo[4.2.1.0 ^2,5 ]nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dialkyl ester, hexacyclo[6.6.0.1 ^2,7 .0 ^3,6 .1 ^9,14 .0 ^10,13 ]hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dialkyl ester, 3,4-di Carboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, etc.

Specific examples of aromatic tetracarboxylic acid dialkyl esters include dialkyl pyromellitic acid dialkyl esters, 3,3',4,4'-biphenyl tetracarboxylic acid dialkyl esters, 2,2' ,3,3'-Dialkyl biphenyl tetracarboxylate, 2,3,3',4'-Dialkyl biphenyl tetracarboxylate, 3,3',4,4'-benzophenone Dialkyl tetracarboxylate, dialkyl 2,3,3',4'-benzophenone tetracarboxylate, dialkyl bis(3,4-dicarboxyphenyl) ether, bis(3 , 4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl ester, etc.

As a tetracarboxylic-acid diester dichloride, the thing obtained by converting the carboxyl group of the said tetracarboxylic-acid dialkyl ester into a chlorocarbonyl group by a well-known method is mentioned.

Examples of alicyclic dicarboxylic acids include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutane Alkanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutane Dicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentane Dicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 1,4-(2-norbornene)dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo[2.2.2]octane-1,4-di Carboxylic acid, bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-dioxa-1,4-bicyclo[2.2.2]octanedicarboxylic acid, 1,3-adamantane Dicarboxylic acid, 4,8-dioxa-1,3-adamantanedicarboxylic acid, 2,6-heterospiro[3.3]heptanedicarboxylic acid, 1,3-adamantanediacetic acid, camphoric acid, etc.

Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, Formic acid, 5-hydroxyisophthalic acid, 2,5-dimethyl terephthalic acid, tetramethyl terephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-anthracene dicarboxylic acid, 1,4-anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4'- Biphenyl dicarboxylic acid, 1,5-biphenylene dicarboxylic acid, 4,4"-terphenyl dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl Ethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 2,2-diphenylhexafluoropropane-4,4'-dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid , 4,4'-bibenzyl dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 4,4'-toluene dicarboxylic acid, 4,4'-carbonyl dibenzoic acid, 4, 4'-diphenylsulfonedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, terephthalic acid, 3,3'-terephthalic dipropionic acid, 4-carboxycinnamic acid, terephthalic acid , 3,3'-[4,4'-(methylenedi-p-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene)]dipropionic acid, 4,4 Dicarboxylic acids such as '-[4,4'-(oxydi-p-phenylene)] dibutyric acid, (isopropylidene di-p-phenylene dioxa) dibutyric acid, bis(p-carboxyphenyl)dimethylsilane, etc. .

Examples of dicarboxylic acids containing heterocycles include 1,5-(9-oxafluorene)dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl- 4,5-thiazoledicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridine Dicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, etc.

The various dicarboxylic acids mentioned above may be in the structure of acid dihalide or acid anhydride. These dicarboxylic acids are particularly preferably dicarboxylic acids capable of imparting a linear structure to polyamide from the viewpoint of maintaining the orientation of liquid crystal molecules. Among these, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid are preferably used , 4,4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis(benzene base) propane dicarboxylic acid, 4,4-terphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,5-pyridine dicarboxylic acid or their acid dihalides, etc. These compounds also have isomers and may be mixtures containing them. In addition, two or more compounds may be used in combination. In addition, the dicarboxylic acids used in this invention are not limited to the said exemplified compound.

These tetracarboxylic dianhydrides, tetracarboxylic acid diesters, tetracarboxylic acid diester dichlorides, dicarboxylic acids, dicarboxylic acid halides, etc. According to characteristics such as charge, use one type or combine two or more types.

Make tetracarboxylic dianhydride, tetracarboxylic acid diester, tetracarboxylic acid diester dichloride, dicarboxylic acid, dicarboxylic acid halide etc. coexist with isocyanate compound and react with diamine component, thereby obtain belonging to the present invention ( In the case of the polymer of the component B, a known synthesis method can be used. Generally, it is a method of making tetracarboxylic dianhydride or its derivative(s) and a diamine component react in an organic solvent. The reaction of a tetracarboxylic dianhydride and a diamine component is relatively easy to perform in an organic solvent, and is advantageous from a viewpoint that a by-product does not generate|occur|produce.

According to a preferred aspect of the present invention, in the polymer composition of the present invention, with respect to the compounding ratio (mass basis) of the aforementioned (A) component and (B) component, the total ((A) component and (B) component When total) is 1, (A) component is 0.01-0.99, More preferably, it is 0.1-0.9, More preferably, it is 0.2-0.5.

<<(C)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 -Vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, gamma-butyrolactone, 3-methoxy-N,N-dimethylpropanamide , 3-ethoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 1,3-dimethylimidazolinone, ethyl amyl ketone, Methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl 2-Pentanone, Propylene Glycol Monoacetate, Propylene Glycol Monomethyl Ether, Propylene Glycol Tert-Butyl Ether, Dipropylene Glycol Monomethyl Ether, Diethylene Glycol, Diethylene Glycol 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 Base-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 not limited to, solvents or compounds that improve film thickness uniformity and surface smoothness when coating a polymer composition, compounds that improve adhesion between a liquid crystal aligning film and a substrate, and the like.

Specific examples of solvents (poor solvents) that improve film thickness uniformity and surface smoothness include the following solvents.

