JP7012945B2 - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Description

The present invention comprises a polymer composition for a liquid crystal alignment agent, particularly a liquid crystal alignment agent for a transverse electric field drive type liquid crystal display element, the composition alone, the composition alone, or the composition. It has a liquid crystal alignment agent, particularly a liquid crystal alignment agent for a transverse electric field drive type liquid crystal display element, a liquid crystal alignment film formed from the liquid crystal alignment agent, particularly a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element, and the liquid crystal alignment film. The present invention relates to a substrate, particularly a substrate for a transverse electric field drive type liquid crystal display element, and a liquid crystal display element having the substrate, particularly a transverse electric field drive type liquid crystal display element.

Liquid crystal display elements are known as lightweight, thin, and low power consumption display devices, and have made remarkable progress in recent years, such as being used in large-scale television applications. The liquid crystal display element is configured by sandwiching the liquid crystal layer with, for example, a pair of transparent substrates provided with electrodes. In the liquid crystal display element, an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in a desired orientation state between the substrates.

That is, the liquid crystal alignment film is a constituent member of the liquid crystal display element, is formed on the surface of the substrate that sandwiches the liquid crystal in contact with the liquid crystal, and plays a role of orienting the liquid crystal in a certain direction between the substrates. The liquid crystal alignment film may be required to have a role of controlling the pretilt angle of the liquid crystal in addition to the role of orienting the liquid crystal in a certain direction such as a direction parallel to the substrate. The ability to control the orientation of the liquid crystal in such a liquid crystal alignment film (hereinafter referred to as the orientation control ability) is given by performing an orientation treatment on the organic film constituting the liquid crystal alignment film.

As a method for aligning a liquid crystal alignment film for imparting an orientation control ability, a photoalignment method is known in addition to the conventional rubbing method. Compared with the conventional rubbing method, the optical alignment method does not require rubbing, there is no concern about dust generation or static electricity, and the alignment process can be applied to the substrate of the liquid crystal display element having an uneven surface. It has the advantage of being able to do it.
There are various photo-alignment methods, 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 according to the anisotropy.

As the photo-alignment method, a decomposition type photo-alignment method, a photocrosslinking type, a photoisomerization type photo-alignment method, and the like are known.
In the decomposition type photo-orientation method, for example, a polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition is caused by utilizing the polarization direction dependence of ultraviolet absorption of the molecular structure, and the polyimide left without decomposition is generated. (For example, refer to Patent Document 1).

In the photocrosslinking type and photoisomerization type photoorientation method, for example, polyvinyl synnamate is used to irradiate polarized ultraviolet rays, and a dimerization reaction (crosslinking reaction) is carried out at the double-bonded portion of two side chains parallel to the polarization. This is a method of causing the liquid crystal to be generated and orienting the liquid crystal in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1). When a side-chain polymer having azobenzene in the side chain is used, it is irradiated with polarized ultraviolet rays to cause an isomerization reaction in the azobenzene portion of the side chain parallel to the polarization, and the liquid crystal is formed in a direction orthogonal to the polarization direction. Orientation (see, eg, Non-Patent Document 2). Further, Patent Document 3 discloses a liquid crystal alignment film obtained by using a photoalignment method by photocrosslinking, photoisomerization or photofries rearrangement.

Japanese Patent No. 3893659 Japanese Unexamined Patent Publication No. 2-3724 WO2014 / 054785

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

As described above, the optical alignment method has a great advantage because it does not require the rubbing step itself as compared with the rubbing method which has been industrially used conventionally as an alignment processing method for a liquid crystal display element. Compared to the rubbing method in which the orientation control ability is substantially constant by rubbing, the optical alignment method can control the orientation control ability by changing the irradiation amount of the polarized light.
However, if the orientation control ability of the main component used in the photo-alignment method is too sensitive to the irradiation amount of polarized light, the orientation of a part or the whole of the liquid crystal alignment film becomes incomplete, and stable liquid crystal orientation cannot be realized. Occurs.

Therefore, an object of the present invention is a polymer composition for producing a liquid crystal alignment film, which can efficiently obtain a high-quality liquid crystal alignment film by expanding the range of the amount of light irradiation in which the orientation control ability is stably generated. The object of the present invention is to provide a composition for producing a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element.
Further, an object of the present invention is, in addition to or in addition to the above object, a liquid crystal alignment agent having the composition, a liquid crystal alignment film produced by using the liquid crystal alignment agent, and a substrate having the liquid crystal alignment film. The present invention provides a liquid crystal display element having the liquid crystal alignment film and / or the substrate, particularly a lateral electric field drive type liquid crystal display element.

The present inventors have found the following inventions.
<1> (A) At least two kinds of polymers having a structure exhibiting photoreactivity and a structure exhibiting liquid crystallinity;
(B) A polymer produced by using at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine compound;
And (C) organic solvent;
A polymer composition containing, particularly a polymer composition for producing a liquid crystal alignment film, and more particularly a composition for producing a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element.
<2> In the above <1>, of at least two kinds of polymers which are the components (A), one polymer (A1) and the other polymer (A2) have different amounts of structures that exhibit photoreactivity with each other. Is good.

<3> In the above <1> or <2>, it is preferable that at least two kinds of polymers which are the components (A) each have a structure which expresses photoreactivity and a structure which expresses only liquid crystallinity. In addition, in this specification, "only liquid crystal" of "structure which expresses only liquid crystal" is a term used when "photoreactivity" and "liquid crystal" are considered, and "photoreaction". The word "only" indicates that "sexuality" is not expressed but "liquid crystallinity" is expressed.

<4> The structures that exhibit photoreactivity in <1> to <3> above are
The following formulas (1) to (6)
(In the formula, A, B, and D are independent, single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO. Represents -O- or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced 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 the same or selected from their substituents. It is a group consisting of 2 to 6 different rings bonded via a bonding group B, and the hydrogen atoms bonded to them are independently −COOR ₀ (in the formula, R ₀ is a hydrogen atom or 1 to 1 to carbon atoms. (Representing an alkyl group of 5), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. The hydrogen atoms bonded to are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group of;
R represents a hydroxy group, an alkoxy group having ₁ to 6 carbon atoms, or represents the same definition as Y1;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = Representing CH-, when the number of Xs is 2, the Xs 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 independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-. It may be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
One of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are independently selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. It is a group; however, when X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring. When the number of Ps is 2 or more, the Ps may be the same or different, and when the number of Qs is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
When both l1 and l2 are 0, A also represents a single bond when T is a single bond;
When l1 is 1, B also represents a single bond when T is a single bond;
H and I are groups independently selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof. )
It is preferable that the structure is any one selected from the group consisting of.

<5> In the above <3> or <4>,
The structures that express only liquid crystallinity are the following formulas (21) to (31).
(In the formula, A and B have the same definition as above;
_Y3 is a group selected from the group consisting of monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, nitrogen-containing heterocycles, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof. Yes, the hydrogen atoms attached to them 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 contains 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, and nitrogen. Represents a heterocycle, 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;
One of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, but in equations (23) to (24), the total of all m is 2 or more, and equations (25) to (26). ), The sum of all m is 1 or more, and m1, m2, and m3 independently represent integers of 1 to 3;
R ₂ is a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms. And represents an alkyl group or an alkyloxy group;
Z ₁ and Z ₂ are preferably any one of the structures selected from the group consisting of single bond, -CO-, -CH ₂ O-, -CH = N-, -CF _2- ).

<6> In any of the above <2> to <5>, the amount of the structure that expresses the photoreactivity of the polymer (A1) expresses the structure that expresses the photoreactivity of the polymer (A1) and the liquid crystal property. When the total with the structure is 100 mol%, it is α mol% (α is 15 or more, preferably 15 to 100, more preferably 20 to 80).
The amount of the structure that expresses the photoreactivity of the polymer (A2) is 0.95 α mol% or less, assuming that the structure that expresses the photoreactivity of the polymer (A2) and the structure that expresses the liquid crystal property are 100 mol%. It is preferably 0.1α to 0.8α mol%, more preferably 0.25α to 0.5α mol%.
<7> In any of the above <2> to <6>, the weight average molecular weight of the polymer (A1) is β (β is 30,000 or more, preferably 30,000 to 300,000, more preferably 40,000 to 200,000. It is more preferably 60,000 to 150,000), and the weight average molecular weight of the polymer (A2) is 0.1β to 0.9β, preferably 0.2β to 0.8β, and more preferably 0.3β to 0.7β. It is good to have it.
<8> In any of the above <2> to <7>, assuming that the total weight of the polymer (A1) and the polymer (A2) is 100 wt%, the polymer (A1) is 20 to 95 wt%, preferably 50 to 90 wt%. %, More preferably 60 to 80 wt%.

<9> In any of the above <1> to <8>, the monomer (M1); and (M-2) having a structure in which at least two polymers exhibit (M-1) photoreactivity and liquid crystallinity. It is preferably formed with a monomer (M2); which has a structure expressing only liquid crystallinity.
<10> In the above <9>, the monomer (M1) preferably has a structure represented by any of the above formulas (1) to (20).
<11> In the above <9> or <10>, it is preferable that the monomer (M2) has a structure represented by the above formulas (21) to (31).

<12> In any of the above <9> to <11>, the monomer (M1) has the following formulas MA1, MA3, MA4, MA5, MA14, MA16 to MA23, MA25, MA28 to MA30, MA32, MA34, MA36, MA38. It is preferably at least one selected from the group consisting of MA42, MA44 and MA46.
<13> In any of the above <9> to <12>, the monomer (M2) is from the group consisting of the following formulas MA2, MA9 to MA13, MA15, MA24, MA26, MA27, MA31, MA35, MA37, MA43 and MA45. It should be at least one selected.

<14> In any of the above <9> to <13>, when the total of the monomer (M1) and the monomer (M2) is 100 mol%, the polymer (A1) contains α mol% (M1) of the monomer (M1). α is formed so as to be 15 or more, preferably 15 to 100, more preferably 20 to 80) and the residue is the monomer (M2).
The polymer (A2) has a monomer (M1) of 0.95α mol% or less, preferably 0.1α to 0.8α mol%, more preferably 0.25α to 0.5α mol%, and a residue of the monomer (M2). ), It is better to be formed.

<15> In the above <1> to <14>, the component (B) is a polymer produced by using at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and two or more diamine compounds. Therefore, it is preferable that the polymer has a structure represented by the formula (Y2-1) as a diamine-derived structure.

However, Z ₃ is an alkylene group having 1 to 20 carbon atoms which may be interrupted by a bond selected from an ether bond, an ester bond, an amide bond and a urea bond, and the bond portion between Z ₃ and the benzene ring is a single bond. , Ether bond, ester bond, urea bond or amide bond.

<16> In the above <1> to <15>, the polymer of the component (B) is preferably polyurea obtained by polymerizing the diisocyanate component and the diamine component.
<17> In the above <1> to <15>, the polymer of the component (B) is a polyurea polyimide precursor obtained by polymerizing a diisocyanate component, a tetracarboxylic acid derivative, and a diamine component. Is good.
<18> In the above <1> to <15>, the polymer of the component (B) is preferably a polyimide precursor obtained by polymerizing a tetracarboxylic acid derivative and a diamine component.

<19> A liquid crystal alignment agent containing the polymer composition according to any one of <1> to <18>, particularly a liquid crystal alignment agent for a transverse electric field drive type liquid crystal display element.
<20> A liquid crystal alignment film formed from the liquid crystal alignment agent according to <19>, particularly a liquid crystal alignment agent for a transverse electric field drive type liquid crystal display element, particularly a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element.

