KR20160007636A - Method for producing substrate having liquid crystal orientation membrane for use in in-plane-switching liquid crystal display element - Google Patents

Abstract

The present invention provides a transverse electric field driving type liquid crystal display element which is imparted with orientation control ability with high efficiency and excellent in exposure characteristics. (A) a photosensitive side-chain polymer which exhibits liquid crystallinity in a predetermined temperature range, (B) a polymer having a primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, An amine compound bonded to a hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and (C) an organic solvent. [II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and [III] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I] And a step of heating the coating film obtained in the step (ii) to obtain a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type to which orientation control ability is imparted, the above problem is solved by the method for producing a substrate having the liquid crystal alignment film .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing a substrate having a liquid crystal alignment film for a liquid crystal display device,

The present invention relates to a method of manufacturing a substrate having a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type. More particularly, the present invention relates to a novel method for manufacturing a liquid crystal display element having excellent exposure characteristics.

BACKGROUND ART Liquid crystal display devices are known as lightweight, thin and low power consumption display devices, and recently, they have been used for large-sized television applications and have achieved remarkable progress. The liquid crystal display element is constituted by sandwiching the liquid crystal layer by a pair of transparent substrates having electrodes, for example. In the liquid crystal display element, an organic film made of an organic material is used as a liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates.

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

Conventionally, a rubbing method is known as an alignment treatment method of a liquid crystal alignment film for imparting alignment control ability. The rubbing method is a method of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide, or polyimide on a substrate with a cloth such as cotton, nylon or polyester in a predetermined direction, To orient the liquid crystal. This rubbing method has been used in a manufacturing process of a conventional liquid crystal display element since a relatively stable liquid crystal alignment state can be realized easily. As the organic film used for the liquid crystal alignment film, a polyimide-based organic film having superior reliability and electrical characteristics such as heat resistance has been mainly selected.

However, in the rubbing method of rubbing the surface of the liquid crystal alignment film made of polyimide or the like, generation of oscillation or static electricity has been a problem in some cases. In addition, since the liquid crystal display element of recent years has a high precision and the surface of the liquid crystal alignment film can not be uniformly rubbed with the cloth due to the irregularity caused by the electrode or the switching active element for driving the liquid crystal on the corresponding substrate, There was no case.

Therefore, as another method of aligning the liquid crystal alignment film without rubbing, a photo alignment method is actively studied.

There are various methods for the photo alignment method, but anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is oriented in accordance with the anisotropy.

As a main photoalignment method, a photoalignment method of a decomposition type is known. For example, polarized ultraviolet rays are irradiated to the polyimide film, and anisotropic decomposition is generated by utilizing the polarization direction dependency of ultraviolet absorption of the molecular structure. Then, the liquid crystal is oriented by the polyimide left ungraded (see, for example, Patent Document 1).

In addition, a photo-crosslinking type or a photoisomerization type optical alignment method is also known. For example, polyvinyl cinnamate is used to irradiate polarized ultraviolet rays to cause a dimerization reaction (crosslinking reaction) at the double bond portions of two side chains parallel to the polarized light. Then, the liquid crystal is oriented in a direction perpendicular to the polarization direction (see, for example, Non-Patent Document 1). When a side chain polymer having azobenzene in the side chain is used, polarized ultraviolet light is irradiated to cause an isomerization reaction in the azobenzene moiety of the side chain parallel to the polarized light to orient the liquid crystal in a direction orthogonal to the polarization direction See, for example, Non-Patent Document 2).

As in the example described above, in the alignment treatment method of the liquid crystal alignment film by the photo alignment method, rubbing is unnecessary, and there is no fear of occurrence of oscillation or static electricity. In addition, it is possible to perform orientation treatment on a substrate of a liquid crystal display element having irregularities on its surface, which is a preferred method of alignment treatment of a liquid crystal alignment film in an industrial production process.

Japanese Patent Publication No. 3893659

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

As described above, the photo-alignment method requires no rubbing process itself as compared with the conventionally used rubbing method as an alignment treatment method of a liquid crystal display element, and thus has a great advantage. Compared with the rubbing method in which the alignment control ability is almost constant by rubbing, in the photo alignment method, the alignment control ability can be controlled by changing the irradiation amount of the polarized light. However, in the photo alignment method, when it is desired to achieve the same degree of alignment control ability as in the case of the rubbing method, a large amount of irradiated light is required, and stable alignment of liquid crystal may not be realized.

For example, in the decomposition-type photo-alignment method described in Patent Document 1 described above, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp with an output power of 500 W for 60 minutes, and a large amount of ultraviolet irradiation . Further, even in the case of the diminution type or optical isomerization type photo-alignment method, a large amount of ultraviolet light irradiation of several tens to several tens J may be required in some cases. Further, in the case of a photo-crosslinking or photo-isomerization photo-alignment method, thermal stability and optical stability of the liquid crystal alignment are inferior, so that there is a problem that orientation defects and display exposure occur when the liquid crystal display device is used. Particularly, in a liquid crystal display element of a transversely-field-driven type, liquid crystal molecules are switched in a plane, alignment deviation of the liquid crystal after the liquid crystal drive is likely to occur, and display exposure caused by AC drive becomes a big problem.

Therefore, in the photo alignment method, it is required to achieve high efficiency of alignment treatment and realization of stable liquid crystal alignment, and a liquid crystal alignment film and a liquid crystal alignment agent capable of highly imparting a high alignment control ability to the liquid crystal alignment film can be performed with high efficiency.

An object of the present invention is to provide a substrate having a liquid crystal alignment film for a liquid crystal display element of a transverse electric field drive type, which is imparted with an alignment control function with high efficiency and excellent in exposure characteristics, and a transverse electric field driven liquid crystal display element having the substrate.

It is another object of the present invention to provide a transverse electric field driving type liquid crystal device which absorbs ionic impurities in a liquid crystal at an interface of a liquid crystal alignment film and has an improved voltage holding ratio and a liquid crystal alignment film for the device .

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found the following inventions.

≪ 1 > (A) a photosensitive side chain polymer which exhibits liquid crystallinity in a predetermined temperature range,

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

(C) an organic solvent

≪ / RTI >

≪ 2 > The photosensitive resin composition according to < 1 >, wherein the component (A) has a photosensitive side chain that causes photo crosslinking, photoisomerization, or light free transition.

<3> The resin composition according to <1> or <2>, wherein the component (B) is a divalent organic group represented by the following formula A- [1]: wherein Y ₁₁ is an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group , And Y ₁₂ is a nitrogen-containing aromatic heterocyclic ring).

[Chemical Formula 1]

<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the component (A) has one kind of photosensitive side chain selected from the group consisting of the following formulas (1) to (6)

(2)

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

S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;

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

Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or a ring selected from the same or different 2 to 6 rings Are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , - CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

Y ₂ is a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, Each independently may be substituted with -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

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

X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO-CH═CH -, and when the number of X's is 2, X's may be the same or different;

Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are each independently -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH- Group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

q1 and q2 are 1 in one and 0 in the other;

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 having 5 to 8 carbon atoms, and combinations thereof; Is -CH = CH-CO-O- or -O-CO-CH = CH-, P or Q on the side bonded to -CH = CH- is an aromatic ring. When the number of P is 2 or more, P may be the same or different, and when Q is 2 or more, Qs may be the same or different;

l1 is 0 or 1;

l2 is an integer of 0 to 2;

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

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

(5) The positive resist composition according to any one of (1) to (3), wherein the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (7) to (10).

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

l represents an integer of 1 to 12;

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

n is an integer of 0 to 12 (provided that n is 0 and B is a single bond).

(3)

<6> The photosensitive resin composition according to any one of <1> to <3>, wherein the component (A) has one kind of photosensitive side chain selected from the group consisting of the following formulas (11) to (13)

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

[Chemical Formula 4]

<7> The photosensitive resin composition according to any one of <1> to <3>, wherein the component (A) has a photosensitive side chain represented by the following formula (14) or (15).

In the formula, A, Y ₁ , l, m ₁ and m 2 have the same definitions as above.

[Chemical Formula 5]

<8> The photosensitive resin composition according to any one of <1> to <3>, wherein the component (A) has a photosensitive side chain represented by the following formula (16) or (17).

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

[Chemical Formula 6]

<9> The photosensitive resin composition according to any one of <1> to <3>, wherein the component (A) has a photosensitive side chain represented by the following formula (18) or (19).

In the formula, A, B, Y ₁ , q ₁ , q 2, m ₁ , and m 2 have the same definitions as above.

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

(7)

<10> The photosensitive resin composition according to any one of <1> to <3>, wherein the component (A) has a photosensitive side chain represented by the following formula (20)

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

[Chemical Formula 8]

<11> The liquid crystal display according to any one of <1> to <10>, wherein the component (A) has at least one liquid crystal side chain selected from the group consisting of the following formulas (21) to (31) .

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

Y ₃ is a group selected from the group consisting of monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, nitrogen containing heterocyclic rings, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, Each hydrogen atom may be independently substituted with -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, A ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;

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

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

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

[Chemical Formula 9]

<12> [I] A process for forming a coating film by applying the composition described in any one of <1> to <11> on a substrate having a conductive film for driving a transverse electric field;

[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];

To obtain a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type to which orientation control ability is imparted.

<13> A substrate having a liquid crystal alignment film for a liquid crystal display device of the lateral electric field type manufactured by the method of <12>.

&Lt; 14 &gt; A transverse electric field driving type liquid crystal display element having the substrate of [13].

<15> preparing a substrate (first substrate) of the above <13>;

[I '] on the second substrate

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

(B) at least one member selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, an alkoxy group, an alkoxyalkyl group, an oxirane group, an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a trialkoxysilyl group, A crosslinkable compound having at least two substituents in one molecule, and

(C) an organic solvent

A step of applying a polymer composition to form a coating film;

Irradiating the coating film obtained in [II '] [I'] with polarized ultraviolet light; and

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

To obtain a liquid crystal alignment film having the alignment control ability, thereby obtaining a second substrate having the liquid crystal alignment film; and

[IV] a step of arranging the first and second substrates so that the liquid crystal alignment layers of the first and second substrates oppose each other through the liquid crystal to obtain a liquid crystal display element;

To obtain a transverse electric field driven liquid crystal display element.

<16> A transverse electric field driving type liquid crystal display device manufactured by the method of <15> above.

On the other hand, the following inventions were found out.