Examples include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, Butyl Carbitol, Ethyl Carbitol, Ethyl Carbitol Acetate, Ethylene Glycol, Ethylene Glycol Monoacetate, Ethylene Glycol Monoisopropyl Ether, Ethylene Glycol Monobutyl Ether, Propylene Glycol, Propylene Glycol Monoacetate, Propylene Glycol Monomethyl Ether, Propylene Glycol Monomethyl 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-methoxy Butyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, Diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, acetic acid Ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, 3-methoxy Ethyl propionate, 3-ethoxypropionate, 3-methoxypropionate, 3-methoxypropylpropionate, 3-methoxybutylpropionate, 1-methoxy-2-propionate Alcohol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1 - monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, Solvents with low surface tension such as n-propyl lactate, n-butyl lactate, and isoamyl lactate, etc.

These poor solvents may be used individually by 1 type, and may mix and use multiple types. When using the above-mentioned solvent, it is preferably 5% by mass to 80% by mass of the entire solvent, more preferably 20% by mass to 60% by mass, so as not to significantly reduce the solubility of the entire solvent contained in the polymer composition.

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

More specifically, examples thereof include Eftop (registered trademark) 301, EF303, EF352 (manufactured by Tohkem Products Corporation), Megafac (registered trademark) F171, F173, R-30 (manufactured by DICCORPORATION), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited), AsahiGuard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC SEI MICHEMICAL 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, based on 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 compound etc. which contain the functional silane shown below are mentioned.

Examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2 -Aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureapropyltrimethoxysilane, 3 -Ureapropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxy Silylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-trimethoxysilylpropyltriethylenetriamine, 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 adhesion between the substrate and the liquid crystal alignment film, and to prevent the decrease in electrical properties caused by the backlight when constituting the liquid crystal display element, the polymer composition may contain the following phenolic plastics, epoxy group-containing compound additives. Specific phenolic plastic additives are shown below, but are not limited to this structure.

Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6- Tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl base) cyclohexane, N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, etc.

When using a compound for improving the adhesion between the liquid crystal aligning film and the substrate, the amount used is preferably 0.1 parts by mass to 30 parts by mass, more preferably 1 part by mass to 100 parts by mass of the resin component contained in the polymer composition. 20 parts by mass. When the usage-amount is less than 0.1 mass parts, the effect which improves adhesiveness cannot be expected, and when it exceeds 30 mass parts, the orientation of a liquid crystal may worsen.

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-methylcoumarin, 7-hydroxy-4-methylcoumarin), coumarin ketone, carbonyl bis-perfume Soybein, aromatic 2-hydroxy ketones, and aromatic 2-hydroxy ketones substituted by amino groups (2-hydroxybenzophenone, single-p-(dimethylamino)-2-hydroxybenzophenone or di-p-(di methylamino)-2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl-β-naphthothiazoline, 2-(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3-methylbenzo Thiazoline, 2-(4-bibenzoylmethylene)-3-methylbenzothiazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2 -(4-bibenzoylmethylene)-3-methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline), Oxazoline (2-benzoylmethylene-3-methyl-β-naphthooxazoline, 2-(β-naphthoylmethylene)-3-methylbenzoxazoline, 2- (α-naphthoylmethylene)-3-methylbenzoxazoline, 2-(4-biphenoylmethylene)-3-methylbenzoxazoline, 2-(β-naphthoyl Methylene)-3-methyl-β-naphthooxazoline, 2-(4-bibenzoylmethylene)-3-methyl-β-naphthooxazoline, 2-(p-fluorobenzene Formylmethylene)-3-methyl-β-naphthooxazoline), benzothiazole, nitroaniline (m-nitroaniline or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p-methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthaloketone, acetophenone Ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol, and 9-anthracenecarboxylic acid), benzopyran, even Indolizine, Merlocoumarin, etc.

Preferred are aromatic 2-hydroxyketones (benzophenones), coumarins, coumarinones, carbonyl dicoumarins, acetophenones, anthraquinones, xanthones, thioxanthones and benzene Acetone ketal.

In addition to the above-mentioned substances in the polymer composition, as long as it does not impair the effect of the present invention, for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film, dielectrics and conductive substances can be added, Furthermore, a crosslinkable compound can be added for the purpose of improving the hardness and density of a film at the time of making it into a liquid crystal aligning film.

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

About the coating method, the method by screen printing, offset printing, flexographic printing, an inkjet method, etc. is common industrially. As other coating methods, there are dipping method, roll coating method, slit coating method, spin coating method (spin coating method), spray coating method, etc., and they can be used according to the purpose.

After coating the polymer composition on a substrate having a conductive film for driving in a transverse electric field, heat it at 50 to 200° C., preferably at 50 to 150° C. The solvent evaporates to obtain a coating film. 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 be reduced, so it is preferably 5nm to 300nm, more preferably 10nm to 10nm. 150nm.

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

<Process [II]>

In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When irradiating polarized ultraviolet rays to the film surface of the coating film, the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a specific point. 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 an 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 light with a wavelength in the range of 290nm to 400nm can be selected to induce photocrosslinking reaction selectively. As the ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The amount of exposure to polarized ultraviolet light depends on the coating film to be used. Regarding the irradiation amount, it is preferably within the range of 1% to 70%, more preferably within the range of 1% to 50%, of the amount of polarized ultraviolet light that realizes the maximum value of ΔA (hereinafter also referred to as ΔAmax). is the difference between the ultraviolet absorbance of the coating film 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.

