KR20160007638A - Method for producing substrate having liquid crystal orientation film for 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) at least one polymer selected from the group consisting of photosensitive side chain polymers that exhibit liquid crystallinity in a predetermined temperature range, (B) polyimide and precursors thereof, and (C) an organic solvent , The above problems are solved. [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 layer 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.

The liquid crystal display device is known as a lightweight, thin and low power consumption display device, and has recently achieved remarkable development, such as being used for a large-sized television application. 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. In this method, polarized ultraviolet rays are irradiated to a polyimide film, for example, and anisotropic decomposition is caused by using 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).

As another optical alignment method, a photo-alignment method of a photo-crosslinking type or a photo isomerization type is also known. In the photo-crosslinking type photo-alignment method, 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 polarized light . Then, the liquid crystal is oriented in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1). In the photo-isomerization type photo-alignment method, when a side-chain polymer having azobenzene as a side chain is used, polarized ultraviolet light is irradiated to generate an isomerization reaction in the azobenzene moiety of a side chain parallel to the polarized light, (For example, refer to 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 has a great advantage because it makes the rubbing process itself unnecessary as compared with the rubbing method which has conventionally been industrially used as an alignment processing method of a liquid crystal display element. 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 orientation control ability as in the case of the rubbing method, a large amount of irradiated light may be required, and stable alignment of the 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 light stability of the liquid crystal alignment are inferior, so that there is a fear that alignment failure and display exposure may 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. Another object of the present invention is to provide a liquid crystal alignment film capable of enlarging a margin area of an irradiated dose of ultraviolet irradiation capable of achieving good alignment of liquid crystal in a liquid crystal alignment film, and a method of manufacturing a substrate having the liquid crystal alignment film.

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) at least one polymer selected from the group consisting of polyimide and its precursor, and

(C) an organic solvent

, Particularly a polymer composition for producing a liquid crystal alignment film for a transverse electric field driven liquid crystal display device.

≪ 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> It is preferable that the precursor of the polyimide as the component (B) in the above item <1> or <2> is obtained by polymerizing a tetracarboxylic acid component and a diamine component.

<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)

[Chemical Formula 1]

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 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, 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).

(2)

<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.

(3)

<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 4]

<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 5]

<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.

[Chemical Formula 6]

<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.

(7)

<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 8]

<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 polymer selected from the group consisting of polyimide and its precursor, 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> In the above-mentioned <15>, it is preferable that the polyimide precursor of the component (B) is obtained by polymerizing a tetracarboxylic acid component and a diamine component.

<17> A transverse electric field driving type liquid crystal display device manufactured by the method of <15> or <16>.

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) at least one polymer selected from the group consisting of polyimide and its precursor,

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];

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> It is preferable that the polyimide precursor of the component (B) is obtained by polymerizing a tetracarboxylic acid component and a diamine component in <P1> or <P2>.

<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) .

[Chemical Formula 9]

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 each of the hydrogen atoms bonded to them is 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-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 , 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 10]

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.

(11)

<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 12]

<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 13]

<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 14]

<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 15]

<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 16]

<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) at least one polymer selected from the group consisting of polyimide and its precursor, 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, 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) at least one polymer selected from the group consisting of polyimide and its precursor, 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.

<P17> In the above <P16>, it is preferable that the polyimide precursor of the component (B) is obtained by polymerizing a tetracarboxylic acid component and a diamine component.

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.

In the present invention, by including in the polymer composition at least one kind of polymer selected from polyimide (B) and a precursor thereof as the component (B), a margin of the dose of ultraviolet radiation capable of realizing good liquid crystal orientation in the liquid crystal alignment film The area can be enlarged, the irradiation amount area can be widened, and a desired effect can be exerted in a wider irradiation area.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram illustrating one example of a method for schematically describing anisotropic introduction treatment in the production method of 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, 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 Fig. 3, an organic group causing fresnel transition or isomerization is used as a photosensitive side chain, Is a diagram showing a small anisotropy.
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 Fig. 4, an organic group causing fresnel transition or isomerization is used as a photosensitive side chain, Is a diagram showing a case where 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) at least one polymer selected from the group consisting of polyimide and its precursor, 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], on a substrate having a conductive film for transversal electric field drive, a photosensitive side-chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, at least one kind selected from the group consisting of polyimide and its precursor A polymer composition containing a polymer 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.