&Lt; P1 &gt; [I] (A) A photosensitive side chain polymer which exhibits liquid crystallinity in a predetermined temperature range,

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

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];

To obtain a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type to which orientation control ability is imparted.

<P2> In the above item <P1>, it is preferable that the component (A) has a photosensitive side chain which causes photo-crosslinking, optical isomerization or light-free transition.

<P3> the <P1> or in the <P2>, (B) component, the formula A- [1] (wherein, Y ₁₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon , And Y ₁₂ is a nitrogen-containing aromatic heterocyclic ring).

[Chemical formula 10]

<P4> The positive resist composition according to any one of <P1> to <P3>, wherein the component (A) has one kind of photosensitive side chain selected from the group consisting of the following formulas (1) to (6) .

(11)

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

S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;

T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;

Y ₁ represents a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings and alicyclic hydrocarbons having 5 to 8 carbon atoms, or the same or different 2 to 6 And the hydrogen atoms bonded to them are each independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

Y ₂ is a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, and hydrogen atoms Each independently may be substituted with -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

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

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

Cou is a coumarin group, or represents a 6-coumarin-7-yl group, a hydrogen atom bonded to them, is independently -NO _2, -CN, respectively, _{-CH = C (CN) 2,} -CH = CH-CN, A halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

q1 and q2 are one in one and zero in the other;

q3 is 0 or 1;

P and Q each independently represent a group selected from the group consisting of a single bond, a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, to be. Provided that when X is -CH = CH-CO-O- or -O-CO-CH = CH-, then P or Q on the side to which -CH = CH- is an aromatic ring;

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

<P5> The positive resist composition according to any one of <P1> to <P3>, wherein the component (A) has one kind of photosensitive side chain selected from the group consisting of the following formulas (7) to (10) .

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

l represents an integer of 1 to 12;

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

n is an integer of 0 to 12 (provided that n is 0 and B is a single bond).

[Chemical Formula 12]

It is preferable that the component (A) in any one of the above items <P1> to <P3> has any one photosensitive side chain selected from the group consisting of the following formulas (11) to (13) .

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

[Chemical Formula 13]

<P7> It is preferable that the component (A) in any one of <P1> to <P3> has a photosensitive side chain represented by the following formula (14) or (15).

In the formula, A, Y ₁ , X, l, m 1 and m 2 have the same definitions as above.

[Chemical Formula 14]

<P8> It is preferable that the component (A) in any one of <P1> to <P3> has a photosensitive side chain represented by the following formula (16) or (17).

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

[Chemical Formula 15]

<P9> It is preferable that the component (A) has a photosensitive side chain represented by the following formula (18) or (19) in any one of <P1> to <P3>.

In the formula, A, B, Y ₁ , q ₁ , q 2, m ₁ , and m 2 have the same definitions as above.

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

[Chemical Formula 16]

<P10> It is preferable that the component (A) in any one of <P1> to <P3> has a photosensitive side chain represented by the following formula (20).

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

[Chemical Formula 17]

<P11> The liquid crystal display device according to any one of <P1> to <P10>, wherein the component (A) has a liquid crystal side chain selected from the group consisting of the following formulas (21) to (31) good.

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

Y ₃ is a group selected from the group consisting of monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, nitrogen containing heterocyclic rings, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, Each hydrogen atom may be independently substituted with -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;

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

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

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

[Chemical Formula 18]

<P12> A substrate having a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type manufactured by any one of <P1> to <P11>.

<P13> A transverse electric field driving type liquid crystal display element having the substrate of the above <P12>.

<P14> preparing a substrate (first substrate) of the above <P12>;

[I '] on the second substrate

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

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

(C) an organic solvent

A step of applying a polymer composition to form a coating film;

Irradiating the coating film obtained in [II '] [I'] with polarized ultraviolet light;

And

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

To obtain a liquid crystal alignment film having the alignment control ability, and obtaining a second substrate having the liquid crystal alignment film; and

[IV] a step of opposing the first and second substrates so that the liquid crystal alignment layers of the first and second substrates are opposed to each other through the liquid crystal to obtain a liquid crystal display element;

To obtain a transverse electric field driven liquid crystal display element.

&Lt; P15 &gt; A transverse electric field driven liquid crystal display device manufactured by the above &lt; P14 &gt;.

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

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

(C) an organic solvent

A liquid crystal alignment layer for liquid crystal display element, and a liquid crystal alignment layer for liquid crystal alignment layer.

Wherein the component (B) is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group and Y ₁₂ is a divalent organic group represented by the formula A- [1] wherein Y ₁₁ is an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, A nitrogen-containing aromatic heterocyclic ring).

According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type, which has high controllability of alignment control with high efficiency and excellent in exposure characteristics, and a transverse electric field driven liquid crystal display device having the substrate.

Since the transverse electric-field-driven liquid crystal display device manufactured by the method of the present invention has the alignment control ability at a high efficiency, the display characteristics are not hindered even when the liquid crystal display device is continuously driven for a long period of time.

Further, according to the present invention, it is possible to provide a transversely-field-driven liquid crystal device having an improved voltage holding ratio by adsorbing ionic impurities in the liquid crystal at the liquid crystal alignment film interface, and a liquid crystal alignment film for the device.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing an example of a schematic illustration of anisotropic introduction treatment in the process for producing a liquid crystal alignment film used in the present invention, in which a crosslinkable organic group is used as a photosensitive side chain, Fig.
Fig. 2 is an example of a schematic illustration of an introduction process of anisotropy in the process for producing a liquid crystal alignment film used in the present invention, in which a cross-linkable organic group is used as a photosensitive side chain, and when the introduced anisotropy is large Fig.
Fig. 3 is an example of a schematic illustration of an introduction process of anisotropy in the process for producing a liquid crystal alignment film used in the present invention, in which an organic group causing fresnel transition or isomerization is used as a photosensitive side chain, And the anisotropy is small.
Fig. 4 is an example of a schematic illustration of an introduction process of anisotropy in the process for producing a liquid crystal alignment film used in the present invention, in which an organic group causing fresnel transition or isomerization is used as a photosensitive side chain, And the anisotropy is large.

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

The polymer composition used in the production method of the present invention has a photosensitive side chain type polymer capable of exhibiting liquid crystallinity (hereinafter, simply referred to as a side chain type polymer), and a coating film obtained by using the above polymer composition is a liquid crystal Is a film having a photosensitive side chain type polymer capable of expressing the properties of the polymer. The coating film is subjected to orientation treatment by polarized irradiation without rubbing treatment. After the polarized light irradiation, the side-chain polymer film is heated to form a coating film (hereinafter, also referred to as a liquid crystal alignment film) imparted with orientation control capability. At this time, a slight anisotropy expressed by polarized light is a driving force, and the liquid crystalline side chain polymer itself is efficiently rearranged by self-organization. As a result, a highly efficient alignment treatment as a liquid crystal alignment film can be realized, and a liquid crystal alignment film having high alignment control capability can be obtained.

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

&Lt; Manufacturing Method of Substrate Having Liquid Crystal Alignment Film &gt; &lt; Production Method of Liquid Crystal Display Element &

A method of manufacturing a substrate having a liquid crystal alignment film of the present invention includes:

[I] A photosensitive resin composition comprising: (A) a photosensitive side chain polymer which exhibits liquid crystallinity in a predetermined temperature range;

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

(C) an organic solvent

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];

Respectively.

By this process, it is possible to obtain a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type to which alignment control ability is imparted, and a substrate having the liquid crystal alignment film can be obtained.

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

The second substrate may be a substrate which does not have a conductive film for driving a transversal electric field, instead of a substrate having a conductive film for driving a transversal electric field, but the steps [I] to [III] The second substrate having the liquid crystal alignment film having the alignment control ability can be obtained by using the steps [I '] to [III'] in this specification for convenience .

A method of manufacturing a transverse electric field driven liquid crystal display element,

[IV] a step of arranging the first and second substrates obtained above so as to oppose each other with the liquid crystal alignment layer facing the liquid crystal alignment layers of the first and second substrates to obtain a liquid crystal display element;

Respectively. As a result, a transverse electric field driven liquid crystal display element can be obtained.

The respective steps [I] to [III] and [IV] of the production method of the present invention will be described below.

&Lt; Process [I] &gt;

In the step [I], a photosensitive side-chain type polymer that exhibits liquid crystallinity in a predetermined temperature range is formed on a substrate having a conductive film for transverse electric field drive, a compound having one primary amino group and one nitrogen- , And an amine compound in which the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and an organic solvent is applied to form a coating film.

<Substrate>

The substrate is not particularly limited, but when the liquid crystal display element to be manufactured is a transmissive type, it is preferable that a substrate having high transparency is used. In this case, there is no particular limitation, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used.

Also, considering the application to a reflective liquid crystal display device, an opaque substrate such as a silicon wafer can be used.

&Lt; Conductive film for driving a transverse electric field &

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

When the liquid crystal display element is a transmissive type, ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide) can be used as the conductive film. However, the conductive film is not limited to these.

In the case of a reflection-type liquid crystal display element, a material for reflecting light such as aluminum may be used as the conductive film, but the present invention is not limited thereto.

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

&Lt; Polymer composition &gt;

The polymer composition is applied onto a substrate having a conductive film for driving a transverse electric field, in particular, on a conductive film.

(A) a photosensitive side-chain polymer which exhibits liquid crystallinity in a predetermined temperature range, (B) a polymer having one primary amino group and one nitrogen-containing aromatic heterocyclic ring in the molecule, An amine compound in which the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and (C) an organic solvent.

<< (A) Side chain type polymer >>

(A) is a photosensitive side chain type polymer which exhibits liquid crystallinity in a predetermined temperature range.

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

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

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

The side chain type polymer (A) has a side chain having photosensitivity to the main chain, and may react with light to cause a crosslinking reaction, an isomerization reaction, or a light free electric potential. The structure of the side chain having photosensitivity is not particularly limited, but a structure that causes a crosslinking reaction or a light-free potential in response to light is preferable, and it is more preferable to cause a crosslinking reaction. In this case, even when exposed to external stress such as heat, the realized orientation control ability can be stably maintained for a long period of time. The structure of the photosensitive side chain type polymer membrane capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable that the structure has a mesogen component which is rigid in the side chain structure. In this case, when the side chain type polymer is used as the liquid crystal alignment film, a stable liquid crystal alignment can be obtained.