<Process [III]>

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

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

The heating temperature is preferably within a temperature range at which the side chain type polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystallinity expression temperature). In the case of a film surface such as a coating film, it is expected that the liquid crystallinity expression temperature of the coating film surface is lower than the liquid crystallinity expression temperature when the photosensitive side chain type polymer that can express liquid crystallinity is observed as a whole. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystallinity expression temperature of the coating film surface. That is, the temperature range of the heating temperature after irradiating polarized ultraviolet rays is preferably a temperature that is 10°C lower than the lower limit of the temperature range of the liquid crystallinity expression temperature of the side chain type polymer used, and is lower than the upper limit of the liquid crystal temperature range. A temperature of 10° C. is used as the temperature of the upper limit range. When the heating temperature is lower than the above temperature range, there is a tendency that the anisotropic amplification effect brought by heat in the coating film is not sufficient. In addition, when the heating temperature is too high compared with the above temperature range, the state of the coating film may be close to anisotropy. It tends to be in an isotropic liquid state (isotropic phase). In this case, it may be difficult to reorient in one direction due to self-assembly.

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

By having the above steps, in the production method of the present invention, efficient introduction of anisotropy to the coating film can be realized. Moreover, the board|substrate with a liquid crystal aligning film can be manufactured efficiently.

<Process [IV]>

The [IV] step is to prepare the substrate (first substrate) having a liquid crystal alignment film on the conductive film for driving a transverse electric field obtained in [III] with the substrate (first substrate) obtained in the above [I'] to [III'] similarly without The substrate (the second substrate) with the liquid crystal alignment film of the conductive film is placed opposite to each other with the liquid crystal alignment films facing each other, and a liquid crystal cell is produced by a known method, thereby producing a lateral electric field drive type liquid crystal display element. process. It should be noted that, in the steps [I'] to [III'], except that in the step [I], a substrate without a conductive film for driving a transverse electric field is used instead of a substrate having a conductive film for driving a transverse electric field, It can carry out similarly to process [I]-[III]. The difference between steps [I]-[III] and steps [I']-[III'] lies in the presence or absence of the above-mentioned conductive film, so the description of steps [I']-[III'] is omitted.

If a production example of a liquid crystal unit or a liquid crystal display element is cited, the following method can be illustrated: prepare the above-mentioned first substrate and the second substrate, spread spacers on the liquid crystal alignment film of one substrate, and use the liquid crystal alignment film surface as The inner side is pasted to another substrate, and the liquid crystal is injected under reduced pressure and sealed; or the liquid crystal is dropped on the surface of the liquid crystal alignment film where the spacers are scattered, and the substrate is pasted and sealed. In this case, it is preferable to use a substrate having an electrode having a comb-tooth 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, more preferably 2 μm to 10 μm. The spacer diameter determines the distance between a pair of substrates 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, a polymer composition is apply|coated on a board|substrate to form a coating film, and polarized ultraviolet-ray is irradiated. Next, by heating, efficient introduction of anisotropy into the side chain type polymer film is realized, and the board|substrate with a liquid crystal aligning film equipped with the liquid crystal orientation control capability is manufactured.

In the coating film used in the present invention, efficient introduction of anisotropy into the coating film is achieved by utilizing the principle of molecular reorientation induced by photoreaction of side chains and self-assembly based on liquid crystallinity. In the production method of the present invention, when the side-chain type polymer has a structure having a photocrosslinkable group as a photoreactive group, after forming a coating film on the substrate using the side-chain type polymer, irradiate polarized ultraviolet rays, and then heat After that, a liquid crystal display element is produced.

Hereinafter, an embodiment using a side-chain type polymer having a photocrosslinkable group as a photoreactive group is referred to as a first embodiment, and the use of a polymer having a photo-Fries rearrangement group or a different An embodiment of a side chain type polymer having a structured group as a photoreactive group will be described as a second embodiment.

Fig. 1 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 embodiment of the present invention. A diagram of an example of anisotropy introduction processing. Fig. 1(a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, and Fig. 1(b) is a diagram schematically showing the state of the side chain type polymer film after polarized light irradiation 1 (c) is a diagram schematically showing 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 of when the ultraviolet irradiation dose in the step is within the range of 1% to 15% of the maximum ultraviolet irradiation dose for ΔA.

Fig. 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 embodiment of the present invention. A diagram of an example of anisotropy introduction processing. Fig. 2 (a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, and Fig. 2 (b) is a schematic diagram showing the state of the side chain type polymer film after polarized light irradiation 2 (c) is a diagram schematically showing the state of the side chain type polymer film after heating, especially when the introduced anisotropy is large, that is, in the first embodiment of the present invention, [ II] Schematic diagram of the case where the ultraviolet irradiation dose in the step is within the range of 15% to 70% of the ultraviolet irradiation dose for maximizing ΔA.

Fig. 3 schematically illustrates the structure in which a photoisomerizable group or a photofries rearrangement group represented by the above formula (18) is used as a photoreactive group in the second embodiment of the present invention The figure of an example of the anisotropy introduction process in the manufacturing method of the liquid crystal aligning film made of the side chain type polymer of . Fig. 3 (a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, and Fig. 3 (b) is a schematic diagram showing the state of the side chain type polymer film after polarized light irradiation 3 (c) is a diagram schematically showing 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 of the case where the ultraviolet irradiation dose in the step is within the range of 1% to 70% of the ultraviolet irradiation dose that maximizes ΔA.