<21> [I] A step of applying the polymer composition according to any one of <1> to <18> above onto a substrate having a conductive film for driving a transverse electric field to form a coating film;
[II] A step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II].
A method for producing a liquid crystal alignment film, which comprises a liquid crystal alignment film having an orientation control ability, particularly a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element.
<22> The liquid crystal alignment film of the above <21>, particularly a substrate having a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element, particularly a substrate for a transverse electric field drive type liquid crystal display element.
<23> [I] A step of applying the polymer composition according to any one of <1> to <18> above onto a substrate having a conductive film for driving a transverse electric field to form a coating film;
[II] A step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II].
A method for manufacturing a substrate having a liquid crystal alignment film, which comprises a liquid crystal alignment film having an orientation control ability, particularly a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element.

<24> A liquid crystal display element having a substrate obtained in <23>, particularly a substrate for a horizontal electric field drive type liquid crystal display element, particularly a horizontal electric field drive type liquid crystal display element.
<25> A process of manufacturing a substrate (first substrate) according to the above <23>;
[I'] A step of applying the polymer composition according to any one of <1> to <18> above on a second substrate to form a coating film;
[II'] A step of irradiating the coating film obtained in [I'] with polarized ultraviolet rays;
[III'] The step of heating the coating film obtained in [II'];
A step of obtaining a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment of the first and second substrates via the liquid crystal. A step of arranging the first and second substrates so as to face each other so that the films face each other to obtain a liquid crystal display element;
A method for manufacturing a liquid crystal display element, which comprises a liquid crystal display element, particularly a lateral electric field drive type liquid crystal display element.

INDUSTRIAL APPLICABILITY According to the present invention, a polymer composition for producing a liquid crystal alignment film, specifically horizontal It is possible to provide a composition for producing a liquid crystal alignment film for an electric field driven liquid crystal display element.
Further, according to the present invention, a liquid crystal alignment agent having the composition, a liquid crystal alignment film produced by using the liquid crystal alignment agent, a substrate having the liquid crystal alignment film, and the like, in addition to the above effects or in addition to the above effects. A liquid crystal display element having a liquid crystal alignment film and / or the substrate, particularly a transverse electric field drive type liquid crystal display element can be provided.

The present application comprises a polymer composition for a liquid crystal alignment agent, particularly a liquid crystal alignment agent for a transverse electric field drive type liquid crystal display element, the composition alone, the composition alone, or the composition. A liquid crystal alignment agent, particularly a liquid crystal alignment agent for a transverse electric field drive type liquid crystal display element, a liquid crystal alignment film formed from the liquid crystal alignment agent, particularly a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element, and a substrate having the liquid crystal alignment film. In particular, a substrate for a transverse electric field drive type liquid crystal display element and a liquid crystal display element having the substrate, particularly a transverse electric field drive type liquid crystal display element are provided. Hereinafter, detailed explanations will be given in order.

<Polymer composition>
The present application provides a polymer composition, particularly a polymer composition for a liquid crystal alignment agent, and more particularly for a liquid crystal alignment agent for a transverse electric field drive type liquid crystal display element.
The polymer composition of the present application is
(A) At least two polymers having a structure exhibiting photoreactivity and a structure exhibiting liquid crystallinity; (B) At least one selected from a diisocyanate component and a tetracarboxylic acid derivative, and a diamine compound. Polymer; and (C) containing an organic solvent.
Further, among at least two kinds of polymers as the component (A), it is preferable that one polymer (A1) and the other polymer (A2) have different amounts of structures that exhibit photoreactivity with each other.

It is preferable that at least two kinds of polymers as the component (A) have a structure exhibiting photoreactivity and liquid crystallinity, and a structure exhibiting only liquid crystallinity, respectively. In addition, in this specification, "only liquid crystal" of "structure which expresses only liquid crystal" is a term used when "photoreactivity" and "liquid crystal" are considered, and "photoreaction". The word "only" indicates that "sexuality" is not expressed but "liquid crystallinity" is expressed.

<(A) Polymer having a structure exhibiting photoreactivity and a structure exhibiting liquid crystallinity>
As used herein, the term "structure exhibiting photoreactivity" refers to a structure that reacts with light in a certain wavelength range, particularly light in a wavelength range of 250 nm to 400 nm, for example, the structure is a polymer as a component (A). It is better to have it in the side chain of.

Further, in the present specification, "photoreactivity" is not particularly limited, but refers to exhibiting a cross-linking reaction, an isomerization reaction, or a photo-Fries rearrangement in response to light, and preferably exhibits a cross-linking reaction. Is good. When a polymer having a "structure that exhibits photoreactivity" is used, the realized orientation control ability can be stably maintained for a long period of time even when exposed to external stress such as heat.
As used herein, the term "structure that exhibits liquid crystallinity" refers to a structure that exhibits liquid crystallinity in a certain temperature range, particularly in a temperature range of 100 to 300 ° C., for example, a mesogen group or a mesogen component in the side chain of a polymer. It is preferable that the structure has.
When a polymer having a "structure that exhibits liquid crystallinity" is used, stable liquid crystal orientation can be obtained when the polymer is used as a liquid crystal alignment film.

The structure of the polymer may have, for example, a main chain and a side chain bonded to the main chain, and the side chain may have a "structure that exhibits photoreactivity" and a "structure that exhibits liquid liquidity". The "structure that expresses photoreactivity" and the "structure that expresses liquid crystallinity" may be present in the same side chain or in different side chains. It is preferable that the polymer has a structure in which one side chain exhibits photoreactivity and liquid crystallinity, and another side chain has a structure in which only liquid crystallinity is exhibited.
When the "structure exhibiting photoreactivity" and the "structure exhibiting liquid crystallinity" are on the same side chain, a mesogen component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, or an azobenzene group is used. When the side chain has a "structure that expresses photoreactivity" that is bonded to the tip and exhibits a cross-linking reaction or an isomerization reaction in response to light, the side chain is a "structure that expresses liquid crystallinity". There is a case where the structure has a phenylbenzoate group that also serves as a mesogen component and undergoes a photofreeze rearrangement reaction, which is a “structure that exhibits photoreactivity”.

Specific examples of the main chains of at least two polymers which are the components (A) of the present invention are not particularly limited, but are independently, but independently, hydrocarbons, (meth) acrylates, itaconates, fumarates, maleates, and α-. It is preferably composed of at least one selected from the group consisting of radically polymerizable groups such as methylene-γ-butyrolactone, styrene, vinyl, maleimide and norbornene and siloxane.

<< Structure that expresses photoreactivity >>
The structure exhibiting photoreactivity, particularly the structure exhibiting photoreactivity and liquid crystallinity, is preferably a structure represented by any one selected from the group consisting of the formulas (1) to (6). In the formula, A, B, D, S, Y ₁ , Y ₂ , R, X, Cou, q1 and q2, q3, P and Q, l1, l2, H, and I have the same definitions as described above. Have.

The side chain is preferably any one of the photosensitive side chains selected from the group consisting of the following formulas (7) to (10).
In the formula, A, B, D, Y ₁ , X, Y ₂ , and R have the same definition as above;
l represents an integer from 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer from 0 to 12 (where B is a single bond when n = 0).

The side chain is preferably any one of the photosensitive side chains selected from the group consisting of the following formulas (11) to (13).
In the formula, A, X, l, m, m1 and R have the same definitions as above.

The side chain is preferably a photosensitive side chain represented by the following formula (14) or (15).
In the formula, A, Y1, _l , m1 and m2 have the same definitions as above.

The side chain is preferably a photosensitive side chain represented by the following formula (16) or (17).
In the formula, A, X, l and m have the same definitions as above.

The side chain is preferably a photosensitive side chain represented by the following formula (18) or (19).
In the formula, A, B, Y1, q1, q2, m1 and m2 have the same definitions as above.
R ₁ is 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 alkyl having 1 to 5 carbon atoms. Represents an oxy group.

The side chain is preferably a photosensitive side chain represented by the following formula (20).
In the formula, A, Y ₁ , X, l and m have the same definitions as above.

<< Structure that expresses only liquid crystal properties >>
The structure that expresses only liquid crystallinity is preferably a structure represented by any one selected from the group consisting of the formulas (21) to (31). In the formula, A, B, Y ₃ , R ₃ , q1, q2, l, m, m1, m2, m3, R ₂ , Z ₁ , and Z ₂ have the same definitions as described above.

<< Amount of structure exhibiting photoreactivity of each of at least two polymers as component (A) >>
When the total of the structure expressing photoreactivity and the structure expressing only liquid crystallinity is 100 mol% in each of at least two kinds of polymers which are the components (A).
The amount of the structure exhibiting the photoreactivity of the polymer (A1) is α mol% (α is 15 or more, preferably 15 to 100, more preferably 20 to 80).
The amount of the structure exhibiting the photoreactivity of the polymer (A2) is preferably less than the amount of the structure exhibiting the photoreactivity of the polymer (A1), specifically 0.95α mol% or less, preferably 0.95α mol% or less. It is preferably 0.1α to 0.8α mol%, more preferably 0.25α to 0.5α mol%.
It is considered that the components (A) have the following actions by using polymers having different amounts of structures exhibiting photoreactivity. That is, the orientation by ultraviolet irradiation is determined by the polymer (polymer (A1)) having a relatively large number of structures exhibiting photoreactivity. On the other hand, a polymer (polymer (A2)) having a relatively small number of structures exhibiting photoreactivity but a relatively large number of structures exhibiting liquid crystallinity is oriented according to the orientation determined by the polymer (A1). Of the at least two types of polymers, each polymer can share the action of each and effectively exert the action.

<< Weight average molecular weight of each of at least two polymers as component (A) >>
Further, of at least two kinds of polymers which are the components (A), one of them has a weight average molecular weight of β (β is 30,000 or more, preferably 30,000 to 300,000, more preferably 40,000 to 200,000, still more preferably. 60,000 to 150,000),
On the other hand, the weight average molecular weight is preferably 0.1β to 0.9β, preferably 0.2β to 0.8β, and more preferably 0.3β to 0.7β.
Unless otherwise specified, the weight average molecular weight is measured by the GPC (Gel Permeation Chromatography) method in the present specification.
In particular, the polymer (A1) having a relatively large amount of structure exhibiting photoreactivity has a weight average molecular weight of β (β is 30,000 or more, preferably 30,000 to 300,000, more preferably 40,000 to 20). 10,000, more preferably 60,000 to 150,000),
The polymer (A2) having a relatively small amount of the structure exhibiting photoreactivity has a weight average molecular weight of 0.1β to 0.9β, preferably 0.2β to 0.8β, and more preferably 0.3β to. It should be 0.7β.