The polymer composition used in the production method of the present invention comprises (A) a photosensitive side chain polymer which exhibits liquid crystallinity in a predetermined temperature range, (B) at least one polymer selected from the group consisting of polyimide and a precursor thereof 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 17]

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 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, 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 18]

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 19]

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 20]

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.

[Chemical Formula 21]

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.

[Chemical Formula 22]

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.

(23)

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 -.

&Lt; EMI ID =

<< 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.

(25)

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;

(26)

(27)

(28)

[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.

[Chemical Formula 29]

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 or polyamic acid and is not a photosensitive side chain type polymer capable of exhibiting liquid crystallinity.

<< Component (B) >>

The polymer composition used in the present invention has at least one polymer selected from the group consisting of a polyimide and a precursor thereof as the component (B). Preferably, the component (B) is at least one polymer selected from a polyimide precursor obtained by polymerizing a tetracarboxylic acid component and a diamine component, and a polyimide obtained by imidizing the polyimide precursor. Examples of the polyimide precursor include polyamic acid (also referred to as polyamic acid), polyamic acid ester, and the like.

<<< tetracarboxylic acid component >>>

As the tetracarboxylic acid component which is a raw material of the component (B), for example, the following tetracarboxylic acid dianhydride may be mentioned.

Examples of the tetracarboxylic acid dianhydride having an alicyclic or aliphatic structure include 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetra Carboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane Tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,2,4,5- Cyclohexanetetracarboxylic acid dianhydride, cyclohexanetetracarboxylic acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, bicyclo [3.3.0] , 4,6,8-tetracarboxylic acid dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, cis- 3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dianhydride, Tricyclo [4.2.1.0 ^2,5] nonane -3,4,7,8- tetracarboxylic acid -3,4: 7,8-2 anhydride, hexahydro cyclo [6.6.0.1 ^2,7 .0 ^3,6 .1 ^9,14 .0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid 4,5: 11,12-2 anhydride, 3,4-dicarboxyphenyl -1,2,3 , 4-tetrahydro-1-naphthalenesuccinic dianhydride, and the like.

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

The above-mentioned tetracarboxylic acid dianhydride can be used alone or in combination of two or more, depending on the properties of the liquid crystal alignment film to be formed, such as liquid crystal aligning property, voltage holding property, and accumulated charge.

As the tetracarboxylic acid component which is a raw material of the component (B), a tetracarboxylic acid dialkyl ester or a tetracarboxylic acid dialkyl diester dichloride may be used. Further, when the tetracarboxylic acid component contains such a tetracarboxylic acid dialkyl ester or a tetracarboxylic acid dialkyl ester dichloride, the polymer becomes a polyamic acid ester which is a polyimide precursor. The tetracarboxylic acid dialkyl ester that can be used is not particularly limited and includes, for example, aliphatic tetracarboxylic acid diesters and aromatic tetracarboxylic acid dialkyl esters.

Specific examples thereof are given below.

Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester , 1,2,3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid di Alkyl esters, 3,4-dicarboxy-1-cyclohexylsuccinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dialkyl ester, 1,2,3 , 4-butanetetracarboxylic acid dialkyl ester, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3 ', 4,4'-dicyclohexyltetracar Malic acid Alkyl esters, 2,3,5-tricarboxycyclopentyl acetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 ^2,5] nonane -3,4,7,8- tetracarboxylic acid -3,4: 7,8-di-alkyl ester, cyclo hexa [6.6.0.1 ^2,7 .0 ^{3, 6} .1 ^9,14 .0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid 4,5: 11,12- di-alkyl ester, 3,4-dicarboxy-1,2 , 3,4-tetrahydro-1-naphthalenesuccinic dianhydride, and the like.