Fig. 4 schematically illustrates the use of a side chain type polymer having a photo-Fries rearrangement group represented by the above formula (19) as a photoreactive group in a second embodiment of the present invention. The figure of an example of the anisotropy introduction process in the manufacturing method of the liquid crystal aligning film. Fig. 4 (a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, and Fig. 4 (b) is a schematic diagram showing the state of the side chain type polymer film after polarized light irradiation 4 (c) is a diagram schematically showing 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 of the case where the ultraviolet irradiation dose in the step is within the range of 1% to 70% of the ultraviolet irradiation dose for maximizing ΔA.

In the first aspect of the present invention, by introducing anisotropy to the coating film, when the ultraviolet irradiation amount in the [II] step is in the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA, first, in 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. Due to the random arrangement of the side chains 2 of the coating film 1, the mesogen components and photosensitive groups of the side chains 2 are also randomly oriented, and the coating film 1 is isotropic.

In the first aspect of the present invention, by introducing anisotropy to the coating film, when the ultraviolet irradiation amount in the [II] step is in the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ΔA, first, in 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. Due to the random arrangement of the side chains 4 of the coating film 3, the mesogen components and photosensitive groups of the side chains 4 are also randomly oriented, and the coating film 2 is isotropic.

In the second aspect of the present invention, by introducing anisotropy to the coating film, a structure using 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 the range of 1% to 70% of the ultraviolet irradiation dose that maximizes 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. Due 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 oriented, and the side chain type polymer film 5 is isotropic.

In the second aspect of the present invention, liquid crystal alignment using a side chain polymer having a structure of the photo-Friesian rearrangement group represented by the above formula (19) is applied by introducing anisotropy to the coating film. When the ultraviolet irradiation amount in the [II] step is within the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, first, the coating film 7 is formed on the substrate. 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. Due to the random arrangement of the side chains 8 of the coating film 7, the mesogen components and photosensitive groups of the side chains 8 are also randomly oriented, and the coating film 7 is isotropic.

In the first form of this embodiment, when the ultraviolet irradiation amount in the [II] step is in the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA, the isotropic coating film 1 is irradiated with polarized ultraviolet rays. Thereby, as shown in FIG. 1(b), among the side chains 2 arranged in a direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 2a having a photosensitive group is preferentially generated. Photoreactions such as dimerization. As a result, the density of the photoreacted side chains 2a becomes slightly higher 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 form of this embodiment, when the ultraviolet irradiation amount in the [II] step is within the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the isotropic coating film 3 is irradiated with polarized ultraviolet rays. Thus, as shown in (b) of FIG. 2 , among the side chains 4 arranged in a direction parallel to the polarization direction of 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 form of this embodiment, a liquid crystal aligning film using a side chain type polymer having a photoisomerizable group or a photofries rearrangement group represented by the above formula (18) is applied, [II] When the ultraviolet irradiation amount in the step is within the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the isotropic coating film 5 is irradiated with polarized ultraviolet rays. Thus, as shown in (b) of FIG. 3 , among the side chains 6 arranged in a direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 6 a having a photosensitive group preferentially generates light. Fries rearrangement and other photoreactions. As a result, the density of the photoreacted side chains 6a becomes slightly higher 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 form of this embodiment, the coating film using the side chain type polymer having the structure of the photofries rearrangement group represented by the above formula (19) is applied, and the ultraviolet irradiation amount in the step [II] is When ΔA is within the range of 1% to 70% of the maximum ultraviolet irradiation amount, the isotropic coating film 7 is irradiated with polarized ultraviolet rays. Thereby, as shown in FIG. 4 (b), among the side chains 8 arranged in a direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 8a 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 form of this embodiment, when the ultraviolet irradiation amount in the [II] step is in the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA, the coating film 1 after irradiating polarized light is heated to produce into a liquid crystal state. Thereby, as shown in FIG. 1(c), in the coating film 1, the amount of crosslinking reaction that occurs 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, the amount of crosslinking reaction occurring in a direction parallel to the polarization direction of the irradiated ultraviolet rays is very small, so 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 that 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 containing the mesogen components 2 for reorientation. As a result, the very small anisotropy of the coating film 1 induced by the photocrosslinking reaction is amplified by heat, and larger anisotropy is imparted to the coating film 1 .

Similarly, in the first form of this embodiment, when the ultraviolet irradiation amount in the [II] step is in the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the coating film 3 after polarized light irradiation is heated to Made into a liquid crystal state. Thus, as shown in (c) of FIG. 2 , in the side chain type polymer film 3 , crosslinking occurs between a direction parallel to the polarization direction of the irradiated ultraviolet rays and a direction perpendicular to the polarization direction of the irradiated ultraviolet rays. The amount of response 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 re-aligned. As a result, the small anisotropy of the coating film 3 induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 3 .