By using at least two polymers having different weight average molecular weights as the component (A), when the polymer is formed as a liquid crystal alignment film, the polymer having a large weight average molecular weight is a relatively lower layer of the liquid crystal alignment film. While it tends to be formed in (a layer relatively close to the substrate), a polymer having a small weight average molecular weight tends to be formed in a relatively upper layer (a layer relatively far from the substrate) of the liquid crystal alignment film. be.
It is considered that having such a configuration has the following effects.
That is, the polymer (A1) having a relatively large number of structures exhibiting photoreactivity and a large weight average molecular weight is formed in a relatively lower layer (a layer relatively close to the substrate) of the liquid crystal alignment film. On the other hand, the polymer (A2) having a relatively small structure exhibiting photoreactivity and a small weight average molecular weight is formed in a relatively upper layer (a layer relatively far from the substrate) of the liquid crystal alignment film. In this situation, when the polymer (A1) in the relatively lower layer (the layer relatively close to the substrate) is irradiated with the polarized ultraviolet rays, the polymer (A1) in the relatively lower layer is oriented according to the polarized ultraviolet rays. On the other hand, it is considered that the polymer (A2) in the relatively upper layer (the layer relatively far from the substrate) has the effect of orienting along the orientation of the polymer (A1).
Assuming that the total weight of the polymer (A1) and the polymer (A2) is 100 wt%, the polymer (A1) is 20 to 95 wt%, preferably 50 to 90 wt%, more preferably 60 to 80 wt%, while the polymer. (A2) should be the remainder.

<Method for producing each of at least two polymers as component (A)>
As long as the at least two polymers which are the components (A) of the present invention have the above-mentioned constitution, the production method thereof is not particularly limited. For example, at least two polymers which are the components (A) of the present invention have only (M-1) a monomer (M1) having a structure exhibiting photoreactivity and liquid crystal property; and (M-2) liquid crystal property. It is preferably formed with a monomer (M2); which has a structure to be expressed. It should be noted that the copolymer can be copolymerized with other monomers as long as the photoreactiveness and / or liquid crystallinity development ability is not impaired.
As described above, at least two kinds of polymers which are the components (A) of the present invention are formed having the monomer (M1) and the monomer (M2), but the sum of the monomers (M1) and the monomers (M2) is added. When it is 100 mol%, the polymer (A1) of at least two kinds of polymers has a monomer (M1) of α mol% (α is 15 or more, preferably 15 to 100, more preferably 20 to 80). Moreover, it is preferable that the residue is formed so that it is a monomer (M2).
Further, in the polymer (A2), the monomer (M1) is 0.95α mol% or less, preferably 0.1α to 0.8α mol%, more preferably 0.25α to 0.5α mol%, and the residue is the monomer. It is better to be formed as in (M2).
The monomer (M1) and the monomer (M2) used in the polymer (A1) and the polymer (A2) are preferably common to each other.

<< Monomer (M1) having a structure exhibiting photoreactivity and liquid crystallinity and its manufacturing method >>
At least two kinds of polymers which are the components (A) of the present invention have the above-mentioned monomer (M1) having a structure exhibiting photoreactivity and liquidity; and (M-2) a monomer having a structure expressing only liquidity. (M2); It is better to obtain by forming, specifically, copolymerizing with.

[Monomer having a structure exhibiting photoreactivity and liquid crystallinity (M1)]
The monomer (M1) having a structure exhibiting photoreactivity and liquidity can form a polymer having a structure exhibiting photoreactivity and liquidity at the side chain site of the polymer when the polymer is formed. It is a monomer that can be produced.
The following structures and derivatives thereof are preferable as the structures that exhibit photoreactivity in the side chain site.

More specific examples of the monomer (M1) include radical polymerizable groups such as hydrocarbons, (meth) acrylates, itaconates, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and siloxanes. A structure exhibiting photoreactivity and liquid liquidity consisting of a polymerizable group composed of at least one selected from the group consisting of the above formulas (1) to (6) and at least one of the above formulas (1) to (6), preferably, for example, for example. A structure exhibiting photoreactivity and liquid crystallinity consisting of at least one of the above formulas (7) to (10), and exhibiting photoreactivity and liquid crystallinity consisting of at least one of the above formulas (11) to (13). Structure, structure expressing photoreactivity and liquidity represented by the above formula (14) or (15), structure expressing photoreactivity and liquidity represented by the above formula (16) or (17), The structure may have a structure expressing photoreactivity and liquidity represented by the above formula (18) or (19), and a structure expressing photoreactivity and liquidity represented by the above formula (20). preferable.

The monomer (M1) is polymerized in the following formulas MA1, MA3, MA4, MA5, MA14, MA16 to MA23, MA25, MA28 to MA30, MA32, MA34, MA36, MA38 to MA42, MA44 and MA46, and their compounds. The polymerizable group of the compound having methacrylate as the sex group was replaced with a polymerizable group selected from the group consisting of acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornen and siloxane. It is preferably at least one selected from the compounds. In particular, the monomer (M1) preferably has a (meth) acrylate as a polymerizable group, and preferably, for example, the end of the side chain is COOH.
MA1 to MA46 can be synthesized as follows.

MA1 can be synthesized by the synthetic method described in Patent Document (WO2011-084546).
MA2 can be synthesized by the synthetic method described in Patent Document (Japanese Patent Laid-Open No. 9-118717).
MA3 can be synthesized by the synthetic method described in the non-patent document (Macromolecules 2002, 35, 706-713).
MA4 can be synthesized by the synthesis method described in Patent Document (WO2014 / 054785).
MA5 can be synthesized by the synthetic method described in Patent Document (Japanese Patent Laid-Open No. 2010-18807).
MA6 to MA9 can be synthesized by the synthesis method described in Patent Document (WO2014 / 054785).
As the MA10, M6BC (manufactured by Midori Chemical Co., Ltd.), which can be purchased commercially, can be used.
MA11 to 13 can be synthesized by the synthesis method described in Patent Document (WO2014 / 054785).

MA14-18 can be purchased commercially, and M4CA, M4BA, M2CA, M3CA, and M5CA (all of which are manufactured by Midori Chemical Co., Ltd.) can be used.
MA19-23 can be synthesized by the synthesis method described in Patent Document (WO2014 / 054785).
MA24 can be synthesized by the synthesis method described in the non-patent document (Polymer Journal, Vol.29, No.4, pp303-308 (1997)).
MA25 can be synthesized by the synthesis method described in Patent Document (WO2014 / 054785).
MA26 and MA27 are synthetic methods described in non-patent documents (Macromolecules (2012), 45 (21), 8547-8554) and non-patent documents (Liquid Crystals (1995), 19 (4), 433-40), respectively. Can be synthesized at.
MA28-33 can be synthesized by the synthesis method described in Patent Document (WO2014 / 054785).
MA34 to 39 can be synthesized by the synthesis method described in Patent Document (WO2014 / 054785).
MA40 and 41 can be synthesized by the synthesis method described in Patent Document (Japanese Patent Laid-Open No. 2009-511431).
MA42 can be synthesized by the synthesis method described in Patent Document (WO2014 / 054785).
MA43 can be synthesized by the synthesis method described in Patent Document (WO2012-115129).
MA44 can be synthesized by the synthesis method described in Patent Document (WO2013-133578).
MA45 can be synthesized by the synthesis method described in Patent Document (WO2008-072652).
MA46 can be synthesized by the synthesis method described in Patent Document (WO2014 / 054785).

[Monomer (M2) having a structure that expresses only liquid crystallinity and a method for producing the same]
The monomer (M2) having a structure that expresses only liquid crystallinity is a monomer in which a polymer derived from the monomer expresses liquid crystallinity and the polymer can form a mesogen group at a side chain site.

As the mesogen group having a side chain, even if it is a group having a mesogen structure by itself such as biphenyl or phenylbenzoate, or a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid. good. The following structure is preferable as the mesogen group contained in the side chain.

More specific examples of the monomer (M2) having a structure expressing only liquidity include hydrocarbons, (meth) acrylates, itaconates, fumarate, maleates, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, and the like. The structure has a structure consisting of at least one of the above formulas (21) to (31) and a polymerizable group composed of at least one selected from the group consisting of radically polymerizable groups such as norbornene and siloxane. Is preferable.

The monomer (M2) is the polymerizable property of the above formulas MA2, MA9 to MA13, MA15, MA24, MA26, MA27, MA31, MA35, MA37, MA43 and MA45, and compounds having methacrylate as a polymerizable group among those compounds. At least one selected from the group consisting of compounds in which the group is replaced with a polymerizable group selected from the group consisting of acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and siloxane. It is good to be. In particular, the monomer (M2) preferably has a (meth) acrylate as a polymerizable group, and preferably, for example, the end of the side chain is COOH.

<< Monomer with crosslinkable group (M3) >>
The polymer (A1) and / or the polymer (A2) is a monomer having a (M-3) crosslinkable group, specifically, the following formulas (G-1), (G-2), (G-3) and ( It may be formed having a monomer (M3) having at least one group selected from the group consisting of G-4), more specifically, a monomer having a structure represented by the following formula (0). ..

[Monomer having a structure represented by the formula (0)]
More specific examples of the monomer having the structure represented by the above formula (0) include hydrocarbons, (meth) acrylates, itaconates, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, and the like. It is preferable to have a polymerizable group composed of at least one selected from the group consisting of a radically polymerizable group such as norbornene and a siloxane, and a structure represented by the above formula (0).

Among such monomers, examples of the monomer having an epoxy group include compounds such as glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and allylglycidyl ether. Among them, glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5- Examples include hexene, 1,7-octadienmonoepoxyside, and the like.

Specific examples of the monomer having tyran include those in which the epoxy structure of the above-mentioned monomer having an epoxy group is replaced with tyran.
Specific examples of the monomer having aziridine include those in which the epoxy structure of the above-mentioned monomer having an epoxy group is replaced with aziridine or 1-methylaziridine.

Examples of the monomer having an oxetane group include a (meth) acrylic acid ester having an oxetane group. Among such monomers, 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-methyl-oxetane, 3- (acryloyloxymethyl) -3- Methyl-oxetan, 3- (methacryloyloxymethyl) -3-ethyl-oxetan, 3- (acryloyloxymethyl) -3-ethyl-oxetan, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3-( Acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetan, 3- (acryloyloxymethyl) -2-phenyl-oxetane, 2- (methacryloyloxymethyl) oxetane, 2 -(Acryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyloxymethyl) -4-trifluoromethyloxetane are preferred, 3- (methacryloyloxymethyl) -3- Examples thereof include ethyl-oxetane and 3- (acryloyloxymethyl) -3-ethyl-oxetane.

As the monomer having a thietan group, for example, a monomer in which the oxetane group of the monomer having an oxetane group is replaced with the thietan group is preferable.

As the monomer having an azetidine group, for example, a monomer in which the oxetane group of the monomer having an oxetane group is replaced with the azetidine group is preferable.

Among the above, a monomer having an epoxy group and a monomer having an oxetane group are preferable, and a monomer having an epoxy group is more preferable, from the viewpoint of availability and the like. Of these, glycidyl (meth) acrylate is preferable from the viewpoint of availability.

<< Monomer having a nitrogen-containing aromatic heterocyclic group (M4) >>
The polymer (A1) and / or the polymer (A2) is a monomer (M4) having at least one group selected from the group consisting of (M-4) nitrogen-containing aromatic heterocyclic groups, amide groups and urethane groups, if desired. ); May be formed.

The nitrogen-containing aromatic heterocycle consists of a group consisting of the following formulas [20a], formula [20b] and formula [20c] (in the formula, Z ₂ is a linear or branched alkyl group having 1 to 5 carbon atoms). It is preferably an aromatic cyclic hydrocarbon containing at least one, preferably 1 to 4 structures of choice.

Specifically, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a benzazole ring, a purine ring, a thiaziazole ring, a pyridazine ring, a pyrazoline ring, Examples include triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thynoline ring, phenanthroline ring, indole ring, quinoxalin ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, and acridin ring. Can be done. Further, the carbon atom of these nitrogen-containing aromatic heterocycles may have a substituent containing a heteroatom.
Of these, for example, a pyridine ring is preferable.