Specific examples of the aromatic tetracarboxylic acid dialkyl ester include pyromellitic acid dialkyl ester, 3,3 ', 4,4'-biphenyltetracarboxylic acid dialkyl ester, 2,2', 3,3'-biphenyltetra 2,3 ', 4'-biphenyltetracarboxylic acid dialkyl ester, 3,3', 4,4'-benzophenonetetracarboxylic acid dialkyl ester, 2,3,3 ', 4'- , Bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfonyl alkyl ester, 1,2,5,6 -Naphthalenetetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalenetetracarboxylic acid dialkyl ester, and the like.

<<< Diamine Ingredients >>>

Examples of the diamine component as the raw material of the component (B) include the following alicyclic diamines, aromatic diamines, heterocyclic diamines, aliphatic diamines and urea bond-containing diamines.

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyl Dicyclohexylamine, isophoronediamine, and the like.

Examples of the aromatic diamines include aromatic diamines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, Diamino-2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, , 5-dichlorobenzene, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminostilbene, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diamine, Diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis Benzene, 1,4-bis (4-aminophenoxy) benzene, 3,5-bis (4- Benzoic acid, 4,4'-bis (4-aminophenoxy) bibenzyl, 2,2-bis [ Bis [4- (4-aminophenoxy) phenyl] propane, bis [4- Bis (4-aminophenyl) phenyl] sulfone, 1,1-bis (4-aminophenyl) cyclohexane, 4-aminophenyl) fluorene, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- , 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrrene, 1,6-diamino Pyrene, 1,8-diaminopyrene, 2,7-diaminofluorene, 1,3-bis (4-aminophenyl) tetramethyldisiloxane, benzidine, 2,2'-dimethylbenzidine, (4-aminophenyl) ethane Bis (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) propane, Bis (4-aminophenyl) heptane, 1,9-bis (4-aminophenyl) Bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) pentane, Bis (4-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) heptane, ) Nonane, 1,10-bis (4-aminophenoxy) decane, di (4-aminophenyl) propane-1,3-dioate, di Di (4-aminophenyl) heptane-1, 7-dioate, di (4-aminophenyl) (4-aminophenyl) nonane-1,9-dioate, di (4-aminophenyl) ) Decane-1,10-diate, 1,3-bis [4- (4-aminophenoxy) phenoxy] propane, 1,4-bis [4- (4-aminophenoxy) phenoxy] Bis [4- (4-aminophenoxy) phenoxy] pentane, 1,6-bis [4- -Aminophenoxy) phenoxy] heptane, 1,8-bis [4- (4-aminophenoxy) phenoxy] octane, 1,9- 1,10-bis [4- (4-aminophenoxy) phenoxy] decane, and the like.

Examples of the aromatic-aliphatic diamine include diamines represented by the following formula [DAM].

(30)

(Wherein,

Ar represents a benzene ring or a naphthalene ring,

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

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

Specific examples of the aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, Amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- 3- (5-methylaminopentyl) aniline, 4- (5-methylaminopentyl) aniline, Aniline, 2- (6-aminonaphthyl) methylamine, 3- (6-aminonaphthyl) methylamine, 2- .

Examples of the heterocyclic diamine include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3 Diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole And the like.

Examples of the aliphatic diamine include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, Diaminoethane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino- Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9- Diamino-5-methyl nonane, 1,12-diaminododecane, 1,18-diaminooctadecane, 1,2-bis (3-aminopropoxy) ethane and the like.

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

In the component (B), the diamine component to be polymerized with the tetracarboxylic acid component may contain a diamine having a side chain for vertical alignment within a range not hindering the effect of the present invention.

The diamine component in the component (B) may contain the following diamines.

(31)

(Wherein m and n are each an integer of 1 to 11, m + n is an integer of 2 to 12, h is an integer of 1 to 3, and j is an integer of 0 to 3.)