The structure of the polymer includes, for example, a main chain and a side chain bonded to the main chain, and the side chain thereof is bonded to a mesogen component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group or an azobenzene group, A structure having a photosensitive group which is bonded to the tip and reacts with light to perform a crosslinking reaction or an isomerization reaction, or a structure having a main chain and a side chain bonded to the main chain, the side chain of which may be a mesogen component, And a phenylbenzoate group having a phenylbenzoate group.

More specific examples of the structure of the photosensitive side chain type polymer membrane capable of exhibiting liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate,? -Methylene-? -Butyrolactone, styrene, A structure having a main chain composed of at least one kind selected from the group consisting of a radical polymerizable group such as vinyl, maleimide and norbornene and a siloxane and a side chain comprising at least one of the following formulas (1) to (6) .

[Chemical Formula 19]

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

S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;

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

Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or a ring selected from the same or different 2 to 6 rings Are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , - CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

Y ₂ is a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, Each independently may be substituted with -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

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

X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO-CH═CH -, and when the number of X's is 2, X's may be the same or different;

Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are each independently -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH- Group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

q1 and q2 are 1 in one and 0 in the other;

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 having 5 to 8 carbon atoms, and combinations thereof; Is -CH = CH-CO-O- or -O-CO-CH = CH-, P or Q on the side bonded to -CH = CH- is an aromatic ring. When the number of P is 2 or more, P may be the same or different, and when Q is 2 or more, Qs may be the same or different;

l1 is 0 or 1;

l2 is an integer of 0 to 2;

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

When l1 is 1, B is also a single bond when T is 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 one of the photosensitive side chains selected from the group consisting of the following formulas (7) to (10).

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

l represents an integer of 1 to 12;

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

n is an integer of 0 to 12 (provided that n is 0 and B is a single bond).

[Chemical Formula 20]

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

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

[Chemical Formula 21]

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

In the formula, A, Y ₁ , l, m ₁ and m 2 have the same definitions as above.

[Chemical Formula 22]

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

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

(23)

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

In the formula, A, B, Y ₁ , q ₁ , q 2, m ₁ , and m 2 have the same definitions as above.

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

&Lt; EMI ID =

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

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

(25)

The side chain type polymer (A) preferably has any one kind of liquid crystal side chain selected from the group consisting of the following formulas (21) to (31).

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

Y ₃ is a group selected from the group consisting of monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, nitrogen containing heterocyclic rings, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, Each hydrogen atom may be independently substituted with -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, A ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;

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

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

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

(26)

<< Preparation of Photosensitive Side Chain Polymer >>

The photosensitive side chain type polymer capable of exhibiting liquid crystallinity can be obtained by polymerizing a photoreactive side chain monomer having a photosensitive side chain and a liquid crystal side chain monomer.

[Photoreactive side chain monomer]

The photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at a side chain portion of the polymer when the polymer is formed.

As the photoreactive group of the side chain, the following structures and derivatives thereof are preferable.

(27)

More specific examples of the photoreactive side chain monomers include monomers such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate,? -Methylene-? -Butyrolactone, styrene, vinyl, maleimide and norbornene A polymerizable group composed of at least one kind selected from the group consisting of a radical polymerizable group and a siloxane and a photosensitive side chain comprising at least one of the above-mentioned formulas (1) to (6) (14) or (15), a photosensitive side chain composed of at least one of the above-mentioned formulas (7) to (10), a photosensitive side chain comprising at least one of the formulas (11) The photosensitive side chain represented by the formula (16) or (17), the photosensitive side chain represented by the formula (18) or (19) and the photosensitive side chain represented by the formula (20).

The present invention relates to novel compounds (1) to (11) represented by the following formulas (1) to (11) as photoreactive and / or liquid crystalline side chain monomers, To give the compounds (12) to (17).

In the formula, R represents a hydrogen atom or a methyl group; S represents an alkylene group having a carbon number of 2 ~ ^10; R 10 represents a Br or CN; S represents an alkylene group having a carbon number of 2 ~ 10; u is 0 or 1 And Py represents a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group. V represents 1 or 2;

(28)

[Chemical Formula 29]

(30)

[Liquid crystalline side chain monomer]

The liquid crystal side chain monomer is a monomer from which the polymer originating from the monomer can express liquid crystallinity and the polymer can form a mesogen group at a side chain site.

As the mesogen group of the side chain, there may be used a group which has a mesogen structure alone such as biphenyl or phenylbenzoate, or a mesogen structure by hydrogen bonding of side chains such as benzoic acid. The mesogen group of the side chain is preferably the following structure.

(31)

More specific examples of the liquid crystalline side chain monomers include monomers such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate,? -Methylene-? -Butyrolactone, styrene, vinyl, maleimide and norbornene A radical polymerizable group and a siloxane, and a side chain comprising at least one of the above-mentioned formulas (21) to (31).

The side chain type polymer (A) can be obtained by a polymerization reaction of a photoreactive side chain monomer that exhibits the liquid crystallinity described above. In addition, copolymerization of a photoreactive side chain monomer and a liquid crystal side chain monomer that do not exhibit liquid crystallinity and copolymerization of a photoreactive side chain monomer and a liquid crystal side chain monomer that exhibit liquid crystallinity can be obtained. Further, it can be copolymerized with other monomers within a range that does not inhibit the liquid crystalline property.

As other monomers, for example, industrially available monomers capable of radical polymerization can be given.

Specific examples of other monomers include unsaturated carboxylic acids, acrylic acid ester compounds, methacrylic acid ester 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, and fumaric acid.

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, Acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate, 2-ethoxy ethyl acrylate, 2-ethoxyethyl acrylate, Methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate , And 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate , Phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, Methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl methacrylate, 2-ethylhexyl methacrylate, Adamantyl methacrylate, 2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate. Cyclic ethers such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate and (3-ethyl-3-oxetanyl) methyl (Meth) acrylate compound having a group can also be used.

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

Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

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

The method of producing the side chain type polymer of the present embodiment is not particularly limited, and a general-purpose method which is handled industrially can be used. Specifically, it can be produced by cation polymerization, radical polymerization or anionic polymerization using a vinyl group of a liquid crystal side chain monomer or a photoreactive side chain monomer. Of these, radical polymerization is particularly preferable from the viewpoints of ease of reaction control and the like.

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

The radical thermal polymerization initiator is a compound which generates a radical by heating at a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, diacyl peroxides such as acetyl peroxide and benzoyl peroxide and hydroperoxides such as (Di-tert-butyl peroxide, dicumyl peroxide, di-lauroyl peroxide, etc.), peroxyketal (dibutyl peroxide, (Peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfate Azo compounds such as azobisisobutylonitrile and 2,2'-di (2-hydroxyethyl) azobisisobutyronitrile, and the like can be used in combination with an organic peroxide such as potassium persulfate, potassium persulfate, sodium persulfate, ammonium persulfate, . These radical thermal polymerization initiators may be used singly or in combination of two or more.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such a radical photopolymerization initiator include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone , 2-ethyl anthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, iso Benzoinone, 2-methyl-1- [4- ((2, 3-diethoxybenzoyl) Methyl 4-methylthio) phenyl] -2-morpholinopropane-1-one, ethyl 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Dimethylaminobenzoic acid isoamyl, 4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxysty Bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis Bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s- triazine, 4- [pN, N-di (ethoxycarbonylmethyl ) - 2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) (Trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p- dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl- '-Bimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) 2,2'-bis (2,4-dichlo 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2' bis (2,4-dibromophenyl) -Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl- (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1 (3-methyl-2-morpholinopropionyl) carbazole, (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium , 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, Di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) Benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2- (3-methyl- Ylidene) -1-naphthalen-2-yl-ethanone, or 2- (3- Butyl-1,3-benzothiazol -2 (3H) - ylidene) -1- (2-benzoyl and the like) ethanone. These compounds may be used alone or in combination of two or more.

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

The organic solvent used in the polymerization reaction of the photosensitive side chain type polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the resulting polymer dissolves. Specific examples thereof are given below.

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, But are not limited to, pyridine, dimethyl sulfone, hexamethyl sulfoxide,? -Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, Ketones, 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 mono Butyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate Diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, N-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, isopropanol, n-butanol, isobutanol, Propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propyl acetate Methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, Propyl propionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy- Propane amide, 3-butoxy-N, N-dimethylpropanamide and the like.

These organic solvents may be used alone or in combination. In addition, a solvent which does not dissolve the produced polymer may be used in combination with the above-described organic solvent within a range in which the produced polymer is not precipitated.

Further, in the radical polymerization, oxygen in the organic solvent causes the polymerization reaction to be inhibited. Therefore, it is preferable to use an organic solvent which has been degassed to the extent possible.

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

In the above-mentioned radical polymerization reaction, when the ratio of the radical polymerization initiator to the monomer is small, the molecular weight of the obtained polymer is small, and if it is small, the molecular weight of the obtained polymer is large. To 10 mol%. In the polymerization, various monomer components, solvents, initiators, etc. may be added.

[Recovery of Polymer]

In the case of recovering the resulting polymer from the reaction solution of the photosensitive side chain type polymer capable of exhibiting liquid crystallinity obtained by the above-described reaction, the reaction solution may be put into a poor solvent and the polymer may be precipitated . Examples of the poor solvent for use in the precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, . The polymer precipitated by charging into a poor solvent can be recovered by filtration and then dried at room temperature or under reduced pressure or under normal pressure. In addition, by repeating the operation of redissolving the polymer recovered and recovered in an organic solvent and re-precipitating and recovering the polymer twice to 10 times, impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and when three or more poor solvents selected from these are used, the purification efficiency is further increased, which is preferable.

The molecular weight of the side chain type polymer (A) of the present invention is preferably in the range of, for example, 1, 2, 3, 4, 5, Preferably from 2,000 to 1,000,000, and more preferably from 5,000 to 100,000.

[Preparation of polymer composition]

The polymer composition used in the present invention is preferably prepared as a coating liquid so as to be suitable for formation of a liquid crystal alignment film. That is, the polymer composition used in the present invention is preferably prepared as a solution in which a resin component for forming a resin coating is dissolved in an organic solvent. Here, the resin component is a resin component containing a photosensitive side chain type polymer capable of exhibiting the liquid crystallinity described above. At this time, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

In the polymer composition of the present embodiment, the above-mentioned resin component may be all of the photosensitive side chain type polymers capable of exhibiting the above-described liquid crystallinity, but in addition to the above, Of other polymer may be mixed. At that time, the content of the other polymer in the resin component is from 0.5% by mass to 80% by mass, and preferably from 1% by mass to 50% by mass.