When the polymer (A1) or the polymer (A2) has a group selected from a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group, the polymer composition of the present invention is ionic when used as a liquid crystal alignment film. A more durable liquid crystal alignment film may be used to reduce the elution of impurities and promote the cross-linking reaction of the above-mentioned cross-linking group, more specifically, the cross-linking reaction of the group represented by the above formula (0). Obtainable. In order to produce a polymer having a group selected from a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group, the monomer (M4) may be mixed with the above-mentioned monomer (M1) and monomer (M2), and optionally a monomer (M3). It may be copolymerized.

The monomer (M4) is selected from the group consisting of radically polymerizable groups such as hydrocarbons, (meth) acrylates, itaconates, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and siloxane. It is preferable to have a polymerizable group composed of at least one kind and a structure having a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group. The NH of the amide group and the urethane group may or may not be substituted. Examples of the substituent which may be substituted include an alkyl group, an amino-protecting group, a benzyl group and the like.

Among such monomers, examples of the monomer having a nitrogen-containing aromatic heterocyclic group include, for example, 2- (2-pyridylcarbonyloxy) ethyl (meth) acrylate and 2- (3-pyridylcarbonyloxy). Ethyl (meth) acrylate, 2- (4-pyridylcarbonyloxy) ethyl (meth) acrylate, and the like can be mentioned.

Specific examples of the monomer having an amide group or a urethane group include 2- (4-methylpiperidin-1-ylcarbonylamino) ethyl (meth) acrylate and 4- (6-methacryloyloxyhexyloxy) benzoic acid. Examples thereof include N- (tersary butyloxycarbonyl) piperidine-4-yl ester, 4- (6-methacryloyloxyhexyloxy) benzoic acid 2- (tersary butyloxycarbonylamino) ethyl ester and the like.

(M-4) The monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group is the above-mentioned formulas MA6 to MA8, MA33, and the same. The polymerizable group of the compound having methacrylate as a polymerizable group in the compound is selected from the group consisting of acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and siloxane. It is preferably at least one selected from the group consisting of compounds replaced with a group.

As described above, it can be copolymerized with other monomers as long as the photoreactiveness and / or liquid crystallinity is not impaired.
Examples of other monomers include industrially available radical polymerization-reactive monomers.

Specific examples of other monomers include unsaturated carboxylic acids, acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic acid anhydrides, styrene compounds and vinyl compounds.

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

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, 2,2,2-trifluoroethyl acrylate and tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Examples thereof include 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, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate and tert-butyl. Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Examples thereof include propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate and the like.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether and the like.
Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene and the like.
Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

The method for producing at least two kinds of polymers of the present invention is not particularly limited, and a general-purpose method that is industrially treated can be used. Specifically, the above-mentioned monomer (M1) having a structure expressing photoreactivity and liquidity; and (M-2) a cation using a vinyl group of a monomer (M2) having a structure expressing only liquidity. It can be produced by polymerization, radical polymerization, or anionic polymerization. Of these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.

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

The radical thermal polymerization initiator is a compound that generates radicals by heating to a temperature higher than the decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), and hydroperoxides (peroxidation). Hydrogen, tert-butylhydroxide, cumenehydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.) Etc.), Alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, etc.) Examples thereof include sodium persulfate, ammonium persulfate, etc.) and azo compounds (azobisisobutyronitrile, and 2,2'-di (2-hydroxyethyl) azobisisobutyronitrile, etc.). Such a radical thermal polymerization initiator may be used alone 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 radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone and 2-hydroxy. -2-Methylpropiophenone, 2-Hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthron, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-( 4-Molholinophenyl) -butanone-1, 4-ethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (3,4'-tri ( t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphinoxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3' , 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(2'-Methtylyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [P-N, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s- Triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-Mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2'-bi Su (2-chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4, 4', 5,5'-Tetraphenyl-1,2'-biimidazole, 2,2'bis (2,4-dibromophenyl) -4,4', 5,5'-Tetraphenyl-1,2' -Bimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2) -Dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, bis (5-2,4-cyclopentadiene-1- Il) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-Tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di ( Methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2- (3- (3-) Methyl-3H-benzothiazole-2-iriden) -1-naphthalen-2-yl-etanone, or 2- (3-methyl-1,3-benzothiazole-2 (3H) -iriden) -1- (2-) Benzoyl) Etanone and the like can be mentioned. These compounds may be used alone or in admixture 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 monomer (M1) having a structure that expresses photoreactivity and liquidity; and (M-2) the monomer (M2) having a structure that expresses only liquidity are copolymerized to form at least two polymers of the present invention. The organic solvent used in the reaction for obtaining each is not particularly limited as long as the produced polymer can be dissolved. Specific examples are given below.

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactum, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide , Gamma-butylollactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cell solve, ethyl cell solve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl Ether, Diethylene Glycol, Diethylene Glycol Monoacetate, Diethylene Glycol Dimethyl Ether, Dipropylene Glycol Monoacetate Monomethyl Ether, Dipropylene Glycol Monomethyl Ether, Dipropylene Glycol Monoethyl Ether, Dipropylene Glycol Monoacetate Monoethyl Ether, Dipropylene Glycol Monopropyl Ether, Dipropylene Glycol Monoacetate Monopropyl Ether, 3-Methyl-3-methoxybutyl Acetate, Tripropylene Glycol Methyl Ether, 3-Methyl-3-methoxybutanol, Diisopropyl Ether, Ethyl Isobutyl Ether, Diisobutylene, Amyl Acetate, Butyl Butyrate, Butyl Ether , Diisobutylketone, 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, acetic acid Ethyl, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion Acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglime, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3- Examples thereof include ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like.

These organic solvents may be used alone or in combination. Further, even if the solvent does not dissolve the produced polymer, it may be mixed with the above-mentioned organic solvent and used as long as the produced polymer does not precipitate.
Further, in radical polymerization, oxygen in the organic solvent causes the polymerization reaction to be inhibited, so it is preferable to use an organic solvent degassed to the extent possible.

The polymerization temperature at the time of radical polymerization can be selected from any temperature of 30 ° C. to 150 ° C., but is preferably in the range of 50 ° C. to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution will be too high and uniform stirring will be difficult. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. The initial reaction can be carried out at a high concentration and then an organic solvent can be added.

In the above-mentioned radical polymerization reaction, when the ratio of the radical polymerization initiator is large with respect to the monomer, the molecular weight of the obtained polymer is small, and when the ratio is small, the molecular weight of the obtained polymer is large. It is preferably 0.1 mol% to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added at the time of polymerization.

[Recovery of polymer]
When the produced polymer is recovered from the reaction solution obtained by the above reaction, the reaction solution may be put into a poor solvent to precipitate the polymer. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water and the like. The polymer put into a poor solvent and precipitated can be collected by filtration and then dried at room temperature or by heating under normal pressure or reduced pressure. Further, by re-dissolving the polymer recovered by precipitation in an organic solvent and repeating the operation of re-precipitation recovery 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because the efficiency of purification is further improved.

<< (B) component >>
The polymer composition used in the present invention has, as the component (B), a polymer produced by using at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine compound. The polymer of the component (B) is a polyurea produced by using a diisocyanate component and a diamine component, a polyimide precursor produced by using a diisocyanate component and a tetracarboxylic acid derivative, and a diisocyanate component and a tetracarboxylic acid derivative. And a polyurea polyimide precursor produced using a diamine component, that is, a copolymer of polyurea and a polyimide precursor.

Further, in the second aspect of the present invention, in the polymer composition used in the present invention, a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound are polymerized and then imidized as the component (B). It has a polyurea polyimide produced by the above.

<<< Diisocyanate component >>>
Examples of the diisocyanate component which is a raw material of the component (B) include aromatic diisocyanates and aliphatic diisocyanates. Preferred diisocyanate components are aromatic diisocyanates and aliphatic diisocyanates.

Here, the aromatic diisocyanate refers to a diisocyanate structure (O = C = N—RN = C = O) in which the R group contains a structure containing an aromatic ring. Further, the aliphatic diisocyanate means that the R group of the isocyanate structure has a cyclic or acyclic aliphatic structure.

Specific examples of the aromatic diisocyanate include o-phenylenedi isocyanate, m-phenylenedi isocyanate, p-phenylenedi isocyanate, toluene diisocyanates (for example, trilene 2,4-diisocyanate), and 1,4-diisocyanic acid-2-methoxybenzene. , 2,5-Diisocitrate xylenes, 2,2'-bis (Phenyl 4-diisocitrate) propane, 4,4'-diphenylmethane diisocitrate, 4,4'-diphenylether diisocitrate, 4,4'-diisocitrate Examples thereof include diphenyl sulfone, diphenyl sulfone 3,3'-diisosocyanate, benzophenone 2,2'-diisosocyanate and the like. Preferred examples of the aromatic diisocyanate include trilene 2,4-diisocyanate.

Specific examples of the aliphatic diisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, tetramethylethylene diisocyanate and the like. Preferred examples of the aliphatic diisocyanate include isophorone diisocyanate. Among them, isophorone diisocyanate and trilene 2,4-diisosocyanate are preferable from the viewpoint of polymerization reactivity and voltage retention, and isophorone diisocyanate is more preferable from the viewpoint of availability, polymerization reactivity and voltage retention.

<< Tetracarboxylic acid derivative >>
Examples of the tetracarboxylic acid derivative that is the raw material of the component (B) include the following tetracarboxylic dianhydride.

Examples of the tetracarboxylic acid dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 1,2-dimethyl-1,2,3,4-cyclobutane. Tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetra Carboxydic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,4,5-tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,4,5-pentanetetracarboxylic dianhydride Anhydride, Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid dianhydride, 3,3', 4,4'-dicyclohexyltetracarboxylic acid dianhydride, 2,3. 5-Tricarboxycyclopentylacetichydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dianhydride, tricyclo [4.2.1.0] ^2,5 ] Nonan-3,4,7,8-tetracarboxylic acid-3,4: 7,8-dianhydride, hexacyclo [6.6.0.1 ^2,7 . 0 ^3,6 . ^{19 and 14} . 0 ^10,13 ] Hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1- Examples thereof include naphthalene succinic acid dianhydride.

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid. Dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,3,3', 4'- Benzophenone tetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfonate dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Examples thereof include dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid anhydride.

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

Further, as the tetracarboxylic acid component which is the raw material of the component (B), a tetracarboxylic acid dialkyl ester or a tetracarboxylic acid dialkyl diester dichloride may be used. 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 examples thereof include an aliphatic tetracarboxylic acid diester and an aromatic tetracarboxylic acid dialkyl ester.
Specific examples are given below.

Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, and the like. 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-Cyclopentane tetracarboxylic acid dialkyl ester, 2,3,4,5-tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy- 1-Cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dialkyl ester, 1,2,3,4-butanetetracarboxylic acid dialkyl ester, 1, 2,4,5-pentanetetracarboxylic acid dialkyl ester, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3', 4,4'-dicyclohexyltetracarboxylic acid Acid dialkyl ester, 2,3,5-tricarboxycyclopentylacetic 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 ] Nonan-3,4,7,8-tetracarboxylic acid-3,4: 7,8-dialkylester, hexacyclo [6.6.0.1 ^2,7 . 0 ^3,6 . ^{19 and 14} . 0 ^10,13 ] Hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene Examples thereof include succinic acid dianhydride.