By introducing these diamines, it is advantageous to further improve the voltage holding ratio (also referred to as VHR) of a liquid crystal display element using a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention. These diamines are preferred from the viewpoint of excellent accumulation charge reduction effect of such liquid crystal display elements.

In addition, as the diamine component in the component (B), a diaminosiloxane represented by the following formula can also be used.

(32)

(Wherein m is an integer of 1 to 10)

The diamine component in the component (B) may be used alone or in combination of two or more, depending on the properties such as liquid crystal aligning property, voltage holding property, and accumulated charge when used as a liquid crystal alignment film. The mixing ratio at that time is not limited.

The molecular weight of the polymer (polyimide precursor, polyimide) of the component (B) may be determined by GPC (Gel Permeation Chromatography) considering the strength of the obtained liquid crystal alignment film, workability in forming the liquid crystal alignment film, and uniformity of the liquid crystal alignment film. Is preferably from 5,000 to 1,000,000, and more preferably from 10,000 to 150,000, by weight.

A known synthetic method can be used to obtain the polymer of the component (B) by the polymerization reaction of the tetracarboxylic acid component and the diamine component of each raw material. Generally, the tetracarboxylic acid component and the diamine component are reacted in an organic solvent. The reaction between the tetracarboxylic acid component and the diamine component is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is generated.

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

Specific examples thereof are given below.

Examples of the organic solvent usable herein include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N- But are not limited to, sulfoxide, tetramethylurea, pyridine, dimethylsulfone,? -Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, Methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol mono isopropyl ether, ethylene glycol monoisopropyl ether, Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethyl 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 monoethyl ether, Dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethylisobutyl ether, diisobutylene Butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, Ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate , Propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3- Methoxypropyl methacrylate, propyl methoxy propionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3- -Dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, and the like. These may be used alone or in combination. In addition, a solvent which does not dissolve the polyamic acid may be used in combination with the solvent insofar as the produced polyamic acid does not precipitate.

In addition, water in the organic solvent inhibits the polymerization reaction, and further causes hydrolysis of the resulting polyamic acid. Therefore, it is preferable to use an organic solvent that is dehydrated and dried as much as possible.

When the tetracarboxylic acid component and the diamine component are reacted in an organic solvent, a method in which a solution in which a diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid component is added as it is or dispersed or dissolved in an organic solvent , A method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic acid component and a diamine component, and the like. . When the tetracarboxylic acid component or the diamine component is composed of a plurality of compounds, they may be reacted in a previously mixed state, or they may be subjected to sequential reactions individually, or the low molecular weight compounds reacted individually may be mixed and reacted to form a high molecular weight You can.

The polymerization temperature at that time may be any temperature between -20 DEG C and 150 DEG C, but is preferably in the range of -5 DEG C to 100 DEG C. When the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid becomes too high and it becomes difficult to perform uniform stirring. Therefore, The total concentration of the acid component and the diamine component in the reaction solution is preferably 1 to 50 mass%, more preferably 5 to 30 mass%. The reaction is carried out at a high concentration in the initial stage, and then an organic solvent can be added.

In the polymerization reaction of the polyamic acid, the ratio of the total number of moles of the tetracarboxylic acid component to the total number of moles of the diamine component is preferably 0.8 to 1.2. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polyamic acid.

<<< Polyimide >>>

The polyimide can be obtained by subjecting a polyimide precursor such as the above-mentioned polyamic acid or polyamic acid ester to dehydration ring closure. In the polyimide, the dehydration / removal rate (imidization rate) of the amidic acid group does not necessarily have to be 100%, but may be arbitrarily adjusted depending on the purpose and purpose in the range of 0% to 100%.

Examples of the method for imidizing the polyimide precursor include thermal imidization in which a solution of a polyamic acid or a polyamic acid ester is directly heated, and catalyst imidization in which a catalyst is added to a solution of a polyamic acid or a polyamic acid ester.