Such another polymer includes, for example, a polymer which is composed of poly (meth) acrylate, polyamic acid, polyimide or the like and is not a photosensitive side chain type polymer capable of exhibiting liquid crystallinity.

<Amine compound>

The polymer composition for use in the present invention is a polymer composition containing a specific amine compound, specifically, a compound having one primary amino group and one nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group Amine compound.

The specific amine compound is not particularly limited as long as it exhibits the following effects i) and / or ii) when the polymer composition used in the present invention forms a liquid crystal alignment film. i) adsorbing ionic impurities in the liquid crystal at the liquid crystal alignment film interface and / or ii) exhibiting an improved voltage retention rate.

The amount of the specific amine compound is not particularly limited as long as it exhibits the above effect, but it is preferably 0.01 to 10 parts by mass, and preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the polymer composition used in the present invention.

Specific examples of the aliphatic hydrocarbon group include a linear alkylene group, an alkylene group having a branched structure, and a divalent hydrocarbon group having an unsaturated bond. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.

Specific examples of the divalent non-aromatic cyclic hydrocarbon group include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, A cyclododecane ring, a cyclododecane ring, a cyclododecane ring, a cyclododecane ring, a cyclododecane ring, a cyclotodecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, , A tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring, and the like. Preferably a ring of 3 to 20 carbon atoms, more preferably a ring of 3 to 15 carbon atoms, and more preferably a ring of non-aromatic cyclic hydrocarbon group of 3 to 10 carbon atoms.

The nitrogen-containing aromatic heterocyclic ring contained in the amine compound is a group consisting of the following formulas [20a], [20b] and [20c] (wherein Z ₂ is a linear or branched alkyl group having 1 to 5 carbon atoms) Is preferably an aromatic cyclic hydrocarbon containing at least one, preferably one to four, structures selected from the group consisting of

(32)

Specific examples thereof include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, A pyrimidine ring, a pyrazoline ring, a pyrazoline ring, a pyrazolidine ring, a triazazole ring, a pyrazine ring, a benzimidazole ring, a benzimidazole ring, a quinoline ring, a phenanthroline ring, an indole ring, quinoxaline A ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an acridine ring, and the like. The carbon atom of these nitrogen-containing aromatic heterocyclic rings may have a substituent containing a hetero atom.

More preferred amine compounds are represented by the following formula A- [1] wherein Y ₁₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y ₁₂ is a nitrogen-containing aromatic heterocyclic ring Amine compound.

In the formula A- [1], Y ₁₂ is not particularly limited as long as it is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

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The preferable Y ₁₁ in the formula A- [1] is a divalent organic group having one kind selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. As the non-aromatic cyclic hydrocarbon group, there may be mentioned the structures described above. Y ₁₁ is more preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms such as an aliphatic hydrocarbon group, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, Undecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring and the like. Y ₁₁ is particularly preferably a linear or branched alkylene group having 1 to 10 carbon atoms.

In addition, -CH ₂ - in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in Y ₁₁ is preferably -O-, -NH-, -CO-O-, -O-CO -, -CO-NH-, -S ( O) 2 -NH-CO-, -CO-, -S-, -, -CF 2 -, -C (CF 3) 2 -, -C (CH 3) _{2 -, -Si (CH 3)} 2 -, -O-Si (CH 3) 2 -, -Si (CH 3) 2 -O-, -O-Si (CH 3) 2 -O-, 2 -valent ring Or a heterocyclic ring. The hydrogen atom bonded to any carbon atom may be substituted with a linear or branched alkylene group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, do.

Specific examples of the bivalent cyclic hydrocarbon group include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a phenylene ring, a cyclopropane ring, , Cyclopentane ring, cyclohexane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclododecane ring, cyclododecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, A cyclohexadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclooctadecane ring, a cyclononadecane ring, a cyclooctadecane ring, a cyclooctanoic acid ring, a tricycloicoic acid ring, a tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, A ring, an adamantane ring, and the like.

Examples of the divalent heterocyclic ring include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring A thiadiazole ring, a benzimidazole ring, a benzoimidazole ring, a quinoline ring, a phenanthroline ring, a thiadiazole ring, a thiadiazole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, , An indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an acridine ring, and the like.

Y ₁₂ in the formula A- [1] is a nitrogen-containing aromatic heterocyclic ring and is at least one selected from the group consisting of the formulas [20a], [20b] and [20c] Aromatic ring-containing hydrocarbons. Specific examples thereof include the structures described above. Of these, preferred are pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole ring, quinoxaline ring, Azepine ring, diazepine ring, naphthyridine ring, phenazine ring, phthalazine ring are preferable.

Further, in view of ease of electrostatic interaction, such as a nitrogen-containing aromatic heterocyclic rings and a particular polyimide salts of carboxyl groups and forming hydrogen bond in the, Y ₁₁ is formula [20a], equation [20b] is contained in Y _12, and It is preferably bonded to a substituent which is not adjacent to the formula [20c].

The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₂ in the formula A- [1] may have a halogen atom and / or a substituent of an organic group, and the organic group may be heteroatom such as an oxygen atom, a sulfur atom, Atoms.

Formula A- combination of preferred Y ₁₁ and Y ₁₂ in [1], Y is _11, one selected from the group consisting of non-aromatic cyclic hydrocarbon group of 1 to 20 carbon atoms and an aliphatic hydrocarbon group having 3 to 20 carbon atoms in the And Y ₁₂ is a divalent organic group having a substituent selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, Benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring, or phthalazine ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₂ may have a substituent group of a halogen atom and / or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

More preferably, the amine compound represented by the following formula A- [2]: wherein Y ₁₃ represents a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms, Y ₁₄ represents a single bond or -O -, -NH-, -S-, -SO ₂ - or a divalent organic group having 1 to 19 carbon atoms, and the sum of the carbon atoms of Y ₁₃ and Y ₁₄ is 1 to 20. Y ₁₅ is a nitrogen-containing An aromatic heterocyclic ring).

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Y ₁₃ in the formula A- [2] is a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms. Specific examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, A cyclopentadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclooctadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, A naphthalene ring, a nonadecane ring, a cyclohexanoic acid ring, a tricycloic acid ring, a tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring and the like. More preferably a linear or branched alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, A cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring, and an adamantane ring. And particularly preferably a linear or branched alkylene group having 1 to 10 carbon atoms.

-CH ₂ - in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in Y ₁₃ is preferably -O-, -NH-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -S-, -S (O) 2 -, -CF 2 -, -C (CF 3) 2 -, -C (CH 3) 2 - , -Si (CH ₃ ) ₂ -, -O-Si (CH ₃ ) ₂ -, -Si (CH ₃ ) ₂ -O-, -O-Si (CH ₃ ) ₂ -O- and a divalent cyclic hydrocarbon Or a heterocyclic ring. The hydrogen atom bonded to an arbitrary carbon atom may be substituted with a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, or a hydroxyl group . The cyclic hydrocarbon group and the heterocyclic ring as used herein have the same meanings as defined for Y ₁₁ in the formula A- [1].

Y ₁₄ in the formula A- [2] is a single bond or a divalent organic group of -O-, -NH-, -S-, -SO ₂ - or a C 1-20 alkyl group. The divalent organic group having 1 to 19 carbon atoms is a divalent organic group having 1 to 19 carbon atoms and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or the like. Specific examples of such Y &lt; ₁₄ &gt; are given below.

For example, a single bond, -O-, -NH-, -S-, -SO ₂ -, a hydrocarbon group of 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO- _{-NH-CO-, -CO-, -CF 2} -, -C (CF 3) 2 -, -CH (OH) -, -C (CH 3) 2 -, -Si (CH 3) 2 -, - O-Si (CH ₃ ) ₂ -, -Si (CH ₃ ) ₂ -O-, -O-Si (CH ₃ ) ₂ -O-, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, A cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cyclohexadecane ring, a cyclohexadecane ring, a cycloheptane ring, a cycloheptane ring, a cycloheptane ring, a cycloheptane ring, , A cyclooctadecane ring, a cyclononadecane ring, a cyclooic acid ring, a tricycloicoic acid ring, a tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring, a benzene ring , A naphthalene ring, a tetrahydronaphthalene ring, An imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an imidazole ring, an imidazole ring, an imidazole ring, a pyrene ring, an anthracene ring, a phenanthrene ring, a phenanthrene ring, A pyrimidine ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, a purine ring, a thiadiazole ring, a pyridazine ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, An oxadiazole ring, an oxidine ring, an oxazole ring, a piperazine ring, a piperidine ring, a dioxane ring, an oxadiazole ring, an oxadiazole ring, an oxadiazole ring, an oxidine ring, A ring, a morpholine ring, and the like. As Y ₁₄ may contain two or more of them.

As specific examples of these two or more species,

And the like.

In the formula A- [2], Y ₁₅ is a nitrogen-containing aromatic heterocyclic ring and is the same as defined for Y _{12 in} the formula A- [1]. Specific examples thereof include the same structures as those of Y ₁₂ described above. Of these, preferred are pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole ring, quinoxaline ring, An azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring are preferable.

Further, in view of ease of electrostatic interaction, such as a nitrogen-containing aromatic heterocyclic rings and a particular polyimide salts of carboxyl groups and forming hydrogen bond in the, Y ₁₄ is that equation [20a], formula [20b] or a group represented by the formula contained in Y ₁₅ Is bonded to the carbon atom not adjacent to [20c].

The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₅ in the formula A- [2] may have a halogen atom and / or a substituent of an organic group, and the organic group may be a hetero atom such as an oxygen atom, a sulfur atom, .