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. Carboxylic acid dialkyl ester, 2,3,3', 4'-biphenyltetracarboxylic acid dialkyl ester, 3,3', 4,4'-benzophenone tetracarboxylic acid dialkyl ester, 2,3,3', 4'-benzophenone Tetracarboxylic acid dialkyl ester, bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl ester, 2 , 3,6,7-naphthalenetetracarboxylic acid dialkyl ester and the like.

Examples of the tetracarboxylic acid diester dichloride include a diester dichloride obtained by converting the carboxyl group of the tetracarboxylic acid dialkyl ester into a chlorocarbonyl group by a known method.

These tetracarboxylic dianhydride, tetracarboxylic acid diester, tetracarboxylic acid diester dichloride, etc. are one type or two, respectively, depending on the characteristics such as liquid crystal orientation, voltage holding characteristics, and accumulated charge when the liquid crystal alignment film is formed. More than one type can be used together.

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

Examples of alicyclic diamines are 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, and isophorone diamine. And so on.

Examples of aromatic diamines are o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino-. 2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4' -Diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-Diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminostylben, 4,4'-diaminostylben, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4 '-Diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,5-bis (4-aminophenoxy) benzoic acid, 4,4'-bis (4-aminophenoxy) bibenzyl, 2 , 2-bis [(4-aminophenoxy) methyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,1-bis (4-aminophenyl) cyclohexane, α, α'-bis (4-Aminophenyl) -1,4-diisopropylbenzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) Aminophenyl) Hexafluoropropane, 4,4'-diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrene, 1,6-diaminopyrene, 1,8-diaminopyrene, 2,7-diaminofluorene, 1,3-bis (4-aminophenyl) Enyl) Tetramethyldisiloxane, benzidine, 2,2'-dimethylbenzidine, 1,2-bis (4-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,4-bis (4) -Aminophenyl) butane, 1,5-bis (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) hexane, 1,7-bis (4-aminophenyl) heptane, 1,8-bis (4-Aminophenyl) octane, 1,9-bis (4-aminophenyl) nonane, 1,10-bis (4-aminophenyl) decane, bis (4-aminophenoxy) methane, 1,2-bis (4) -Aminophenoxy) ethane, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,6-bis (4-Aminophenoxy) Hexane, 1,7-Bis (4-Aminophenoxy) Heptane, 1,8-Bis (4-Aminophenoxy) Octane, 1,9-Bis (4-Aminophenoxy) Nonane, 1,10 -Bis (4-aminophenoxy) decane, di (4-aminophenyl) propane-1,3-dioate, di (4-aminophenyl) butane-1,4-dioate, di (4-aminophenyl) pentane-1 , 5-Geoate, Di (4-Aminophenyl) Hexane-1,6-Geoate, Di (4-Aminophenyl) Heptane-1,7-Geoate, Di (4-Aminophenyl) Octane-1,8-Gioate, Di (4-aminophenyl) nonane-1,9-dioate, di (4-aminophenyl) decane-1,10-dioate, 1,3-bis [4- (4-aminophenoxy) phenoxy] propane, 1, 4-bis [4- (4-aminophenoxy) phenoxy] butane, 1,5-bis [4- (4-aminophenoxy) phenoxy] pentane, 1,6-bis [4- (4-aminophenoxy) phenoxy] Hexane, 1,7-bis [4- (4-aminophenoxy) phenoxy] heptane, 1,8-bis [4- (4-aminophenoxy) phenoxy] octane, 1,9-bis [4- (4-amino) Examples thereof include phenoxy) phenoxy] nonane and 1,10-bis [4- (4-aminophenoxy) phenoxy] decane.

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

In the formula, 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 aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, and 4, -Aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-methylaminopropyl) ) Aniline, 4- (3-methylaminopropyl) aniline, 3- (4-aminobutyl) aniline, 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- (4- (4-) Methylaminobutyl) aniline, 3- (5-aminopentyl) aniline, 4- (5-aminopentyl) aniline, 3- (5-methylaminopentyl) aniline, 4- (5-methylaminopentyl) aniline, 2- Examples thereof include (6-aminonaphthyl) methylamine, 3- (6-aminonaphthyl) methylamine, 2- (6-aminonaphthyl) ethylamine, 3- (6-aminonaphthyl) ethylamine and the like.

Examples of heterocyclic diamines are 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, and 3,6-diaminocarbazole. , 2,4-Diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole and the like.

Examples of aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-Diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7- Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylnonane, 1,12-diaminododecane, Examples thereof include 1,18-diaminooctadecane and 1,2-bis (3-aminopropoxy) ethane.

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

Further, in the component (B), as the diamine component to be polymerized with the diisocyanate component, a diamine having a side chain for vertical orientation may be contained as long as the effect of the present invention is not impaired.
Further, the diamine component in the component (B) may contain the following diamines.

In the equation, m and n are integers from 1 to 11, m + n are integers from 2 to 12, h is an integer from 1 to 3, and j is an integer from 0 to 3.

By introducing these diamines, it is advantageous to further improve the voltage retention rate (also referred to as VHR) of the liquid crystal display element using the liquid crystal alignment film formed from the liquid crystal alignment agent of the present invention. These diamines are preferable from the viewpoint of excellent effect of reducing the accumulated charge of such a liquid crystal display element.

In addition, as the diamine component in the component (B), diaminosiloxane or the like as represented by the following formula (in the formula, m is an integer of 1 to 10) can be mentioned.

When the diamine compound further has a nitrogen atom in the middle of the two amino groups, the nitrogen atom existing in the middle of the two amino groups is bonded to a carbonyl or simply with two or more benzene rings. Bonding by bonding is preferable in that salt formation with the component (A) can be prevented.

As a preferable diamine component which is a raw material of the component (B), for example, a diamine having a structure represented by the following formula (Y2-1) can be mentioned.

In formula (Y2-1), Z ₃ is an alkylene group having 1 to 20 carbon atoms which may be interrupted by a bond selected from an ether bond, an ester bond, an amide bond and a urea bond, and Z ₃ and a benzene ring. The bond portion of is a single bond, an ether bond, an ester bond, a urea bond or an amide bond.

Specific examples of the formula (Y2-1) include the following formulas (Y2-2) to (Y2-9).

In the above formulas (Y2-7) and (Y2-8), R ₁₃ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and if the number of carbon atoms is too large, the liquid crystal orientation is deteriorated. , Methyl group or ethyl group is preferable.

From the viewpoint of liquid crystal orientation, the formulas ( _Y2-2 ), (Y2-3), and (Y2-5) are preferable as Y2, and the formula (Y2-2) or the formula (Y2-5) is particularly preferable. ..

In order to introduce the structure represented by the above formula (Y2-1) into the polymer which is the component (B), it is represented by the formula (Y2-1) when the polymer which is the component (B) is produced. A diamine having such a structure may be used.

Such diamines include 4,4'-diaminodiphenylmethane, 1,2-bis (4-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, and 1,4-bis (4-amino). Phenyl) butane, 1,5-bis (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) hexane, 1,7-bis (4-aminophenyl) heptane, 1,8-bis (4) -Aminophenyl) octane, 1,9-bis (4-aminophenyl) nonane, 1,10-bis (4-aminophenyl) decane, bis (4-aminophenoxy) methane, 1,2-bis (4-amino) Phenoxy) ethane, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,6-bis (4) -Aminophenoxy) Hexane, 1,7-bis (4-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,10-bis (4-Aminophenoxy) decane, di (4-aminophenyl) propane-1,3-dioate, di (4-aminophenyl) butane-1,4-dioate, di (4-aminophenyl) pentane-1,5 -Geoate, di (4-aminophenyl) hexane-1,6-dioate, di (4-aminophenyl) heptane-1,7-dioate, di (4-aminophenyl) octane-1,8-dioate, di ( 4-aminophenyl) nonane-1,9-dioate, di (4-aminophenyl) decane-1,10-dioate, 1,3-bis [4- (4-aminophenoxy) phenoxy] propane, 1,4- Bis [4- (4-aminophenoxy) phenoxy] butane, 1,5-bis [4- (4-aminophenoxy) phenoxy] pentane, 1,6-bis [4- (4-aminophenoxy) phenoxy] hexane, 1,7-Bis [4- (4-Aminophenoxy) Hexane] Heptan, 1,8-Bis [4- (4-Aminophenoxy) Phenoxy] Octane, 1,9-Bis [4- (4-Aminophenoxy) Examples thereof include phenoxy] nonane, 1,10-bis [4- (4-aminophenoxy) phenoxy] decane, N, N'-bis (4-aminophenethyl) urea and the like.

When the polymer of the component (B) contains the structure represented by the above formula (Y2-1), the ratio is preferably 15 to 90 mol% and 40 to 85 mol% with respect to all the structural units derived from diamine. % Is more preferable.

The diamine component in these components (B) can be used alone or in combination of two or more depending on the characteristics such as the liquid crystal orientation, the voltage holding characteristic, and the accumulated charge when the liquid crystal alignment film is formed. The mixing ratio at that time is not limited.

Further, the molecular weight of the polymer of the component (B) is measured by the GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained liquid crystal alignment film, the workability at the time of forming the liquid crystal alignment film, and the uniformity of the liquid crystal alignment film. The weight average molecular weight is preferably 5,000 to 1,000,000, more preferably 10,000 to 200,000.

A known synthetic method can be used to obtain a polymer of the above component (B) by a polymerization reaction of at least one selected from the diisocyanate component and the tetracarboxylic acid derivative of each raw material and the diamine component. Generally, it is a method of reacting at least one selected from a diisocyanate component and a tetracarboxylic acid derivative with a diamine component in an organic solvent. The reaction of at least one selected from the diisocyanate component and the tetracarboxylic acid derivative with the diamine component is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.

The organic solvent used for the reaction between at least one selected from the diisocyanate component and the tetracarboxylic acid derivative and the diamine component is not particularly limited as long as the produced polymer can be dissolved.
Specific examples are given below.

Examples of the organic solvent that can be used here include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, and tetramethyl. Urea, pyridine, dimethyl sulfone, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cell solve, ethyl cell solution, methyl cellosolve acetate , Ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert- Butyl Ether, Dipropylene Glycol Monomethyl Ether, Diethylene Glycol, Diethylene Glycol Monoacetate, Diethylene Glycol Dimethyl Ether, Dipropylene Glycol Monoacetate Monomethyl Ether, Dipropylene Glycol Monomethyl Ether, Dipropylene Glycol Monoethyl Ether, Dipropylene Glycol Monoacetate Monoethyl Ether, Dipropylene Glycol Monopropyl Ether, Dipropylene Glycol Monoacetate Monopropyl Ether, 3-Methyl-3-methoxybutyl Acetate, Tripropylene Glycol Methyl Ether, 3-Methyl-3-methoxybutanol, Diisopropyl Ether, Ethyl Isobutyl Ether, Diisobutylene, Amyl Acetate , Butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, lactic acid. Ethyl, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypylene Lopionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3 -Ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like can be mentioned. These may be used alone or in combination. Further, even if the solvent does not dissolve polyurea, it may be mixed with the above solvent and used as long as the polymer of the produced component (B) does not precipitate.

Further, since the water content in the organic solvent causes the polymerization reaction to be inhibited, it is preferable to use the organic solvent dehydrated and dried as much as possible.