When the polyamic acid or the polyamic acid ester is thermally imidized in the solution, the temperature is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and the water generated by the imidization reaction is removed while removing it from the system desirable.

The catalyst imidation of polyamic acid or polyamic acid ester can be carried out by adding a basic catalyst and acid anhydride to a solution of polyamic acid or polyamic acid ester and stirring at -20 to 250 ° C, preferably 0 to 180 ° C have. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferred because it has a suitable basicity for promoting the reaction. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be given. Among them, acetic anhydride is preferable because the purification after completion of the reaction becomes easy. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

Examples of the method for synthesizing the polyamic acid ester include a method in which the tetracarboxylic acid diester is reacted with a halogenating agent such as thionyl chloride, sulfuryl chloride, oxalyl chloride or phosphorus oxychloride, and a diamine component Or a method of reacting a tetracarboxylic acid diester and a diamine component in the presence of a suitable condensing agent or a base. Alternatively, it is also possible to polymerize the polyamic acid in advance and then esterify the carboxylic acid in the amic acid using a polymer reaction.

Specifically, the tetracarboxylic acid diester dichloride and diamine are reacted in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, For 4 hours.

As the base, pyridine, triethylamine, and 4-dimethylaminopyridine can be used, but pyridine is preferable for the reaction to proceed mildly. The amount of the base to be added is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.

When the condensation polymerization is carried out in the presence of a condensing agent, it is possible to use condensation polymerization such as triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N, N ', N'-tetramethyluronium tetrafluoroborate, O (benzotriazol-1-yl) N, N, N ', N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methoxymorpholinium chloride n-hydrate and the like can be used.

Further, in the method using the condensing agent, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0.1 to 1.0 times the molar amount relative to the tetracarboxylic acid diester.

The solvent used in the above reaction may be a solvent used when the polyamic acid shown above is polymerized. However, the solubility of the monomer and the polymer is preferably N-methyl-2-pyrrolidone or? -Butyrolactone These may be used alone or in combination of two or more. The concentration at the time of the synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, from the viewpoint that the precipitation of the polymer hardly occurs and the high molecular weight material is easily obtained. In order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent the introduction of outside air in a nitrogen atmosphere.

When a polyimide precursor such as polyamic acid or polyamic acid ester or a polyimide precursor or polyimide such as polyamic acid or polyamic acid ester produced from a reaction solution of polyimide is recovered, the reaction solution is added to a poor solvent It can be precipitated. Examples of the poor solvent used in the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by pouring into a poor solvent can be recovered by filtration and then dried at normal temperature or under reduced pressure or by heating. In addition, by repeating the operation of re-dissolving the polymer recovered and precipitated in the organic solvent and re-precipitating and recovering the polymer 2 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 improved, which is preferable.

The polyimide precursor obtained by such a polymerization reaction of a tetracarboxylic acid component and a diamine component is, for example, a polymer having a repeating unit represented by the following formula [a]. The polyimide in which the polyimide precursor having such a repeating unit is subjected to dehydration ring closure is polyimide.

(33)

(Wherein R ₁₁ is a tetravalent organic group derived from a tetracarboxylic acid component (the following formula (c)) of the raw material and R ₁₂ is a tetravalent organic group derived from a diamine component of the starting material (the following formula (b) And A ₁₁ and A ₁₂ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different and j is a positive integer.

In the formula [a], each of R ₁₁ and R ₁₂ may be a polymer having the same repeating unit, or may be a polymer having a plurality of R ₁₁ or R ₁₂ and a repeating unit having a different structure.

In the formula [a], R ₁₁ is in because the group derived from a raw material of the tetracarboxylic acid component, (A) component and (B) a polyimide precursor, R ₁₁ is the formula (4) of the component . Since R ₁₂ is a group derived from a diamine component as a raw material, the polyimide precursor of the component (A) is represented by the formula: R ₁₂ is -P ¹ - (Q ¹ ) _P - (Q ² ) _q - (Q ³ ) _r has a side chain represented by the -P ^2, the polyimide precursor of the addition, (B) component, R ₁₂ is -CR ²¹ ₂ in the main chain-has a.