Formula A- [2] Y _13, Y ₁₄ and Y ₁₅ are a preferred combination of, Y is _13, 1 to 10 carbon atoms in the straight-chain or branched alkylene group, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring in, A cycloheptane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cyclododecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring or an adamantane ring , Y ₁₄ is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms,

A cyclopentane ring, a cyclopentane ring, a cyclopentane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cyclododecane ring, a cyclododecane ring, a norbornene ring, A benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring and a phenylene ring, Y ₁₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, A pyrimidine ring, a pyrimidine ring, a pyridazine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a benzimidazole ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, Or a phthalazine ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₅ may have a substituent group of a halogen atom and / or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

A more preferable combination of Y ₁₃ , Y ₁₄ and Y _{15 in} the formula A- [2] is that Y ₁₃ is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring , A cyclohexane ring, a cycloheptane ring, a norbornene ring, or an adamantane ring, Y ₁₄ represents a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms,

A cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a fluorene ring ring, anthracene ring, phenanthrene and the ring, or phenacyl alkylene ring, Y ₁₅ is, pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine A benzimidazole ring, a benzimidazole ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₅ may have a substituent group of a halogen atom and / or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

A more preferable combination of Y ₁₃ , Y ₁₄ and Y _{15 in} the formula A- [2] is that Y ₁₃ is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring , Or a cyclohexane ring, Y ₁₄ is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms,

A cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring, or an anthracene ring, Y ₁₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring or a benzimidazole ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₅ may have a substituent group of a halogen atom and / or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

A particularly preferable combination of Y ₁₃ , Y ₁₄ and Y _{15 in} the formula A- [2] is that Y ₁₃ is a linear or branched alkylene group, a cyclobutane ring or a cyclohexane ring having 1 to 5 carbon atoms, Y ₁₄ is, a single bond, -O-, -CO-O-, -O -CO-, -CO-NH-, -NH-CO-, -CH (OH) -, benzene ring, naphthalene ring, fluorene ring , Or an anthracene ring, and Y ₁₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₅ may have a substituent group of a halogen atom and / or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

Specific examples of the specific amine compound of the component (B) of the present invention include the compounds of M1 to M156.

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(36)

(37)

(38)

[Chemical Formula 39]

(40)

As a more preferable compound,

to be.

<Organic solvent>

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

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N- Dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide,? -Butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, Amide, 3-butoxy-N, N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, But are not limited to, hexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol- Ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, Propylene 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 Methoxybutyl acetate, tripropylene glycol methyl ether, and the like. These may be used alone or in combination.

The polymer composition used in the present invention may contain components other than the above components (A), (B) and (C). Examples thereof include, but are not limited to, a solvent or a compound that improves film thickness uniformity or surface smoothness when the polymer composition is applied, a compound that improves adhesion between the liquid crystal alignment film and the substrate, and the like.

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

Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, , Dipropylene glycol monoacetate monoethyl Propylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, Hexane, n-pentane, n-pentane, n-pentane, n-pentane, n-pentane, n-pentane, n-butane, Methyl propionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, Methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1- 2-propanol, 1-butoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- Lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, lactic acid ethyl ester-2-acetate, dipropylene glycol, 2- (2- ethoxypropoxy) propanol, And a solvent having a low surface tension such as an ester.

These poor solvents may be used alone or in combination. In the case of using the solvent as described above, it is preferably 5% by mass to 80% by mass, more preferably 20% by mass, and most preferably 20% by mass, of the entire solvent so as not to significantly lower the solubility of the solvent contained in the polymer composition. Mass% to 60 mass%.

Examples of the compound that improves film thickness uniformity and surface smoothness include fluorinated surfactants, silicone surfactants, and nonionic surfactants.

More specifically, it is possible to use, for example, EFTOT (registered trademark) 301, EF303, EF352 (manufactured by TOKEM PRODUCTS CO., LTD.), Megapack (registered trademark) F171, F173, R- SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seiyaku Chemical Co., Ltd.), FC431 (manufactured by Sumitomo 3M Company), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Co., ) And the like. The use ratio of these surfactants is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass based on 100 parts by mass of the resin component contained in the polymer composition.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment layer and the substrate include the following functional silane-containing compounds and the like.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-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- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, and the like.

In addition to the enhancement of the adhesion between the substrate and the liquid crystal alignment film, for the purpose of preventing deterioration of the electric characteristics due to the backlight when the liquid crystal display element is constituted, additives such as the following phenoplast series or epoxy group- . Specific phenoplast additives are shown below, but the structure is not limited thereto.

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Specific examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl Glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6- Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) Cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.

When a compound improving the adhesion with the substrate is used, the amount thereof to be used is preferably 0.1 part by mass to 30 parts by mass, more preferably 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the resin component contained in the polymer composition Wealth. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected. If the amount is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

A photosensitizer may also be used as an additive. Colorless sensitizer and triplet sensitizer are preferable.

Examples of the photosensitizer include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscumarin, aromatic 2- (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, (2-benzoylmethylene-3-methyl- beta -naphthothiazoline, 2- (beta -naphthoylmethylene) -3-methylbenzothiazoline, 2- (alpha -naphthoylmethylene) -3 -Methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methylbenzothiazoline, 2- Methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene- Oxazoline, 2- (β-naphthoylmethylene) 2- (4-biphenoylmethylene) -3-methylbenzooxazoline, 2- (? -Naphthoylmethylene) -3-methylbenzooxazoline, 2- ) -3-methyl- beta -naphthooxazoline, 2- (4-biphenoylmethylene) -3-methyl- beta -naphthoxazoline, 2- (p- fluorobenzoylmethylene) Nitro-aniline, 2,4,6-trinitroaniline) or nitro-acenaphthene (5-nitro-acenaphthene), (2 - [(m- (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalene methanol, 2-naphthalene methanol, 2- Naphthalenecarboxylic acid, 9-anthracene methanol, and 9-anthracenecarboxylic acid), benzopyran, azoindolizine, merocoumarin and the like.

Preferred are aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonylbiscumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.

The polymer composition may contain, in addition to the above-mentioned ones, a dielectric substance or a conductive substance, or a liquid crystal alignment film, for the purpose of changing electric characteristics such as dielectric constant and conductivity of the liquid crystal alignment film, A cross-linking compound may be added for the purpose of increasing the hardness and density of the film.

The method of applying the above-described polymer composition onto a substrate having a conductive film for driving a transverse electric field is not particularly limited.

As a coating method, a method generally carried out by screen printing, offset printing, flexographic printing, inkjet printing or the like is generally used. Examples of other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method (spin coating method), a spray method, and the like.

After the polymer composition is applied onto a substrate having a conductive film for driving a transverse electric field, the polymer composition is heated to 50 to 200 占 폚, preferably 50 to 150 占 폚, by heating means such as a hot plate, a heat circulation type oven or an IR Lt; RTI ID = 0.0 &gt; C, &lt; / RTI &gt; The drying temperature at this time is preferably lower than the liquid crystal phase temperature of the side chain type polymer.

When the thickness of the coating film is too large, the power consumption of the liquid crystal display element is deteriorated. When the thickness of the coating film is too thin, the reliability of the liquid crystal display element may be deteriorated, and therefore preferably 5 nm to 300 nm, more preferably 10 nm ~ 150 nm.

It is also possible to set a step of cooling the substrate on which the coated film has been formed to the room temperature after the [I] process and before the subsequent [II] process.

&Lt; Process [II] &gt;

In the step [II], polarized ultraviolet rays are irradiated onto the coating film obtained in the step [I]. When polarized ultraviolet rays are irradiated to the film surface of the coating film, polarized ultraviolet rays are irradiated to the substrate through a polarizer from a certain direction. As ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of the coating film to be used. For example, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selectively used so as to cause photo-crosslinking reaction selectively. As ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The irradiation amount of the polarized ultraviolet ray depends on the coating film to be used. The irradiation dose is the amount of the polarized ultraviolet light that realizes the maximum value of? A (hereinafter also referred to as? Amma) which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorbance in the perpendicular direction Is preferably within a range of 1% to 70%, and more preferably within a range of 1% to 50%.

&Lt; Process [III] &gt;

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

Heating can be performed by a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven. The heating temperature can be determined in consideration of the temperature at which the liquid crystal property of the coating film to be used is expressed.

It is preferable that the heating temperature is within the temperature range of the temperature at which the side chain type polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal forming temperature). In the case of a thin film surface such as a coated film, it is expected that the temperature of liquid crystal display on the surface of the coated film is lower than the liquid crystal expression temperature when the photosensitive side chain polymer capable of exhibiting liquid crystallinity is observed in bulk. Therefore, it is more preferable that the heating temperature is within the temperature range of the liquid crystal display temperature on the surface of the coating film. That is, the temperature range of the heating temperature after irradiation with the polarized ultraviolet light is set to a temperature lower by 10 占 폚 than the lower limit of the temperature range of the liquid crystal display temperature of the side chain type polymer to be used and a temperature lower by 10 占 폚 than the upper limit of the liquid crystal temperature range, The temperature is preferably in the range of &lt; RTI ID = 0.0 &gt; If the heating temperature is lower than the above-mentioned temperature range, the amplifying effect of anisotropy due to heat in the coating film tends to become insufficient. If the heating temperature is too higher than the above temperature range, the coating film state becomes isotropic liquid state ). In this case, it may become difficult to reorient in one direction by self-organization.

The liquid crystal display temperature is preferably at least the glass transition temperature (Tg) at which the surface of the side chain type polymer or the coating film undergoes phase transition from the solid phase to the liquid crystal phase, and isotropic phase transition from the liquid crystal phase to the isotropic phase (isotropic phase) Refers to the temperature below the temperature (Tiso).

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

By the above process, the production method of the present invention can realize introduction of anisotropy into the coating film with high efficiency. A substrate on which a liquid crystal alignment film is formed with high efficiency can be produced.

&Lt; Process [IV] &gt;

The step [IV] includes the steps of: preparing a substrate (first substrate) having a liquid crystal alignment film on a conductive film for driving a transversal electric field obtained in [III] (Second substrate) on which a liquid crystal alignment film having no liquid crystal alignment film formed thereon is opposed to the liquid crystal alignment film so as to face each other with liquid crystal interposed therebetween and a liquid crystal cell is manufactured by a known method to manufacture a transverse electric field driven liquid crystal display element to be. It is to be noted that the steps [I '] to [III'] are the same as the steps [I '] to [III'] except that a substrate having no conductive film for transversal field driving is used instead of the substrate having a conductive film for driving a transversal electric field, I] to [III]. The description of the steps [I '] to [III'] is omitted because the difference between the steps [I] to [III] and the steps [I '] to [III'] is only the presence or absence of the above-described conductive film.