Similarly, in the second mode of the present embodiment, a coating film using a side chain type polymer having a photoisomerizable group or a photofries rearrangement group represented by the above formula (18) is applied. When the ultraviolet irradiation amount in the [II] step is in the range of 1% to 70% of the ultraviolet irradiation amount that makes ΔA the maximum, the coating film 5 after polarized light irradiation is heated to be in a liquid crystal state. Thereby, as shown in FIG. 3(c), in the coating film 5, 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 light Friese rearrangement occurs. The amount of response varies. At this time, the liquid crystal alignment force of the photo-Fries rearrangement body generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet rays is stronger than that of the side chain before the reaction, so self-assembly occurs in the direction perpendicular to the polarization direction of the irradiated ultraviolet rays , the side chains 6 including the mesogen component undergo reorientation. 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 mode of the present embodiment, the coating film using the side chain type polymer having the structure of the photofries rearrangement group represented by the above formula (19) is applied, and the ultraviolet irradiation in the step [II] When the amount is in the range of 1% to 70% of the ultraviolet irradiation amount that makes ΔA the maximum, the coating film 7 after polarized light irradiation is heated to be in a liquid crystal state. Thus, as shown in (c) of FIG. 4 , in the side chain type polymer film 7, the light 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 the Lys rearrangement varies. The photo-Fries rearrangement body 8 (a) has stronger anchoring force than the side chain 8 before rearrangement, so when a certain amount or more of the photo-Fries rearrangement body is produced, the self-rearrangement occurs in a direction parallel to the polarization direction of the irradiated ultraviolet rays. Assembled, the side chains 8 including the mesogen component are re-aligned. 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 by the method of this invention by sequentially irradiating a coating film with polarized ultraviolet rays and heat-processing, and can be made into the liquid crystal aligning film excellent in orientation control ability.

In addition, for the coating film used in the method of the present invention, the irradiation amount of polarized ultraviolet rays irradiated to the coating film and the heating temperature of the heat treatment are optimized. This enables efficient introduction of anisotropy into the coating film.

For efficiently introducing anisotropy into the coating film used in the present invention, the optimal amount of irradiation of polarized ultraviolet light corresponds to causing photocrosslinking reaction, photoisomerization reaction or photosensitive group in the coating film. The amount of Fries rearrangement reaction achieves the optimal amount of polarized UV exposure. As a result of irradiating polarized ultraviolet rays to the coating film used in the present invention, if there are few photosensitive groups in the side chains that undergo photocrosslinking reaction, photoisomerization reaction, or photofries rearrangement reaction, sufficient photoreaction amount cannot be achieved . In this case, even if heating is performed thereafter, sufficient self-assembly will not proceed. On the other hand, for the coating film used in the present invention, as a result of irradiating polarized ultraviolet rays to a structure having a photocrosslinkable group, when the photosensitive group of the side chain undergoing a crosslinking reaction is excessive, the distance between the side chains The cross-linking reaction will be over-propelled. At this time, the resulting film becomes rigid, which may hinder subsequent progress of self-assembly by heating. In addition, for 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 that undergoes the photo-Fries rearrangement reaction becomes excessive. When , the liquid crystallinity of the coating film will decrease excessively. In this case, 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 photo-Fries rearrangement group, if the irradiation amount of ultraviolet rays is too high, the side chain type polymer may be photodecomposed, which may hinder the subsequent progress of self-assembly by heating. .

Therefore, in the coating film used in the present invention, the optimal amount of the photosensitive group of the side chain to undergo photocrosslinking reaction, photoisomerization reaction or photofries rearrangement reaction due to the irradiation of polarized ultraviolet rays is preferably set to 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 setting the amount of the photosensitive group of the side chain that undergoes photoreaction within such a range, self-assembly in the subsequent heat treatment can be efficiently advanced, and efficient anisotropy in the 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, photoisomerization reaction or photosensitive group in the side chain of the side chain type polymer film are optimized. The amount of the Fries rearrangement reaction. In addition, efficient introduction of anisotropy into the coating film used in the present invention is realized together with subsequent heat treatment. In this case, the appropriate 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 rays and the ultraviolet absorption in the direction perpendicular to the polarization direction of the polarized ultraviolet rays after irradiation with polarized ultraviolet rays were measured. 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 to realize it were obtained. In the manufacturing method of this invention, the amount of polarized ultraviolet rays which realize|achieves this ΔAmax as a reference can determine the preferable amount of polarized ultraviolet rays irradiated in manufacture of a liquid crystal aligning film.

In the production method of the present invention, it is preferable to set the irradiation amount of polarized ultraviolet rays irradiated to the coating film used in the present invention within a range of 1% to 70%, more preferably 1% to 70% of the amount of polarized ultraviolet rays that will realize ΔAmax. 50% range. In the coating film used in the present invention, the amount of irradiation of polarized ultraviolet rays within the range of 1% to 50% of the amount of polarized ultraviolet rays that will realize 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 is 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, an appropriate heating temperature as described above 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, it is desirable to set the heating temperature after irradiation with polarized ultraviolet rays to 90°C to 190°C. By setting in this way, larger anisotropy is imparted to the coating film used for this invention.

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

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

Hereinafter, although an Example is used and this invention is demonstrated, this invention is not limited to this Example.

Example

Abbreviations used in Examples are as follows.

<Methacrylic monomer>

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).