When reacting at least one selected from the diisocyanate component and the tetracarboxylic acid derivative with the diamine component in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the diisocyanate component and the tetracarboxylic acid derivative are stirred. A method of adding at least one selected from the above as it is or by dispersing or dissolving it in an organic solvent, or conversely, adding a diamine component to a solution in which at least one selected from a diisocyanate component and a tetracarboxylic acid derivative is dispersed or dissolved in an organic solvent. Examples thereof include a method of alternately adding at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine component, and any of these methods may be used. When at least one selected from the diisocyanate component and the tetracarboxylic acid derivative or the diamine component is composed of a plurality of kinds of compounds, the reaction may be carried out in a premixed state, may be reacted individually and sequentially, and further individually. The reacted low molecular weight compound may be mixed and reacted to obtain a high molecular weight compound.

The polymerization temperature at that time can be selected from any temperature of −20 ° C. to 150 ° C., but is preferably in the range of −5 ° C. to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high, making uniform stirring difficult. Therefore, the total concentration of at least one selected from the diisocyanate component and the tetracarboxylic acid derivative and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial reaction can be carried out at a high concentration and then an organic solvent can be added.

In the polymerization reaction of the polymer as the component (B), the ratio of the total number of moles of at least one selected from the diisocyanate component and the tetracarboxylic acid derivative to the total number of moles of the diamine component is 0.8 to 1.2. Is preferable. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polymer.

When the produced polymer is recovered from the reaction solution of the polymer as the component (B), the reaction solution may be put into a poor solvent and precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water and the like. The polymer put into a poor solvent and precipitated can be collected by filtration and then dried at room temperature or by heating under normal pressure or reduced pressure. Further, by re-dissolving the polymer recovered by precipitation in an organic solvent and repeating the operation of re-precipitation recovery 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more kinds of poor solvents selected from these because the efficiency of purification is further improved.

Among the polymers as the component (B), polyurea is, for example, in the following formula [1] (formula [1], A ₁ is a divalent organic group and A ₂ is a divalent organic group. C ₁ and C ₂ are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and may be the same or different from each other.)
It is a polymer having a repeating unit indicated by.

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

In the above formula [1], A ₁ is a group derived from the diisocyanate component which is a raw material. Further, A ₂ is a group derived from the diamine component which is a raw material.

According to a preferred embodiment of the present invention, A1 is preferably _a group derived from the preferred diisocyanate component mentioned above. Further, as A ₂ , a group derived from the preferable diamine component mentioned above is preferable.

The polyimide precursor is, for example, a polymer having a repeating unit represented by the following formula [2].

In the formula [2], A ₃ is an independently tetravalent organic group, and A ₂ is an independently divalent organic group. R ₁₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and C ₁ to C ₂ are an alkyl group having 1 to 10 carbon atoms which may independently have a hydrogen atom or a substituent. It is an alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms.

Specific examples of the above alkyl group in R ₁₁ include methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group and n-pentyl group. And so on. From the viewpoint of ease of imidization by heating, R ₁₁ is preferably a hydrogen atom or a methyl group.

The polyurea polyimide precursor is, for example, a polymer having a repeating unit represented by the above formula [1] and a repeating unit represented by the above formula [2].

Here, the ratio of the tetracarboxylic acid derivative to the diisocyanate in the polyurea polyimide precursor is preferably 99: 1 to 1:99 in terms of molar ratio.

The polyurea polyimide can be obtained by ring-closing the above-mentioned polyurea polyamic acid or polyurea polyamic acid ester. The ring closure rate (also referred to as imidization rate) of the amic acid group does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose.

Examples of the method for imidizing the polyurea polyamic acid or the polyurea polyamic acid ester include thermal imidization in which the solution of the polyimide precursor is heated as it is or catalytic imidization in which a catalyst is added to the solution of the polyurea polyamic acid or the polyurea polyamic acid ester. ..

The temperature at which the polyurea polyamic acid or the polyurea polyamic acid ester is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and the water generated by the imidization reaction is removed from the system. It is preferable to do it.

Catalytic imidization of polyurea polyamic acid or polyurea polyamic acid ester is carried out by adding a basic catalyst and an acid anhydride to a solution of polyurea polyamic acid or polyurea polyamic acid ester, and -20 ° C to 250 ° C, preferably 0 ° C to 0 ° C. This can be done by stirring at 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 mol to 20 mol times, and the amount of the acid anhydride is 1 mol to 50 mol times the amidic acid group. It is preferably 3 to 30 mol times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine and trioctylamine, and among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like, and among them, acetic anhydride is preferable because it facilitates purification after the reaction is completed. The imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, the reaction temperature, and the reaction time.

When recovering the produced polyurea polyimide from the reaction solution of polyurea polyamic acid, polyurea polyamic acid ester, or polyurea polyimide, the reaction solution may be added to a solvent for precipitation. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like. The polymer put into a solvent and precipitated can be collected by filtration and then dried at room temperature or by heating under normal pressure or reduced pressure. Further, if the operation of re-dissolving the polymer recovered by precipitation in a solvent and re-precipitating and recovering the polymer is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the solvent at this time include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more kinds of solvents selected from these because the efficiency of purification is further improved.

According to a preferred embodiment of the present invention, in the polymerization composition according to the present invention, the compounding ratio (mass basis) of the component (A) and the component (B) described above is the sum of the components (A) and (B). ) Is set to 1, the component (A) is 0.01 to 0.99, more preferably 0.1 to 0.9, and even more preferably 0.2 to 0.5.

<< (C) Organic Solvent >>
The organic solvent used in the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below.
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethylamyl ketone, methylnonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglime, 4-hydroxy-4-methyl-2-pentanone, propylene glycol mono Acetate, 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, Examples thereof include dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether and the like. These may be used alone or in combination.

[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 forming 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 film is dissolved in an organic solvent. Here, the resin component is derived from (A) at least two polymers having a photoreactive structure and a liquid crystal property structure, and (B) a diisocyanate component and a tetracarboxylic acid derivative, which have already been described. It is a resin component containing at least one selected and a polymer produced by using a diamine compound. At that time, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and particularly preferably 1% by mass to 10% by mass.

In the polymer composition of the present embodiment, all of the above-mentioned resin components may be the above-mentioned components (A) and (B), but other than these as long as the liquid crystal display ability and photosensitive performance are not impaired. Other polymers may be mixed. At that time, the content of the other polymer in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.
Examples of such other polymers include polymers made of poly (meth) acrylate and the like, which are not polymers having a structure exhibiting photoreactivity and a structure exhibiting liquid crystallinity.

The polymer composition used in the present invention may contain components other than the above components (A), (B) and (C). Examples thereof include solvents and compounds that improve film thickness uniformity and surface smoothness when the polymer composition is applied, compounds that improve the adhesion between the liquid crystal alignment film and the substrate, and the like. , Not limited to this.

Specific examples of the solvent (poor solvent) for improving the uniformity of the film thickness and the surface smoothness include the following.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol mono. Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether , Dipropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, Dipropylene glycol monoacetate monoethyl ether, Dipropylene glycol monopropyl ether, Dipropylene glycol monoacetate monopropyl ether, 3-Methyl-3-methoxybutyl acetate, Tri Propylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethylisobutyl ether, diisobutylene, amylacetate, butylbutyrate, butyl ether, diisobutylketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3- Methyl methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy- 2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, Propylene glycol- Low levels of 1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester, etc. Examples thereof include a solvent having a surface tension.

These poor solvents may be used alone or in admixture of a plurality of types. When a solvent as described above is used, it is preferably 5% by mass to 80% by mass, more preferably, so as not to significantly reduce the solubility of the entire solvent contained in the polymer composition. Is 20% by mass to 60% by mass.

Examples of the compound for improving the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant.
More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megafuck (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431. (Sumitomo 3M), Asahi Guard (registered trademark) AG710 (Asahi Glass), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (AGC Seimi Chemical), etc. Will be. The ratio of these surfactants used is preferably 0.01 parts by mass to 2 parts by mass, and more preferably 0.01 parts by mass to 1 part with respect to 100 parts by mass of the resin component contained in the polymer composition. It is a mass part.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane. , N- (2-Aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 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-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxy Examples thereof include silane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane and the like.

Furthermore, in addition to improving the adhesion between the substrate and the liquid crystal alignment film, the following phenoplast-based or epoxy group-containing compounds are added for the purpose of preventing deterioration of electrical characteristics due to the backlight when the liquid crystal display element is configured. The agent may be contained in the polymer composition. Specific phenoplast-based additives are shown below, but are not limited to this structure.

Specific examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-Hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N', N',-Tetraglycidyl-m-xylene diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N', N',-tetraglycidyl-4, 4'-diaminodiphenylmethane Etc. are exemplified.

When a compound that improves adhesion to a substrate is used, the amount used is preferably 0.1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. , More preferably 1 part by mass to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it is more than 30 parts by mass, the orientation of the liquid crystal may be deteriorated.

A photosensitizer can also be used as the additive. Colorless sensitizers and triplet sensitizers are preferred.

Photosensitizers include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscmarin, aromatic 2-hydroxyketone, and amino substitutions. , Aromatic 2-hydroxyketone (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthron, thiazolin (2-benzoylmethylene-3) -Methyl-β-naphthiazolin, 2- (β-naphthoylmethylene) -3-methylbenzothiazolin, 2- (α-naphthoylmethylene) -3-methylbenzothiazolin, 2- (4-biphenoylmethylene)- 3-Methylbenzothiazolin, 2- (β-naphthoylmethylene) -3-methyl-β-naphthiazoline, 2- (4-biphenoylmethylene) -3-methyl-β-naphthiazoline, 2- (p-fluoro) Benzoylmethylene) -3-methyl-β-naphthiazolin), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α) -Naftylmethylene) -3-methylbenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthooxazolin, 2-( 4-Bifenoylmethylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β-naphthoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaften (5-nitroacenaften), (2-[(m-hydroxy-p-methoxy) styryl] benzothiazole, benzoinalkyl ether, N-alkylated phthalone, Acetphenon ketal (2,2-dimethoxyphenyletanone), naphthalene, anthracene (2-naphthalene methanol, 2-naphthalene carboxylic acid, 9-anthracene methanol, and 9-anthracene carboxylic acid), benzopyrane, azoindridin, methylcoumarin, etc. There is.
Preferred are aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonylbiscmarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.

In addition to the above-mentioned ones, the polymer composition includes a dielectric and a conductive substance for the purpose of changing the electric properties such as the dielectric constant and the conductivity of the liquid crystal alignment film as long as the effect of the present invention is not impaired. Further, a crosslinkable compound may be added for the purpose of increasing the hardness and the density of the film when the liquid crystal alignment film is formed.

<Liquid crystal alignment agent>
The present application is a liquid crystal aligning agent having or consisting essentially of the above-mentioned polymer composition or consisting only of the above-mentioned polymer composition, particularly for a liquid crystal display element, more particularly laterally. Provided is a liquid crystal alignment agent for an electric field driven liquid crystal display element.

<Liquid crystal alignment film> or <Substrate with liquid crystal alignment film>
The present application provides a liquid crystal alignment film formed from the above-mentioned liquid crystal alignment agent, particularly for a liquid crystal display element, and more particularly for a transverse electric field drive type liquid crystal display element.
Further, the present application applies to a liquid crystal alignment film formed from the above-mentioned liquid crystal alignment agent, particularly for a liquid crystal display element, particularly for a substrate having a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element, particularly for a liquid crystal display element. Provided is a substrate for a transverse electric field drive type liquid crystal display element.