In order to prepare a liquid crystal cell or a liquid crystal display element, the above-described first and second substrates are prepared, a spacer is sprayed on the liquid crystal alignment film of the substrate of the single chamber to make the liquid crystal alignment film face inward, A method in which a substrate of a single chamber is bonded and a liquid crystal is injected under reduced pressure to seal the substrate or a method in which liquid crystal is dropped on a surface of a liquid crystal alignment film on which a spacer is spread, have. At this time, it is preferable to use a substrate having electrodes of a structure like a comb-like driving electrode for lateral electric field driving on one side of the substrate. The diameter of the spacer at this time is preferably 1 m to 30 m, more preferably 2 m to 10 m. This 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 method for producing a substrate on which a coating film of the present invention is formed, a polymer composition is applied on a substrate to form a coating film, and then irradiated with polarized ultraviolet rays. Subsequently, by heating, introduction of high-efficiency anisotropy into the side-chain type polymer film is realized, and a substrate on which a liquid crystal alignment film having the liquid crystal alignment control ability is formed is produced.

In the coating film to be used in the present invention, the introduction of highly efficient anisotropy into the coating film is realized by utilizing the principle of molecular rearrangement caused by the self-organization based on the light reaction of side chains and liquid crystallinity. In the production method of the present invention, in the case of a structure having a photocrosslinkable group as a photoreactive group on a side chain type polymer, a coating film is formed on a substrate using a side chain type polymer, then irradiated with polarized ultraviolet rays, After heating, a liquid crystal display element is manufactured.

Hereinafter, embodiments using side-chain polymers having a structure having a photocrosslinkable group as the photoreactive group will be described as first embodiment, embodiments using the side-chain polymer having a structure having a group causing a photo- Will be referred to as a second embodiment.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view for explaining an introduction process of anisotropy in a process for producing a liquid crystal alignment film using a side chain type polymer having a photo-crosslinkable group as a photo-reactive group in the first aspect of the present invention Fig. Fig. 1 (a) is a diagram schematically showing the state of a side-chain type polymer membrane before polarization irradiation, Fig. 1 (b) is a diagram schematically showing the state of a side- Is a diagram schematically showing the state of the side chain type polymer membrane after heating. Specifically, in the case where the introduced anisotropy is small, that is, in the first embodiment of the present invention, the ultraviolet irradiation amount of the step [II] And is within the range of 1% to 15% of the ultraviolet radiation dose.

2 schematically illustrates introduction of anisotropy in the process for producing a liquid crystal alignment film using a side chain type polymer having a photo-crosslinkable group as a photo-reactive group in the first aspect of the present invention Fig. Fig. 2 (a) is a diagram schematically showing the state of the side-chain polymer film before the polarized light irradiation, Fig. 2 (b) is a diagram schematically showing the state of the side- Is a diagram schematically showing the state of the side chain type polymer membrane after heating. In particular, in the case where the introduced anisotropy is large, that is, in the first embodiment of the present invention, the ultraviolet radiation amount in the step [II] And is within the range of 15% to 70% of the ultraviolet radiation dose.

Fig. 3 is a schematic view showing a liquid crystal alignment layer (hereinafter referred to as &quot; liquid crystal alignment layer &quot;) using a photo-isomerizable group as a photoreactive group or a side chain-type polymer having a structure having a light- Fig. 8 is an example diagram schematically illustrating an introduction process of anisotropy in the manufacturing method of the present invention. Fig. 3 (a) is a diagram schematically showing the state of the side-chain polymer film before the polarized light irradiation, Fig. 3 (b) is a diagram schematically showing the state of the side- Is a diagram schematically showing the state of the side chain type polymer membrane after heating. In the case where the introduced anisotropy is small, that is, in the second aspect of the present invention, the amount of ultraviolet irradiation in the step [II] And is within the range of 1% to 70% of the ultraviolet radiation dose.

Fig. 4 is a graph showing the results of evaluation of the method for producing a liquid crystal alignment layer using a side chain type polymer having a structure having a light-free stress period represented by the above-mentioned formula (19) as a photoreactive group in the second aspect of the present invention Fig. 2 is a view showing an example of a process of introducing anisotropy of the present invention. FIG. 4A is a diagram schematically showing the state of the side-chain polymer film before the polarized light irradiation, FIG. 4B is a diagram schematically showing the state of the side-chain polymer film after the polarized light irradiation, Is a diagram schematically showing the state of the side chain type polymer membrane after heating. Specifically, when the introduced anisotropy is large, that is, in the second embodiment of the present invention, the amount of ultraviolet irradiation in the step [II] And is within the range of 1% to 70% of the ultraviolet radiation dose.

In the first aspect of the present invention, in the case where the ultraviolet irradiation amount in the step [II] is within the range of 1% to 15% of the ultraviolet irradiation amount which maximizes the ΔA in the process of introducing anisotropy into the coating film, A coating film (1) is formed on a substrate. As shown in Fig. 1 (a), the coating film 1 formed on a substrate has a structure in which the side chains 2 are randomly arranged. The mesogenic component of the side chain 2 and the photosensitive film are randomly oriented in accordance with the random arrangement of the side chains 2 of the coating film 1 and the coating film 1 is isotropic.

In the first aspect of the present invention, in the case where the ultraviolet ray irradiation amount in the step [II] is within the range of 15% to 70% of the ultraviolet ray irradiation amount which maximizes? A in the process of introducing anisotropy into the coating film, A coating film (3) is formed on a substrate. As shown in Fig. 2 (a), the coating film 3 formed on the substrate has a structure in which the side chains 4 are randomly arranged. The mesogenic component of the side chain 4 and the photosensitive film are randomly oriented in accordance with the random arrangement of the side chains 4 of the coating film 3 and the coating film 2 is isotropic.

In the second embodiment of the present invention, in the process of introducing anisotropy into the coating film, a photo-isomerization type or a side chain type polymer having a structure having a light-free stress period represented by the above-mentioned formula (18) In the case of using a liquid crystal alignment film, when the amount of ultraviolet irradiation in the step [II] is within the range of 1% to 70% of the amount of ultraviolet irradiation that maximizes DELTA A, a coating film 5 is first formed on the substrate. As shown in Fig. 3 (a), the coating film 5 formed on the substrate has a structure in which the side chains 6 are randomly arranged. The mesogenic component of the side chain 6 and the photosensitive film are randomly oriented in accordance with the random arrangement of the side chains 6 of the coating film 5 and the side chain type polymer film 5 is isotropic.

In the second embodiment of the present invention, in the case where a liquid crystal alignment film using a side chain type polymer having a structure having a light-free stress period represented by the above-described formula (19) is used in the process of introducing anisotropy into the coating film , When the amount of ultraviolet radiation in the step [II] is within the range of 1% to 70% of the amount of ultraviolet radiation which maximizes the amount of ΔA, the coating film 7 is first formed on the substrate. As shown in Fig. 4 (a), the coating film 7 formed on the substrate has a structure in which the side chains 8 are randomly arranged. The mesogenic component of the side chain 8 and the photosensitive film are randomly oriented in accordance with the random arrangement of the side chains 8 of the coating film 7 and the coating film 7 is isotropic.

In the first embodiment, when the amount of ultraviolet irradiation in the step [II] is within a range of 1% to 15% of the amount of ultraviolet irradiation that maximizes DELTA A, the isotropic coating film 1 is irradiated with polarized ultraviolet . Then, as shown in Fig. 1 (b), among the side chains 2 arranged in the direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 2a having a photosensitive group is preferentially subjected to a photoreaction such as a diminishing reaction Cause. As a result, the density of the side chain 2a that has undergone the photoreaction becomes slightly higher in the polarization direction of the irradiated ultraviolet ray, and consequently very small anisotropy is imparted to the coating film 1.

In the first embodiment, when the amount of ultraviolet irradiation in the step [II] is within the range of 15% to 70% of the amount of ultraviolet irradiation that maximizes DELTA A, the isotropic coating film 3 is irradiated with polarized ultraviolet . Then, as shown in Fig. 2 (b), among the side chains 4 arranged in the direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 4a having a photosensitive group is preferentially subjected to a photoreaction such as a dimerization reaction Cause. As a result, the density of the side chain 4a that has undergone the photoreaction becomes higher in the polarization direction of the irradiated ultraviolet ray, and consequently, the coating film 3 is given a small anisotropy.

In the second embodiment, a liquid crystal alignment film using a photo-isomerizable group or a side chain-type polymer having a structure represented by the above-described formula (18) and having a light-free stress state is used to measure the ultraviolet radiation amount Polarized ultraviolet rays are irradiated to the isotropic coating film 5 in the range of 1% to 15% of the ultraviolet ray irradiation amount which maximizes the? A. Then, as shown in Fig. 3 (b), among the side chains 6 arranged in the direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 6a having a photosensitive group preferentially undergoes a photoreaction such as a light- Cause. As a result, the density of the side chain 6a that has undergone the photoreaction slightly increases in the polarization direction of the irradiated ultraviolet ray, and consequently very small anisotropy is imparted to the coating film 5.

In the second embodiment, a coating film using a side-chain type polymer having a structure having a light-free stress period represented by the above-described formula (19) is used, and the amount of ultraviolet irradiation in the step [II] Polarized ultraviolet rays are irradiated to the isotropic coating film 7 in the range of 1% to 70% of the ultraviolet ray irradiation amount. Then, as shown in Fig. 4 (b), the photosensitive group of the side chain 8a having the photosensitive group among the side chains 8 arranged in the direction parallel to the polarization direction of the ultraviolet ray preferentially reacts with light such as the light- Cause. As a result, the density of the side chain 8a that has undergone the photoreaction becomes higher in the polarization direction of the irradiated ultraviolet ray, and consequently, the coating film 7 is given a small anisotropy.

Next, in the first embodiment, in the case where the amount of ultraviolet irradiation in the step [II] is within the range of 1% to 15% of the amount of ultraviolet irradiation that maximizes DELTA A, the coated film 1 after the irradiation of polarized light is heated, Liquid crystal state. Then, as shown in Fig. 1 (c), in the coating film 1, the amount of the crosslinking reaction generated between the direction parallel to the polarization direction of the irradiated ultraviolet ray and the direction perpendicular to the polarization direction of the irradiation ultraviolet ray differs. In this case, since the amount of the crosslinking reaction occurring in the direction parallel to the polarization direction of the irradiating ultraviolet ray is very small, the crosslinking reaction site functions as a plasticizer. Therefore, the liquid crystal property in the direction parallel to the polarization direction of the irradiating ultraviolet ray becomes higher than the liquid crystalline property in the parallel direction, and the side chains 2 containing the mesogen component are self-organized in the direction parallel to the polarization direction of the irradiating ultraviolet rays, do. As a result, the extremely small anisotropy of the coating film 1 caused by the photo-crosslinking reaction is amplified by the heat, and a greater anisotropy is imparted to the coating film 1.