<Diisocyanate component>

ISO1: Toluene-2,4-diisocyanate

ISO2: Isophorone diisocyanate

<Diamine component>

Me-4APhA: N-methyl-2-(4-aminophenyl)ethylamine

DA-1MG: bis(4-aminophenoxy)methane

DA-2MG: 1,2-bis(4-aminophenoxy)ethane

DA-3MG: 1,3-bis(4-aminophenoxy)propane

BAPU: 1,3-bis[2-(4-aminophenyl)ethyl]urea

p-PDA: p-phenylenediamine

DDM: 4,4'-Diaminodiphenylmethane

3AMPDA: 3,5-diamino-N-(pyridin-3-ylmethyl)benzamide

DADPA: 4,4’-Diaminodiphenylamine

Me-DADPA: 4,4'-Diaminodiphenyl(N-methyl)amine

<Tetracarboxylic dianhydride>

CBDA: 1,2,3,4-cyclobutane tetracarboxylic acid 1,2:3,4 dianhydride

PMDA: pyromellitic dianhydride

TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride

BODA: Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride

BDAM: 1,2,4,5-pentanetetracarboxylic dianhydride

BDA: 1,2,3,4-butanetetracarboxylic dianhydride

<Organic solvent>

THF: Tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cellosolve

<polymerization initiator>

AIBN: 2,2'-Azobisisobutyronitrile

<Synthesis Example 1: Methacrylate Polymer Solution>

MA1 (2.99 g, 9.0 mmol) and MA2 (1.83 g, 6.0 mmol) were dissolved in THF (44.57 g), and after degassing with a diaphragm pump, AIBN (0.12 g, 0.5 mmol) was added and degassed again. Then, it was made to react at 50 degreeC for 30 hours, and the polymer solution of the methacrylate was obtained. This polymer solution was added dropwise to diethyl ether (500 ml), and the resulting precipitate was filtered. This deposit was wash|cleaned with diethyl ether, and it dried under reduced pressure in the oven of 40 degreeC, and obtained the methacrylate polymer powder.

NMP36.0g was added to the obtained powder 4.0g, and it stirred at room temperature for 3 hours. A methacrylate polymer solution (M1) having a solid content concentration of 10.0% by weight was obtained. The polymer was completely dissolved at the end of stirring.

<Synthesis Example 2: Polyurea>

As a diamine component, 1.50 g of Me-4APhA was dissolved in NMP12.77 g, 1.68 g of ISO1 was added as a diisocyanate component at room temperature, and reacted at 60 degrees for 18 hours to obtain a polyurea (PU-1) with a concentration of 20 wt% solution.

<Synthesis Examples 3-10: Polyurea>

According to the composition shown in Table 1, polyurea solutions of Synthesis Examples 3 to 10 were synthesized by the same method as that of Synthesis Example 2 (polyurea) above.

<Synthesis Example 11: Polyamic Acid>

Using 1.88 g of CBDA as the tetracarboxylic dianhydride component and 2.98 g of BAPU as the diamine component, reacted in 19.4 g of NMP at room temperature for 18 hours to obtain a solution with a polyamic acid (PAA-1) concentration of 20 wt % .

Table 1:

[Table 1]

<Synthesis Example 12: Polyurea Polyamic Acid>

As a diamine component, 1.99 g of DADPA is dissolved in NMP16.55 g, 1.55 g of ISO2 is added thereto as a diisocyanate component at room temperature, and after stirring for 1 hour, 0.59 g of PMDA is added as an acid dianhydride component, and then at room temperature The reaction was carried out for 6 hours to obtain a solution with a concentration of polyurea·amic acid (PUA-1) of 20 wt%.

<Synthesis Examples 13-21: Polyurea Polyamic Acid>

According to the composition shown in Table 2, the polyurea-amic acid solution of synthesis example 13- was synthesized by the method similar to the said polyurea-amic-acid synthesis example 12.

Table 2:

[Table 2]

(Example 1)

3.0 g of polyurea solutions (PU-1) were added to 3.0 g of the methacrylate polymer solution (M1) obtained by the said synthesis example 1, and it stirred at room temperature for 1 hour. Furthermore, 4.0 g of BCS and 5.0 g of NMP were added to this solution, and it stirred at room temperature for 1 hour, and obtained the polymer solution (A1) whose solid content concentration was 6.0 wt%. This polymer solution becomes the liquid crystal aligning agent for forming a liquid crystal aligning film as it is.

(Examples 2-9, Comparative Examples 1-2)

According to the composition shown in Table 3, the polymer solution of Examples 2-9 was obtained using the same method as Example 1. In addition, Comparative Examples 1-2 were also prepared by the same method.

table 3:

[table 3]

(Example 10)

3.5 g of polyurea and amic acid solutions (PUA-1) were added to 3.0 g of the methacrylate polymer solution (M1) obtained by the said methacrylic-type synthesis example 1, and it stirred at room temperature for 1 hour. Furthermore, 6.7 g of BCS and 3.5 g of NMP were added to this solution, and it stirred at room temperature for 1 hour, and obtained the polymer solution (A10) whose solid content concentration was 6.0 wt%. This polymer solution becomes the liquid crystal aligning agent for forming a liquid crystal aligning film as it is.

(Example 11-19)

According to the composition shown in Table 4, the polymer solution of Examples 11-20 was obtained by the method similar to Example 10.

Table 4:

[Table 4]

[Production of liquid crystal unit]

Using the liquid crystal aligning agent (A1) obtained in Example 1, preparation of the liquid crystal cell was performed in accordance with the procedure shown below. The substrate was a glass substrate with a size of 30 mm×40 mm and a thickness of 0.7 mm, and a substrate on which comb-shaped pixel electrodes formed by patterning an ITO film were arranged was used. The pixel electrode has a comb-tooth shape formed by arranging a plurality of "<"-shaped electrode elements bent at the center. The width in the width direction of each electrode element was 10 μm, and the interval between electrode elements was 20 μm. The pixel electrode forming each pixel is formed by arranging a plurality of "<"-shaped electrode elements bent at the center. Therefore, the shape of each pixel is not a rectangular shape, but has an electrode element bent at the center, Similar to the bold "<" shape. In addition, each pixel is divided up and down with a curved portion at the center thereof, and has a first region above the curved portion and a second region below the curved portion. When comparing the first region and the second region of each pixel, the formation directions of the electrode elements constituting the pixel electrodes are different. That is, when the alignment treatment direction of the liquid crystal alignment film described later is taken as a reference, in the first region of the pixel, the electrode element of the pixel electrode is formed to form an angle (clockwise) of +15°, and in the second region of the pixel In , the electrode elements of the pixel electrode are formed to form an angle of -15° (clockwise). That is, the first region and the second region of each pixel are configured such that directions of in-plane rotation (plane switching) of the liquid crystal induced by applying a voltage between the pixel electrode and the counter electrode are opposite to each other.