(34)

(In the formulas [b] and [c], R ₁₁ and R ₁₂ are the same as defined in formula [a].)

<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.

(35)

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).

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 70% of the ultraviolet 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 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 is excellent in reliability and is preferably used for a liquid crystal television Can be used.

Example

The abbreviations used in the examples are as follows.

&Lt; Methacrylate monomer &gt;

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MA1 was synthesized by the synthetic method described in the patent document (WO2011-084546).

MA2 was synthesized by the synthetic method described in the patent document (Japanese Patent Application Laid-Open No. 9-118717).

&Lt; Tetracarboxylic acid dianhydride &gt;

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

PMDA: pyromellitic acid dianhydride

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

<Diamine>

DDE: 4,4'-diaminodiphenyl ether

DDM: 4,4'-diaminodiphenylmethane

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

<Organic solvent>

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BC: butyl cellosolve

CH ₂ Cl ₂ : Dichloromethane

<Polymerization Initiator>

AIBN: 2,2'-azobisisobutyronitrile

[Synthesis examples of polyamic acid and polyimide]

&Lt; Synthesis Example 1: Polyamic acid &gt;

MA1 (9.97 g, 30.0 mmol) was dissolved in THF (92.0 g) and deaerated by a diaphragm pump. AIBN (0.246 g, 1.5 mmol) was then added and degassed again. Thereafter, the reaction was carried out 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.

To 6.0 g of the obtained powder was added 54.0 g of NMP and the mixture was stirred at room temperature for 3 hours. To obtain a methacrylate polymer solution (M1) having a solid concentration of 10.0 wt%. At the end of the stirring, the polymer was completely dissolved.

&Lt; Synthesis Example 2: Polyamic acid &gt;

MA1 (1.99 g, 6.0 mmol) and MA2 (7.35 g, 24.0 mmol) were treated with AIBN (0.14 g) and THF (85.45 g) in the same manner as in Synthesis Example 1 to obtain a polymer of methacrylate To obtain a solution M2.

&Lt; Synthesis Example 3: Polyamic acid &gt;

(PAA-1) concentration of 10 wt% was obtained by reacting 1.82 g of CBDA as a tetracarboxylic acid dianhydride component and 2.00 g of DDE as a diamine component in 34.43 g of NMP at room temperature for 18 hours. Solution.

&Lt; Synthesis Examples 4 to 7: Polyamic acid &gt;

The polyamic acid solutions of Synthesis Examples 4 to 7 were synthesized in the same manner as in Synthesis Example 3 of the polyamic acid in the composition shown in Table 1 below.

&Lt; Synthesis Example 8: Polyimide &gt;

To 10.0 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 5, 6.7 g of NMP was added and diluted to prepare a polyamic acid solution having a concentration of 6 wt%. 2.2 g of acetic anhydride and 1.0 g of pyridine were added to the polyamic acid solution, and the mixture was allowed to react at 50 캜 for 3 hours to imidate. The obtained polyimide solution was cooled to room temperature, and then charged into 70 g of methanol, and the precipitated solid matter was recovered. Further, this solid was washed twice with methanol, and then dried under reduced pressure at 100 占 폚 to obtain a polyimide earth-yellow powder. 3.0 g of the obtained powder was stirred with NMP 27.0 g at room temperature for 3 hours. A polyimide solution (SPI-1) having a solid concentration of 10.0 wt% was obtained. At the end of the stirring, the polymer was completely dissolved.

(Example 1)

4.8 g of a polyamic acid solution (PAA-1) was added to 1.2 g of the methacrylic acid polymer (M1) obtained in Synthesis Example 1, and the mixture was stirred at room temperature for 1 hour. 4.0 g of BCS was added to this solution, and the mixture was stirred at room temperature for 1 hour to obtain a polymer solution (A1) having a solid concentration of 6.0 wt%. This polymer solution is directly used as a liquid crystal aligning agent for forming a liquid crystal alignment film.