Likewise, in the first embodiment, in the case where the ultraviolet irradiation amount in the step [II] is within the range of 15% to 70% of the ultraviolet irradiation amount that maximizes? A, the coated film 3 after the polarized light irradiation is heated, Liquid crystal state. Then, as shown in Fig. 2 (c), in the side-chain polymer film 3, the amount of the cross-linking reaction occurring between the direction parallel to the polarization direction of the irradiated ultraviolet ray and the direction perpendicular to the polarization direction of the irradiation ultraviolet ray differs. Therefore, the side chains 4 containing the mesogen component are self-organized in a direction parallel to the polarization direction of the irradiating ultraviolet rays and are rearranged. As a result, the small anisotropy of the coating film 3 caused by the photo-crosslinking reaction is amplified by the heat, and the coating film 3 is given greater anisotropy.

Likewise, in the second embodiment, by using a coating film using a photo-isomerizable group or a side chain-type polymer having a structure represented by the above-mentioned formula (18) and having a light-free stress period, When the irradiation amount is within the range of 1% to 70% of the ultraviolet irradiation amount that maximizes DELTA A, the coated film 5 after the irradiation of polarized light is heated to the liquid crystal state. Then, as shown in Fig. 3 (c), in the coating film 5, the amount of the light-free potential reaction generated is different between the direction parallel to the polarization direction of the irradiated ultraviolet ray and the direction perpendicular to the polarization direction. In this case, since the liquid crystal aligning force of the light-free electric potential body formed in the direction perpendicular to the polarization direction of the irradiating ultraviolet ray is stronger than the liquid crystal aligning force of the side chain before the reaction, it self-aligns in the direction perpendicular to the polarization direction of the irradiating ultraviolet ray, Is rearranged. As a result, the very small anisotropy of the coating film 5 caused by the light-free-potential reaction is amplified by the heat, and a greater anisotropy is imparted to the coating film 5.

Likewise, in the second embodiment, by using the coating film using the side-chain type polymer having a structure having the light-free stress period represented by the above-mentioned formula (19), the ultraviolet irradiation amount of the step [II] , The coating film 7 after the irradiation of polarized light is heated to a liquid crystal state. Then, as shown in Fig. 4 (c), in the side-chain polymer film 7, the amount of the light-free potential reaction generated is different between the direction parallel to the polarization direction of the irradiated ultraviolet ray and the direction perpendicular to the polarization direction. Since the anchoring force of the light-free electric potential element 8 (a) is stronger than that of the side chain 8 before the electric potential, when a certain amount or more of the light-free electric potential elements is generated, the anisotropic magnetization is self-organized in a direction parallel to the polarization direction of the irradiated ultraviolet light, Is rearranged. As a result, the small anisotropy of the coating film 7 caused by the light-free-potential reaction is amplified by the heat, and a greater anisotropy is imparted to the coating film 7.

Therefore, the coating film used in the method of the present invention can be made into a liquid crystal alignment film having high orientation anisotropy introduced with high efficiency, by sequentially irradiating the coating film with polarized ultraviolet light and heat treatment.

In the coating film used in the method of the present invention, the irradiation amount of the polarized ultraviolet ray to the coating film and the heating temperature in the heating treatment are optimized. Thus, introduction of anisotropy into the coating film with high efficiency can be realized.

The irradiation dose of the polarized ultraviolet ray which is most suitable for introducing the highly efficient anisotropy into the coating film used in the present invention is the polarizing ultraviolet ray which optimizes the amount of the photosensitive group to react with the light crosslinking reaction, the optical isomerization reaction, . &Lt; / RTI &gt; As a result of irradiating the coating film used in the present invention with polarized ultraviolet rays, a sufficient photoreaction amount can not be obtained if the number of photosensitive groups in the side chain to be subjected to a photo-crosslinking reaction, a photoisomerization reaction, or a light- In that case, sufficient self-organization does not proceed even after heating. On the other hand, in the coating film used in the present invention, the structure having a photocrosslinkable group is irradiated with polarized ultraviolet rays, and as a result, if the photosensitive group of the side chain to be crosslinked is excessive, the cross-linking reaction in the side chain becomes too much. In such a case, the obtained film becomes rigid, which may interfere with the progress of self-organization by the subsequent heating. In the coating film used in the present invention, the polarizing ultraviolet rays are irradiated to the structure having the light-free pressing phenomenon, and as a result, when the photosensitive group of the side chain reacting with the light-free potential is excessive, the liquid crystallinity of the coating film is excessively lowered . In such a case, the liquid crystallinity of the obtained film is also lowered, which may interfere with the progress of self-organization by the subsequent heating. Further, in the case of irradiating polarized ultraviolet rays to a structure having a light-free stress period, if the irradiation amount of ultraviolet light is too high, the side-chain type polymer is photodegraded and the subsequent self- have.

Therefore, in the coating film to be used in the present invention, the optimal amount of photo-crosslinking reaction, photoisomerization reaction, or light-free potential reaction of the photosensitive group of the side chain by irradiation with polarized ultraviolet light is preferably such that the photosensitive group of the side chain- Is preferably 0.1 mol% to 40 mol%, and more preferably 0.1 mol% to 20 mol%. By setting the amount of the photosensitive group of the photoreactive side chain within such a range, the self-organization in the subsequent heat treatment proceeds efficiently, and it becomes possible to form anisotropy with high efficiency in the film.

In the coating film used in the method of the present invention, by optimizing the amount of irradiation of the polarized ultraviolet ray, the amount of the photo-crosslinking reaction or the optical isomerization reaction or the optical free-potential reaction in the side chain of the side chain type polymer membrane . In addition to the subsequent heat treatment, introduction of anisotropy into the coating film used in the present invention, which is highly efficient, is realized. In this case, the preferable amount of the polarized ultraviolet ray can be carried out 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, ultraviolet ray absorption in the direction parallel to the polarization direction of the polarized ultraviolet ray after irradiation with the polarized ultraviolet ray and ultraviolet ray absorption in the perpendicular direction are respectively measured. From the measurement result of ultraviolet absorption,? A which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorbance in the direction perpendicular to the polarized direction of the polarized ultraviolet ray is evaluated. Then, the maximum value DELTA Amax realized in the coating film used in the present invention and the irradiation amount of the polarized ultraviolet ray for realizing the maximum DELTA Amax are obtained. In the manufacturing method of the present invention, it is possible to determine the amount of polarized ultraviolet ray to be irradiated in the production of the liquid crystal alignment film on the basis of the polarized ultraviolet radiation amount for realizing the DELTA Amma.

In the production method of the present invention, the irradiation amount of the polarized ultraviolet ray to the coating film used in the present invention is preferably within a range of 1% to 70% of the amount of the polarized ultraviolet ray realizing DELTA Amma, preferably 1% to 50% And more preferably within the range of &lt; RTI ID = 0.0 &gt; In the coating film used in the present invention, the irradiation amount of the polarized ultraviolet ray within the range of 1% to 50% of the amount of the polarized ultraviolet ray realizing DELTA Amma is preferably 0.1 mol% to 20 mol% % To the amount of polarized ultraviolet rays subjected to photo-crosslinking reaction.

From the above, in the production method of the present invention, in order to realize introduction of highly efficient anisotropy into the coating film, it is preferable to set the preferable heating temperature as described above based on the liquid crystal temperature range of the side chain type polymer . Therefore, for example, in the case where the liquid crystal temperature range of the side chain type polymer used in the present invention is 100 ° C to 200 ° C, it is preferable to set the heating temperature after irradiation with the polarized ultraviolet ray to 90 ° C to 190 ° C. By doing so, a greater anisotropy is imparted to the coating film used in the present invention.

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

As described above, the substrate for a transverse electric field driving type liquid crystal display element manufactured by the method of the present invention or the transverse electric field driving type liquid crystal display element having the substrate has excellent reliability and is preferably used for a liquid crystal television Can be used.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

Example

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

MA1 and MA2 were each synthesized as follows. That is, MA1 was synthesized by a synthesis method described in Patent Document (WO2011-084546). MA2 was synthesized by the synthetic method described in the patent document (Japanese Patent Application Laid-Open No. 9-118717).

Additives T1 (3-aminomethylpyridine) and T2 (1- (3-aminopropyl) imidazole) were commercially available.

(42)

In addition, the abbreviations of the reagents used in this embodiment are shown below.

(Organic solvent)

THF: tetrahydrofuran.

NMP: N-methyl-2-pyrrolidone.

BC: butyl cellosolve.

(Polymerization initiator)

AIBN: 2,2'-azobisisobutyronitrile.

&Lt; Synthesis Example 1 &

MAIB (4.99 g, 15.0 mmol) and MA2 (4.60 g, 15.0 mmol) were dissolved in THF (88.5 g) and degassed using a diaphragm pump. AIBN (0.246 g, 1.5 mmol) . Thereafter, the reaction was conducted at 50 DEG C for 30 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (1000 ml), and the resulting precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C to obtain a methacrylate polymer powder.

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

&Lt; Example 1 &gt;

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

Using this liquid crystal aligning agent A1, a liquid crystal cell was produced in the following order. The substrate was a glass substrate having a size of 30 mm x 40 mm and a thickness of 0.7 mm, and a comb-like pixel electrode formed by patterning an ITO film was disposed.

The pixel electrode has a comb-like shape formed by arranging a plurality of elongated electrode elements bent at a central portion. The width of each electrode element in the short direction was 10 占 퐉, and the interval between the electrode elements was 20 占 퐉. Since the pixel electrode forming each pixel is constituted by arranging a plurality of electrode elements bent in a central portion in the shape of a letter, the shape of each pixel is not rectangular, It has a shape resembling the character of the letter.

Each pixel is divided into upper and lower portions with the bent portion at the center as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side. When the first region and the second region of each pixel are compared with each other, the electrode elements of the pixel electrodes constituting the first region and the second region are formed in different directions. That is, in the first region of the pixel, the electrode element of the pixel electrode is formed so as to form an angle of +15 degrees (clockwise direction) in the direction of alignment of the liquid crystal alignment film, And the electrode elements were formed so as to form an angle of -15 DEG (clockwise direction). That is, in the first region and the second region of each pixel, the direction of the rotation operation (inflation / switching) of the liquid crystal caused by the application of the voltage between the pixel electrode and the counter electrode is opposite to each other Respectively.