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 the hot plate of 70 degreeC, and formed the liquid crystal aligning film with a film thickness of 100 nm. Next, after irradiating the coating film surface with ultraviolet rays of 313 nm at 5 mJ/cm ² through a polarizing plate, it was heated on a 140° C. hot plate for 10 minutes to obtain a substrate with a liquid crystal aligning film. In addition, as a counter substrate, a coating film was similarly formed on a glass substrate having no electrodes and a columnar spacer having a height of 4 μm, and an orientation treatment was performed. A sealing agent (manufactured by Kyoritsu Chemical Co., Ltd., XN-1500T) was printed on the liquid crystal aligning film of one board|substrate. Next, after affixing the other board|substrate so that the liquid crystal aligning film surface faced and the orientation direction became 0 degree|times, the sealant was heat-hardened, and the empty cell was produced. Liquid crystal MLC-2041 (manufactured by MERCK CORPORATION) was injected into the empty cell by a depressurized injection method, and the injection port was sealed to obtain a liquid crystal cell having a liquid crystal display element in an IPS (In-Planes Switching) mode.

Also about the liquid crystal aligning agent (A2-A19) obtained in Examples 2-19, the liquid crystal cell was produced by the method similar to A1.

(Voltage retention rate (VHR) evaluation)

In the evaluation of VHR, a voltage of 5 V was applied to the obtained liquid crystal cell at a temperature of 70° C. for 60 μs, the voltage after 1667 ms was measured, and how much the voltage could be maintained was calculated as a voltage retention rate.

In addition, the measurement of the voltage retention ratio used the voltage retention ratio measurement apparatus VHR-1 manufactured by TOYO Corporation.

Using the liquid crystal aligning agent (B1) obtained in the comparative example 1, manufacture of a liquid crystal cell was performed similarly to the time of using the said liquid crystal aligning agent (A1), and VHR was evaluated by the same method.

The results are shown in Table 5 and Table 6 below.

table 5:

[table 5]

Table 6:

[Table 6]

As shown in Table 5 and Table 6, it became clear that the voltage retention ratio (VHR) of Examples 1-19 based on this invention was high compared with the comparative example 1 which was the same as (A) component and did not contain (B) component.

Explanation of reference signs

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 (18)