<Manufacturing method of liquid crystal alignment film> or <Manufacturing method of substrate having liquid crystal alignment film>
The liquid crystal alignment film described above is
[I] A step of applying the above-mentioned polymer composition or the above-mentioned liquid crystal alignment agent on a substrate, for example, on a substrate having a conductive film for driving a transverse electric field to form a coating film;
[II] A step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II].
It is possible to obtain a liquid crystal alignment film having an orientation control ability, particularly a liquid crystal alignment film for a liquid crystal display element, more particularly a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element, or a substrate having the liquid crystal alignment film.

<< Board >>
The substrate is not particularly limited, but when the liquid crystal display element to be manufactured is a transmissive type, it is preferable to use a highly transparent substrate. In that case, the present invention is not particularly limited, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used.
Further, in consideration of application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can also be used.

<< Conductive film for driving a transverse electric field >>
When the substrate is used for a transverse electric field drive type liquid crystal display element, the substrate has a conductive film for lateral electric field drive.
Examples of the conductive film include, but are not limited to, ITO (Indium Tin Oxide: indium tin oxide), IZO (Indium Zinc Oxide: indium zinc oxide), and the like when the liquid crystal display element is a transmissive type.
Further, in the case of a reflective liquid crystal display element, examples of the conductive film include a material that reflects light such as aluminum, but the conductive film is not limited thereto.
As a method for forming a conductive film on a substrate, a conventionally known method can be used.

<< Process [I] >>
In step [I], on a substrate having a conductive film for driving a transverse electric field, a structure exhibiting liquid crystallinity in a predetermined temperature range, a structure exhibiting (A) photoreactivity of the present invention, and a structure exhibiting liquid crystallinity. A polymer composed of (B) at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine compound; and (C) a polymer composition containing an organic solvent. Is applied to form a coating film. Here, the liquid crystal phase expression temperature of the polymer of the component (A) is the temperature at which at least two kinds of polymers of the component (A) express the liquid crystal phase as a whole.

The method of applying the above-mentioned polymer composition or the above-mentioned liquid crystal alignment agent on a substrate having a conductive film for driving a transverse electric field is not particularly limited.
Industrially, the coating method is generally performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method (rotary coating method), a spray method, and the like, and these may be used depending on the purpose.

After applying the polymer composition or the liquid crystal aligning agent on the substrate having the conductive film for driving the transverse electric field, the temperature is 50 to 200 ° C. by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven. A coating can be obtained preferably by evaporating the solvent at 50-150 ° C. The drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the polymer of the component (A) of the present invention.

If the thickness of the coating film is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may decrease. Therefore, it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. Is.
It is also possible to provide a step of cooling the substrate on which the coating film is formed to room temperature after the step [I] and before the subsequent step [II].

<< Process [II] >>
In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When irradiating the film surface of the coating film with polarized ultraviolet rays, the substrate is irradiated with the polarized ultraviolet rays from a certain direction through the polarizing plate. As the 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 via a filter or the like depending on the type of the coating film to be used. Then, for example, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.

The irradiation amount of polarized ultraviolet rays depends on the coating film used. The irradiation amount is polarized ultraviolet rays that realize the maximum value of ΔA (hereinafter, also referred to as ΔAmax), which is the difference between the ultraviolet absorptance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorptivity in the vertical direction in the coating film. The amount is preferably in the range of 1% to 70%, and more preferably in the range of 1% to 50%.

<< Process [III] >>
In step [III], the coating film irradiated with the ultraviolet rays polarized in step [II] is heated. Orientation control ability can be imparted to the coating film by heating.
For heating, a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven can be used. The heating temperature can be determined in consideration of the temperature at which the liquid crystal property of the coating film to be used is exhibited.

The heating temperature is preferably within the temperature range of the temperature at which the polymer of the component (A) of the present invention exhibits liquid crystallinity (hereinafter referred to as liquid crystallinity development temperature). In the case of a thin film surface such as a coating film, the liquid crystal appearance temperature of the coating film surface is expected to be lower than the liquid crystal appearance temperature when the polymer of the component (A) of the present invention is observed in bulk. Therefore, it is more preferable that the heating temperature is within the temperature range of the liquid crystal appearance temperature on the surface of the coating film. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is set to a temperature 10 ° C lower than the lower limit of the temperature range of the liquid crystal development temperature of the chain polymer to be used, and is 10 ° C lower than the upper limit of the liquid crystal temperature range. It is preferable that the temperature is in the range up to. If the heating temperature is lower than the above temperature range, the effect of amplifying anisotropy due to heat in the coating film tends to be insufficient, and if the heating temperature is too high above the above temperature range, the state of the coating film is in a state. Tends to be close to an isotropic liquid state (isotropic phase), in which case self-assembly can make it difficult to reorient in one direction.
The liquid crystal development temperature is equal to or higher than the glass transition temperature (Tg) at which the surface of the polymer or coating film of the component (A) of the present invention undergoes a phase transition from the solid phase to the liquid crystal phase, and the liquid crystal phase to the isotropic phase ( An isotropic phase) is the temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.

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

By having the above steps, the production method of the present invention can realize highly efficient introduction of anisotropy into the coating film. Then, a substrate with a liquid crystal alignment film can be manufactured with high efficiency.

<Liquid crystal display element> and <Manufacturing method of liquid crystal display element>
The present application provides a liquid crystal display element having a substrate having the liquid crystal alignment film obtained above, particularly a transverse electric field drive type liquid crystal display element.

Specifically, by preparing a second substrate in addition to the substrate having the liquid crystal alignment film (first substrate) obtained above, a transverse electric field drive type liquid crystal display element can be obtained.
When a substrate having no transverse electric field driving conductive film is used instead of the substrate having the transverse electric field driving conductive film, the second substrate is the same as the first substrate, the transverse electric field driving conductive film. In some cases, a substrate having the above is used. Further, it is preferable that the second substrate has a liquid crystal alignment film as in the case of the first substrate.

The method for manufacturing a liquid crystal display element, particularly a lateral electric field drive type liquid crystal display element, is as follows.
[IV] A step of arranging the first and second substrates obtained above so as to face each other so that the liquid crystal alignment films of the first and second substrates face each other via the liquid crystal display;
Have. This makes it possible to obtain a liquid crystal display element, particularly a transverse electric field drive type liquid crystal display element.

<Process [IV]>
The [IV] step is the same as the substrate (first substrate) having the liquid crystal alignment film on the conductive film for driving the transverse electric field obtained in [III], and the above [I'] to [III']. The obtained substrate with a liquid crystal alignment film (second substrate) is placed facing each other so that both liquid crystal alignment films face each other via a liquid crystal, and a liquid crystal cell is produced by a known method to produce a transverse electric field. This is a process of manufacturing a drive-type liquid crystal display element. The steps [I'] to [III'] can be performed in the same manner as in the steps [I] to [III] except for the difference in the presence or absence of the conductive film for driving the transverse electric field in the step [I]. Since the only difference between the steps [I] to [III] and the steps [I'] to [III'] is the presence or absence of the above-mentioned conductive film, the description of the steps [I'] to [III'] is omitted. do.

To give an example of manufacturing a liquid crystal cell or a liquid crystal display element, the above-mentioned first and second substrates are prepared, a spacer is sprayed on the liquid crystal alignment film of one of the substrates, and the liquid crystal alignment film surface is on the inside. In this way, the other substrate is bonded and the liquid crystal is injected under reduced pressure to seal it, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacer is sprayed and then the substrate is bonded and sealed. , Etc. can be exemplified. At this time, when manufacturing a transverse electric field drive type liquid crystal display element, it is preferable to use a substrate having an electrode having a structure like a comb tooth for driving a transverse electric field as a substrate on one side.
The diameter of the spacer is preferably 1 μm to 30 μm, more preferably 2 μm to 10 μm. This spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.

As described above, the polymer composition or the liquid crystal alignment agent of the present invention, the liquid crystal alignment film formed by using the composition or the liquid crystal alignment agent, or the substrate having the alignment film, and the liquid crystal alignment film or the substrate are provided. The liquid crystal display element formed therein has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television or the like.

MA1 as a monomer having a photoreactive group, MA2 as a monomer having a liquid crystal group, HBAGE as a monomer having a cross-linking group, and A1 as a monomer having an amide group are shown below as used in Examples.
MA1 and MA2 were synthesized as follows, respectively. That is, MA1 was synthesized by the synthetic method described in Patent Document (WO2011-084546). MA2 was synthesized by the synthetic method described in Patent Document (Japanese Patent Laid-Open No. 9-118717). The polymer formed with MA1 as a monomer has photoreactivity and liquid crystallinity, and the polymer formed with MA2 as a monomer has only liquid crystallinity.
The copolymerized monomer A1 was synthesized by the synthetic method described in WO2014 / 054785 pamphlet.
As HBAGE (hydroxybutylacrylate glycidyl ether), one that can be purchased commercially was used.

<Diisocyanate component>
ISPDA: Isophoron diisocyanate

<Diamine component>
DDM: 4,4'-diaminodiphenylmethane Me-4APhA: N-methyl-2- (4-aminophenyl) ethylamine Me-DADPA: 4,4'-diaminodiphenyl (N-methyl) amine DA-2MG: 1,2 -Bis (4-aminophenoxy) ethane

<Tetracarboxylic dianhydride>
TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride

In addition, the abbreviations of the reagents used in this example are shown below.
(Organic solvent)
THF: Tetrahydrofuran NMP: N-Ethyl-2-pyrrolidone BCS: Butyl cellosolob (polymerization initiator)
AIBN: 2,2'-azobisisobutyronitrile

<Example of photo-aligned polymer synthesis P1>
MA1 (1.66 g: 0.1 mol%) and MA2 (13.79 g: 0.9 mol%) were dissolved in THF (146.42 g), degassed with a diaphragm pump, and then AIBN (0.82 g). ) Was added and degassed again. Then, the reaction was carried out at 60 ° C. for 8 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (300 ml) and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure to obtain a methacrylate polymer powder P1.

<Examples of photo-aligned polymer synthesis P2-P3>
Memethacrylate polymer powders P2 to P3 were synthesized by the same method as in Photo-Oriented Polymer Synthesis Example P1 except that the compositions shown in Table 1 were used.

<Polymer synthesis example L1>
As a tetracarboxylic dianhydride component, TDA is 4.85 g, as a diisocyanate component, ISPDA is 3.67 g, and as a diamine component, DDM is 5.89 g, Me-DADPA is 0.35 g, and Me-4APhA is 0.25. Using 85.06 g of NMP, the reaction was carried out at room temperature for 18 hours to obtain a solution having a polyamic acid (L1) concentration of 15 wt%.

<Polymer synthesis example L2>
As a tetracarboxylic dianhydride component, 4.47 g of TDA, 3.45 g of ISPDA as a diisocyanate component, 6.01 g of DA-2MG and 1.32 g of Me-DADPA as a diamine component were used in NMP86.67 g. , A solution of polyurea (L2) having a concentration of 15 wt% was obtained by reacting at room temperature for 18 hours.

<Polymer synthesis example L3>
Using 7.11 g of ISPDA as a diisocyanate component, 6.45 g of DA-2MG as a diamine component, and 1.41 g of Me-DADPA, the mixture was reacted in 84.84 g of NMP at room temperature for 18 hours to have a polyurea (L3) concentration of 15 wt%. Solution was obtained.

<Example 1>
The methacrylate polymer powder P1 (0.11 g) obtained in the photo-aligned polymer synthesis example P1 and the methacrylate polymer powder P2 (0.25 g) obtained in the photo-aligned polymer synthesis example P2 were added to NMP (8.04 g). In addition, it was dissolved by stirring at room temperature for 1 hour. The polyamic acid solution L1 (5.6 g) obtained in Polymer Synthesis Example L1 and BCS (6.0 g) were added to this solution and stirred to obtain a polymer solution T1. This polymer solution T1 was used as a liquid crystal alignment agent for forming a liquid crystal alignment film as it was.