(Examples 2 to 8 and Comparative Examples 1 and 2)

The polymer solutions of Examples 2 to 10 were obtained in the same manner as in Example 1, with the compositions shown in Table 2 below. Also, Comparative Examples 1 and 2 were adjusted in the same manner.

[Production of liquid crystal cell]

Example 1 Using the obtained 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 having a bent 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 had a shape resembling the character of the letter. Each pixel is divided into upper and lower portions with the central bent portion 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 directions of rotation (inflation / switching) of the liquid crystal caused by the application of the voltage between the pixel electrode and the counter electrode are opposite to each other .

The liquid crystal aligning agent (A1) obtained in Synthesis 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 was irradiated with 1 mJ / cm 2 of 313 nm ultraviolet rays through a polarizing plate, and then heated on a hot plate at 150 ° C for 10 minutes (first sintering), and the substrate cooled to room temperature was heated again at 150 ° C And then heated with a hot plate for 10 minutes (secondary baking) to obtain a substrate having a liquid crystal alignment film formed thereon. In the same manner, the irradiation amount of ultraviolet rays is set to 10 mJ / cm 2 at an interval of 1 mJ / cm 2 for 10 mJ / cm 2 to 10 mJ / cm 2, to 10 mJ / cm 2 for 10 mJ / mJ / cm &lt; 2 &gt;, respectively. 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.

The liquid crystal aligning agents (A2 to A9) obtained in Examples 2 to 9 were also manufactured by the same method as in A1.

(Observation of Orientation)

A liquid crystal cell was produced by the above-mentioned method. Thereafter, a re-aroma treatment was performed in an oven at 120 캜 for 60 minutes. Thereafter, the polarizing plate was observed through a polarizing microscope in a cross-Nicol state. When the liquid crystal cell was rotated and turned to the black display state, a state in which there was no luminescent spot or orientation defect was made good. The irradiated amount of ultraviolet rays was observed on the substrates different from each other as described above, and the results are shown in Table 3 for a good irradiation dose margin with good orientation.

(Evaluation of voltage holding ratio (VHR)) [

The evaluation of the VHR was carried out by applying a voltage of 5 V for 60 seconds at a temperature of 70 占 폚 to the obtained liquid crystal cell, measuring the voltage after 1667 ms and calculating the voltage holding ratio.

For the measurement of the voltage holding ratio, a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technica Co., Ltd. was used.

The liquid crystal cell was produced in the same manner as in the case of using the above liquid crystal aligning agent (A1) by using the liquid crystal aligning agent (B1) obtained in Comparative Example 1 and the liquid crystal aligning agent (B2) obtained in Comparative Example 2, In the same way, the VHR was evaluated.

The results are shown in Table 3 below.

As shown in Table 3, in Examples 1 to 5 according to the present invention, the irradiation dose region (irradiation margin) was widened as compared with Comparative Example 1 in which component (A) was common and component (B) And it was found that a desired effect can be exerted in a wider irradiation area. In the comparison between Examples 6 to 10 and Comparative Example 2, it was found that the same can be said.

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 (17)

(A) a photosensitive side chain type polymer which exhibits liquid crystallinity in a predetermined temperature range,
(B) at least one polymer selected from the group consisting of polyimide and its precursor, 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 polyimide precursor of component (B) is obtained by polymerizing a tetracarboxylic acid component and a diamine component. 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 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, 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.
[Chemical Formula 1]

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 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;
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.
(2)

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.
(3)

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 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;
1 represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3).
[Chemical Formula 4]

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 5]

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 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;
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.
[Chemical Formula 6]

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 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;
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).
(7)

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 8]

[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) at least one polymer selected from the group consisting of polyimide and its precursor, 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. The method of claim 15,
Wherein the polyimide precursor of component (B) is obtained by polymerizing a tetracarboxylic acid component and a diamine component. A transverse electric field driving type liquid crystal display element manufactured by the method according to claim 15 or 16.

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