1. A polymer composition comprising: (A) A photosensitive side chain type polymer that exhibits liquid crystallinity in a specific temperature range, (B) polyurea, and (C) Organic solvents. 2. The composition according to claim 1, wherein the component (A) has a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofries rearrangement. 3. The composition according to claim 1 or 2, wherein the polyurea as the component (B) is obtained by polymerizing a diisocyanate component and a diamine component. 4. The composition according to claim 1 or 2, wherein the polyurea as the (B) component is obtained by making a diisocyanate component, a carboxylic acid derivative having two or more carboxylic acid moieties and/or an anhydride thereof, and It is obtained by polymerizing the diamine component. 5. The composition according to claim 3 or 4, wherein the diisocyanate component is an aromatic diisocyanate and/or an aliphatic diisocyanate. 6. The composition according to any one of claims 1 to 5, wherein the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (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 with 1 to 12 carbon atoms, and the hydrogen atoms bonded to them are optionally substituted by halogen groups; T is a single bond or an alkylene group with 1 to 12 carbons, and the hydrogen atoms bonded to them are optionally substituted by halogen groups; Y represents _a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, and alicyclic hydrocarbons with 5 to 8 carbon atoms, or the same or different substituents selected from these substituents The group formed by bonding 2 to 6 rings of the above group by means of the bonding group B, the hydrogen atoms bonded to them are each independently optionally replaced by -COOR ₀ , -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons or an alkoxy group with 1 to 5 carbons, where R ₀ represents a hydrogen atom or an alkane with 1 to 5 carbons base; _Y2 is a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons with 5 to 8 carbon atoms, and combinations thereof, and is bonded to them The hydrogen atoms in are independently optionally replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkyl group with 1 to 5 carbons Alkoxy substitution; R represents a hydroxyl group, an alkoxy group with 1 to 6 carbons, or the same definition as _Y1 ; 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 bonded to them are each independently optionally replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH= Substituted by CH-CN, halogen group, alkyl group with 1 to 5 carbons or alkoxy group with 1 to 5 carbons; 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 divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons with 5 to 8 carbon atoms, and combinations thereof; Among them, 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 represents a single bond; When l1 is 1, when T is a single bond, B also represents a single bond; H and I are each independently a group selected from divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, and combinations thereof. 7. The composition according to any one of claims 1 to 5, wherein the component (A) has any photosensitive side chain selected from the group consisting of the following formulas (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 represents _a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, and alicyclic hydrocarbons with 5 to 8 carbon atoms, or the same or different substituents selected from these substituents The group formed by bonding 2 to 6 rings of the above group by means of the bonding group B, the hydrogen atoms bonded to them are each independently optionally replaced by -COOR ₀ , -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons or an alkoxy group with 1 to 5 carbons, where R ₀ represents a hydrogen atom or an alkane with 1 to 5 carbons base; 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, 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; _Y2 is a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons with 5 to 8 carbon atoms, and combinations thereof, and is bonded to them The hydrogen atoms in are independently optionally replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkyl group with 1 to 5 carbons Alkoxy substitution; R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as _Y1 . 8. The composition according to any one of claims 1 to 5, wherein the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (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 m2 represents an integer from 1 to 3; R represents a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, and alicyclic hydrocarbons with 5 to 8 carbon atoms, or the same or different substituents selected from these substituents A group in which 2 to 6 rings are bonded via a bonding group B, the hydrogen atoms bonded to them are each independently optionally replaced by -COOR ₀ , -NO ₂ , -CN, -CH=C(CN) _2. -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons or an alkoxy group with 1 to 5 carbons, where R ₀ represents a hydrogen atom or an alkyl group with 1 to 5 carbons , or R represents a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms. 9. The composition according to any one of claims 1 to 5, 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 represents _a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, and alicyclic hydrocarbons with 5 to 8 carbon atoms, or the same or different substituents selected from these substituents The group formed by bonding 2 to 6 rings of the above group by means of the bonding group B, the hydrogen atoms bonded to them are each independently optionally replaced by -COOR ₀ , -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons or an alkoxy group with 1 to 5 carbons, where R ₀ represents a hydrogen atom or an alkane with 1 to 5 carbons base; 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 of 1-12, and m1 and m2 represent an integer of 1-3. 10. The composition according to any one of claims 1 to 5, 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 of 1-12, and m represents an integer of 0-2. 11. The composition according to any one of claims 1 to 5, wherein the component (A) has a photosensitive side chain represented by 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 represents _a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, and alicyclic hydrocarbons with 5 to 8 carbon atoms, or the same or different substituents selected from these substituents The group formed by bonding 2 to 6 rings of the above group by means of the bonding group B, the hydrogen atoms bonded to them are each independently optionally replaced by -COOR ₀ , -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons or an alkoxy group with 1 to 5 carbons, where R ₀ represents a hydrogen atom or an alkane with 1 to 5 carbons base; One of q1 and q2 is 1 and the other is 0; l represents an integer from 1 to 12; 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 with 1 to 5 carbons, or an alkoxy group with 1 to 5 carbons base. 12. The composition according to any one of claims 1 to 5, 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 represents _a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, and alicyclic hydrocarbons with 5 to 8 carbon atoms, or the same or different substituents selected from these substituents The group formed by bonding 2 to 6 rings of the above group by means of the bonding group B, the hydrogen atoms bonded to them are each independently optionally replaced by -COOR ₀ , -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons or an alkoxy group with 1 to 5 carbons, where R ₀ represents a hydrogen atom or an alkane with 1 to 5 carbons base; 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 of 1-12, and m represents an integer of 0-2. 13. The composition according to any one of claims 1 to 12, wherein the component (A) has any liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31), In the formula, A and B have the same definition as above; _Y3 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 heterocycle, and an alicyclic hydrocarbon with a carbon number of 5 to 8, and combinations thereof, and the bond The hydrogen atoms associated with them are each independently optionally substituted by -NO ₂ , -CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkoxy group with 1 to 5 carbons; 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 Azacyclic rings, alicyclic hydrocarbons with 5 to 8 carbons, alkyl groups with 1 to 12 carbons or alkoxy groups with 1 to 12 carbons; One of q1 and q2 is 1 and the other is 0; l represents an integer of 1 to 12, m represents an integer of 0 to 2, wherein, 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 of 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and an alicyclic hydrocarbon with 5 to 8 carbons, and Alkyl or alkoxy; Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -. 14. A method for manufacturing a substrate with a liquid crystal alignment film for a transverse electric field driven type liquid crystal display element, which obtains the liquid crystal alignment film endowed with orientation control ability by possessing the following steps: [1] The composition described in any one of claims 1 to 13 is coated on a substrate having a transverse electric field driving conductive film 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]. 15. A substrate having a liquid crystal alignment film for a lateral electric field driven liquid crystal display element, manufactured by the method according to claim 14. 16. A lateral electric field driven liquid crystal display element comprising the substrate according to claim 15. 17. A method for manufacturing a transverse electric field driven liquid crystal display element, which obtains the liquid crystal display element by having the following steps: A step of preparing the substrate according to claim 15, that is, the first substrate; The process of obtaining the second substrate having the following liquid crystal aligning film, which is provided with the following steps [I'], [II'] and [III'] to obtain a liquid crystal aligning film endowed with orientation control ability; and [IV] The step of arranging the first substrate and the second substrate facing each other in such a manner that the liquid crystal alignment films of the first substrate and the second substrate face each other through the liquid crystal, thereby obtaining a liquid crystal display element, Described operation [I '], [II '] and [III '] are: [I'] A step of forming a coating film by coating a polymer composition containing: (A) a photosensitive side chain-type polymer exhibiting liquid crystallinity in a specific temperature range to form a coating film; molecule, (B) polyurea and (C) 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']. 18. A transverse electric field driven liquid crystal display element manufactured by the method according to claim 17.