<< Preparation of liquid crystal cell >>

The liquid crystal aligning agent A1 obtained in Example 1 was spin-coated on the prepared substrate on which the electrode was formed. Subsequently, the substrate was dried with a hot plate at 70 DEG C for 90 seconds to form a liquid crystal alignment film having a thickness of 100 nm. Subsequently, the coated film surface was irradiated with ultraviolet rays of 313 nm through a polarizing plate at 20 mJ / cm 2 and then heated on a hot plate at 150 캜 for 10 minutes to obtain a substrate on which a liquid crystal alignment film was formed. A coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 占 퐉, on which no electrode was formed as a counter substrate, and the alignment treatment was carried out. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one of the substrates. Subsequently, another substrate was adhered to the liquid crystal alignment film so that the alignment direction thereof was 0 deg., And the sealant was thermally cured to prepare empty cells. Liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into this empty cell by a vacuum injection method and the injection port was sealed to obtain a liquid crystal cell having a configuration of an IPS (In-Planes Switching) mode liquid crystal display element.

&Lt; Evaluation of voltage holding ratio (VHR) &gt;

Using the liquid crystal cell prepared above, an AC voltage of 16 Vpp was applied for 168 hours under a constant temperature condition of 70 캜 at a frequency of 30 Hz. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left at room temperature for 1 hour. The obtained cell was subjected to a voltage of 5 V for 60 seconds under a temperature of 70 DEG C, and a voltage after 16.67 ms was measured. The voltage holding ratio (VHR) was calculated as to how long the voltage was maintained. For the measurement of the voltage holding ratio, a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technica Co., Ltd. was used.

Table 1 shows the composition of the liquid crystal aligning agent of Example 1 and the results of VHR.

&Lt; Example 2 &gt;

A polymer solution A2 of Example 2 was obtained in the same manner as in Example 1 except that T2 was used in place of Tl in Example 1 and liquid crystal cells were prepared in the same manner as in Example 1 to measure the voltage holding ratio did. The results are shown in Table 1.

<Control 1>

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

From Table 1, it can be seen that the voltage holding ratio (VHR) is improved by using the additive in Examples 1 and 2, as compared with Control 1 in which the additive is not used.

<After-image evaluation>

The liquid crystal cell for IPS mode prepared in Example 1 was provided between two polarizing plates arranged so that the polarization axis thereof was orthogonal to each other and the backlight was turned on in the voltage unapplied state so that the arrangement angle of the liquid crystal cell Respectively. The rotation angle when the liquid crystal cell was rotated from the angle at which the second area of the pixel is darkest to the angle at which the first area is darkest is calculated as the initial alignment azimuth angle. Subsequently, an alternating voltage of 16 V _PP was applied for 168 hours at a frequency of 30 Hz in an oven at 60 캜. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left at room temperature for 1 hour. After being left standing, the orientation azimuth was similarly measured, and the difference in orientation azimuth before and after the AC drive was calculated as the angle DELTA (deg.). The same measurements were made in the other examples. As a result, in all of the examples, the angle? Was 0.1 or less. Since the side chain type polymer membrane exhibiting liquid crystallinity is irradiated with ultraviolet rays and then heated in the temperature range of the liquid crystal display temperature, the liquid crystal alignment ability is imparted with high efficiency in the entire polymer due to self-organization, The discrepancy was hardly observed.

1
1: Side chain type polymer membrane
2, 2a: side chain
2
3: Side chain type polymer membrane
4, 4a: Side chain
3
5: Side chain type polymer membrane
6, 6a: Side chain
4
7: Side chain type polymer membrane
8, 8a: Side chain

Claims (16)

(A) a photosensitive side chain type polymer which exhibits liquid crystallinity in a predetermined temperature range,
(B) an amine compound having one primary amino group and one nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and
(C) an organic solvent
&Lt; / RTI &gt; The method according to claim 1,
(A) has a photosensitive side chain that causes photo-crosslinking, photoisomerization, or light-free transition. 3. The method according to claim 1 or 2,
Wherein the component (B) is an amine represented by the following formula A- [1] (wherein Y ₁₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y ₁₂ is a nitrogen-containing aromatic heterocyclic ring) &Lt; / RTI &gt;
[Chemical Formula 1]

4. The method according to any one of claims 1 to 3,
(A) is represented by the following formulas (1) to (6)
(Wherein, A, B, D represents a single bond, -O-, -CH ₂ each independently -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO- O-, or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or a ring selected from the same or different 2 to 6 rings Are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , - CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
Y ₂ is a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, Each independently may be substituted with -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or has the same definition as Y ₁ ;
X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO-CH═CH -, and when the number of X's is 2, X's may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are each independently -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH- Group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
q1 and q2 are 1 in one and 0 in the other;
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 having 5 to 8 carbon atoms, and combinations thereof; Is -CH = CH-CO-O- or -O-CO-CH = CH-, P or Q on the side bonded to -CH = CH- is an aromatic ring. When the number of P is 2 or more, P may be the same or different, and when Q is 2 or more, Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer of 0 to 2;
When l1 and l2 are both 0, when T is a single bond, A also represents a single bond;
When l1 is 1, B is also a single bond when T is 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.
Wherein the photosensitive side chain is selected from the group consisting of the following.
(2)

4. The method according to any one of claims 1 to 3,
(A) is represented by the following formulas (7) to (10)
(Wherein, A, B, D represents a single bond, -O-, -CH ₂ each independently -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO- O-, or -O-CO-CH = CH-;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or a ring selected from the same or different 2 to 6 rings Are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , - CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO-CH═CH -, and when the number of X's is 2, X's may be the same or different;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, m1 and m2 represent an integer of 1 to 3;
n is an integer of 0 to 12 (provided that when n = 0, B is a single bond);
Y ₂ is a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, Each independently may be substituted with -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y ₁ )
Wherein the photosensitive side chain is selected from the group consisting of the following.
(3)

4. The method according to any one of claims 1 to 3,
(A) is represented by the following formulas (11) to (13)
(Wherein, A is each independently a single _{bond, -O-, -CH 2 -, -COO-} , -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O-CO-CH = CH-;
X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO-CH═CH -, and when the number of X's is 2, X's may be the same or different;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, and m1 represents an integer of 1 to 3;
R represents a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings and alicyclic hydrocarbons having 5 to 8 carbon atoms, or the same or different rings of 2 to 6 selected from the substituents thereof And a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN , the _{-CH = C (CN) 2,} -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms or may be substituted with an oxy, or hydroxy, or 1 to 6 carbon atoms in the Alkoxy group)
Wherein the photosensitive side chain is selected from the group consisting of the following.
[Chemical Formula 4]

4. The method according to any one of claims 1 to 3,
(A) is a compound represented by the following formula (14) or (15)
(Wherein, A is each independently a single _{bond, -O-, -CH 2 -, -COO-} , -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O-CO-CH = CH-;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or a ring selected from the same or different 2 to 6 rings Are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , - CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
1 represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3).
[Chemical Formula 5]

4. The method according to any one of claims 1 to 3,
(A) is a compound represented by the following formula (16) or (17)
(Wherein A is a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO- CO-CH = CH-;
X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO-CH═CH -, and when the number of X's is 2, X's may be the same or different;
l represents an integer of 1 to 12, and m represents an integer of 0 to 2)
&Lt; / RTI &gt;
[Chemical Formula 6]

4. The method according to any one of claims 1 to 3,
(A) is a compound represented by the following formula (18) or (19)
(Wherein, A, B are each independently a single _{bond, -O-, -CH 2 -, -COO-} , -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O- , Or -O-CO-CH = CH-;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or a ring selected from the same or different 2 to 6 rings Are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , - CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
q1 and q2 are 1 in one and 0 in the other;
l represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3;
R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms or an alkyloxy group having 1 to 5 carbon atoms. Wherein the photosensitive side chain is selected from the group consisting of acrylic acid and methacrylic acid.
(7)

4. The method according to any one of claims 1 to 3,
Component (A) of the following formula (20): (wherein, A represents a single _{bond, -O-, -CH 2 -, -COO-} , -OCO-, -CONH-, -NH-CO-, -CH = CH -CO-O-, or -O-CO-CH = CH-;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or a ring selected from the same or different 2 to 6 rings Are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , - CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO-CH═CH -, and when the number of X's is 2, X's may be the same or different;
1 represents an integer of 1 to 12, and m represents an integer of 0 to 2).
[Chemical Formula 8]

11. The method according to any one of claims 1 to 10,
(A) has the following formulas (21) to (31): wherein A and B have the same definitions as above;
Y ₃ is a group selected from the group consisting of monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, nitrogen containing heterocyclic rings, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, Each hydrogen atom may be independently substituted with -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, A ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
q1 and q2 are 1 in one and 0 in the other;
m represents an integer of 0 to 2, provided that the sum of all m in the formulas (23) to (24) is 2 or more, and the formulas (25) to (26) , The sum of all m is 1 or more, m1, m2 and m3 each independently represent an integer of 1 to 3;
R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, Or an alkyloxy group;
Z ₁ and Z _{2 each} represent a single bond, -CO-, -CH ₂ O-, -CH═N-, or -CF ₂ -).
[Chemical Formula 9]

[I] a step of coating the composition described in any one of claims 1 to 11 on a substrate having a conductive film for transverse electric field driving to form a coating film;
[II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and
[III] a step of heating the coating film obtained in [II];
To obtain a liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type to which orientation control ability is imparted. A substrate having a liquid crystal alignment film for a liquid crystal display device of a transverse electric field driving type manufactured by the method according to claim 12. A transverse electric field driving type liquid crystal display element having the substrate according to claim 13. Preparing a substrate (first substrate) according to claim 13;
[I '] on the second substrate
(A) a photosensitive side chain type polymer which exhibits liquid crystallinity in a predetermined temperature range,
(B) an amine compound having one primary amino group and one nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and
(C) an organic solvent
A step of applying a polymer composition to form a coating film;
Irradiating the coating film obtained in [II '] [I'] with polarized ultraviolet light; and
A step of heating the coating film obtained in [III '] [II'];
To obtain a liquid crystal alignment film having the alignment control ability, thereby obtaining a second substrate having the liquid crystal alignment film; and
[IV] a step of arranging the first and second substrates so that the liquid crystal alignment layers of the first and second substrates oppose each other through the liquid crystal to obtain a liquid crystal display element;
To obtain a transverse electric field driven liquid crystal display element. A transverse electric field driving type liquid crystal display element manufactured by the method according to claim 15.

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