<Example 2>
The methacrylate polymer powder P1 (0.11 g) obtained in the photo-aligned polymer synthesis example P1 and the methacrylate polymer powder P2 (0.25 g) obtained in the photo-aligned polymer synthesis example P2 were added to NMP (8.04 g). In addition, it was dissolved by stirring at room temperature for 1 hour. The polyurea solution L2 (5.6 g) obtained in Polymer Synthesis Example L2 and BCS (6.0 g) were added to this solution and stirred to obtain a polymer solution T2. This polymer solution T2 was used as a liquid crystal alignment agent for forming a liquid crystal alignment film as it was.

<Example 3>
The methacrylate polymer powder P1 (0.11 g) obtained in the photo-aligned polymer synthesis example P1 and the methacrylate polymer powder P2 (0.25 g) obtained in the photo-aligned polymer synthesis example P2 were added to NMP (8.04 g). In addition, it was dissolved by stirring at room temperature for 1 hour. The polyurea solution L3 (5.6 g) obtained in Polymer Synthesis Example L3 and BCS (6.0 g) were added to this solution and stirred to obtain a polymer solution T3. This polymer solution T3 was used as a liquid crystal alignment agent for forming a liquid crystal alignment film as it was.

<Control 1>
The methacrylate polymer powder P2 (0.36 g) obtained in Photo-Oriented Polymer Synthesis Example P2 was added to NMP (8.04 g), and the mixture was dissolved by stirring at room temperature for 1 hour. The polyamic acid solution L1 (5.6 g) obtained in Polymer Synthesis Example L1 and BCS (6.0 g) were added to this solution and stirred to obtain a polymer solution CT1. This polymer solution CT1 was used as a liquid crystal alignment agent for forming a liquid crystal alignment film as it was.

<Control 2>
The methacrylate polymer powder P2 (0.36 g) obtained in Photo-Oriented Polymer Synthesis Example P2 was added to NMP (8.04 g), and the mixture was dissolved by stirring at room temperature for 1 hour. The polyurea solution L2 (5.6 g) obtained in Polymer Synthesis Example L2 and BCS (6.0 g) were added to this solution and stirred to obtain a polymer solution CT2. This polymer solution CT2 was used as a liquid crystal alignment agent for forming a liquid crystal alignment film as it was.

<Control 3>
The methacrylate polymer powder P2 (0.36 g) obtained in Photo-Oriented Polymer Synthesis Example P2 was added to NMP (8.04 g), and the mixture was dissolved by stirring at room temperature for 1 hour. The polyurea solution L3 (5.6 g) obtained in Polymer Synthesis Example L3 and BCS (6.0 g) were added to this solution and stirred to obtain a polymer solution CT3. This polymer solution CT3 was used as a liquid crystal alignment agent for forming a liquid crystal alignment film as it was.

<Control 4>
The methacrylate polymer powder P3 (0.36 g) obtained in Photo-Oriented Polymer Synthesis Example P3 was added to NMP (8.04 g), and the mixture was dissolved by stirring at room temperature for 1 hour. The polyamic acid solution L1 (5.6 g) obtained in Polymer Synthesis Example L1 and BCS (6.0 g) were added to this solution and stirred to obtain a polymer solution CT4. This polymer solution CT4 was used as a liquid crystal alignment agent for forming a liquid crystal alignment film as it was.

<Control 5>
The methacrylate polymer powder P3 (0.36 g) obtained in Photo-Oriented Polymer Synthesis Example P3 was added to NMP (8.04 g), and the mixture was dissolved by stirring at room temperature for 1 hour. The polyurea solution L2 (5.6 g) obtained in Polymer Synthesis Example L2 and BCS (6.0 g) were added to this solution and stirred to obtain a polymer solution CT5. This polymer solution CT5 was used as a liquid crystal alignment agent for forming a liquid crystal alignment film as it was.

<Control 6>
The methacrylate polymer powder P3 (0.36 g) obtained in Photo-Oriented Polymer Synthesis Example P3 was added to NMP (8.04 g), and the mixture was dissolved by stirring at room temperature for 1 hour. The polyurea solution L3 (5.6 g) obtained in Polymer Synthesis Example L3 and BCS (6.0 g) were added to this solution and stirred to obtain a polymer solution CT6. This polymer solution CT6 was used as a liquid crystal alignment agent for forming a liquid crystal alignment film as it was.

<Control 7>
The methacrylate polymer powder P1 (0.36 g) obtained in the photo-aligned polymer synthesis example P1 and the methacrylate polymer powder P2 (0.84 g) obtained in the photo-aligned polymer synthesis example P2 were added to NMP (12.8 g). In addition, it was dissolved by stirring at room temperature for 1 hour. BCS (6.0 g) was added and stirred to obtain a polymer solution CT7. This polymer solution CT7 was used as a liquid crystal alignment agent for forming a liquid crystal alignment film as it was.

For the liquid crystal alignment agents T1 to 3 of Examples 1 to 3 and the liquid crystal alignment agents CT1 to CT6 of Controls 1 to 6, the polymer types used and their wt% are used, and in the examples, two types of photoalignment polymers are used. Is the amount of photoreactive groups in each photo-aligned polymer, the monomer species from which the "photoreactive groups" and "liquid crystal groups" are derived in each photo-aligned polymer, and the "amount of photoreactive groups" in the monomer. , And the "total photoreactive group amount" in the liquid crystal alignment agent derived from them are summarized in Table 2 below.
The "photoreactive group amount in each photo-aligned polymer" and the "total photoreactive group amount" in Table 2 can be obtained, for example, as follows.

That is, in the liquid crystal alignment agent T1 of Example 1, the photoalignment polymer species P1 and P2 are used, and P1 is used in an amount of 30 wt% and P2 is used in an amount of 70 wt% in the total weight thereof. As described above, the monomer from which the "photoreactive group" in the photooriented polymer species P1 is derived is MA1. MA2 has only a "liquid crystal group". The "photoreactive group amount in each photo-oriented polymer" is the value of mol% of the "photoreactive group" when the total of the "liquid crystal group" and the "photoreactive group" is 100 mol%. Therefore, the "photoreactive group amount" of the polymer type P1 is 100 × {0.1 / (0.1 + 0.9)}, which is 10 mol%. Similarly, the "photoreactive group amount" in the photo-aligned polymer species P2 is 20 mol%.
The "total photoreactive group amount" in the photo-aligned polymer is obtained from the weight ratio of the photo-aligned polymer species P1 and P2 and the "photoreactive group amount" in the photo-aligned polymer species P1 and P2, and is 0. 0.17 mol% is obtained from 1 mol% × 0.3 (P1 type is derived from 30 wt%) + 0.2 mol% × 0.7 (P2 type is derived from 70 wt%).

<Manufacturing of liquid crystal cell>
The liquid crystal alignment agent (T1) obtained in Example 1 is filtered through a 0.45 μm filter, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 70 ° C. for 90 seconds, and then has a film thickness of 100 nm. The liquid crystal alignment film of was formed. Next, the coating film surface was irradiated with ultraviolet rays of 313 nm at 5 to 50 mJ / cm ² via a polarizing plate, and then heated on a hot plate at 150 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Two such substrates with a liquid crystal alignment film are prepared, a spacer of 6 μm is installed on the surface of the liquid crystal alignment film of one of the substrates, and then the two substrates are combined so that the rubbing directions are parallel to each other, and the liquid crystal injection port is used. The surrounding area was sealed, leaving a cell gap of 4 μm to prepare an empty cell. A liquid crystal MLC-3019 (manufactured by Merck Group, Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell in which the liquid crystals were aligned in parallel.
Similarly, liquid crystal cells were prepared using the liquid crystal alignment agents T2 and T3 obtained in Examples 2 and 3 and the liquid crystal alignment agents CT1 to 7 obtained in Controls 1 to 7.

<Orientation evaluation>
The liquid crystal cells produced in Examples 1 to 3 and Controls 1 to 7 are placed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and the backlight is turned on in a state where no voltage is applied to transmit the light. The arrangement angle of the liquid crystal cells was adjusted so that the brightness of the light was the smallest. Visually check the LCD cell. If the liquid crystal cell was well oriented and the flow orientation was not confirmed, it was marked with "◯", if it was oriented but the flow orientation was confirmed, it was marked with "Δ", and if it was not oriented, it was marked with "x".

<Voltage retention rate (VHR) evaluation>
Using the liquid crystal cell produced above, a voltage of 5 V was applied for 60 μs at a temperature of 70 ° C., the voltage after 16.67 ms was measured, and how much the voltage could be maintained was calculated as the voltage retention rate (VHR). .. A voltage holding rate measuring device VHR-1 manufactured by Toyo Corporation was used for measuring the voltage holding rate.
The VHR results of Examples 1 to 3 and Controls 1 to 7 are shown in Table 3 together with the results of <Orientation Evaluation> and the "total photoreactive group amount" in the photoaligned polymer component.

From Table 2, in Examples 1 to 3, two photo-oriented polymers having different photoreactive group amounts are used, and by blending with a polyamic acid or a polyurea solution, good orientation is achieved in a wide range of UV irradiation doses. And it can be seen that it shows good VHR.
Specifically, when Examples 1 to 3 and Controls 1 to 3 are compared, the total photoreactive group amounts of both are almost the same (Examples 1 to 3: 0.17; Controls 1 to 3: 0. 20) and a polymer having an epoxy group (derived from HBAGE) and a nitrogen-containing aromatic heterocyclic group is used in both of them, whereby the VHR shows almost the same value. However, in both cases, in Example 1, two kinds (P1 and P2) are used as the polymer species, while in Control 1, only one kind (P2) is used as the polymer kind. Due to this difference, good orientation was confirmed up to a UV irradiation amount of 30 mJ / cm ² in Example 1, while no orientation was observed at a UV irradiation amount of 30 mJ / cm ² in Control 1, and Example 1 was more controllable. It can be seen that, as compared with No. 1, it shows better orientation in a wide range of UV irradiation doses.
Comparing Examples 1 to 3 and Controls 4 to 6, they have the same total photoreactive group amount (Examples 1 to 3: 0.17; Controls 4 to 6: 0.17), but they are light. While two types (P1 and P2) are used as the oriented polymer species, only one type (P3) is used as the photo-aligned polymer species in Control 3. Due to this difference, good orientation was confirmed up to a UV irradiation amount of 30 mJ / cm ² in Examples 1 to 3, while flow orientation was confirmed in Control 1 at a UV irradiation amount of 30 mJ / cm ² , and Examples 1 to 3 were confirmed. It can be seen that the one shows better orientation in a wide range of UV irradiation doses as compared with Controls 4 to 6. Further, it can be seen that in Examples 1 to 3, VHR is improved as compared with Control 7.

Claims (14)

(A) A polymer having a structure that expresses photoreactivity and a structure that expresses only liquidity, and is (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene. At least two polymers having a main chain derived from a radically polymerizable group selected from the group consisting of ;
(B) A polymer produced by using at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine compound;
And (C) organic solvent;
A polymer composition containing
Of the at least two types of polymers (A), one polymer (A1) and the other polymer (A2) differ in the amount of structures that exhibit photoreactivity with each other.
The structure that expresses the photoreactivity is
The following formulas (1) to (6)
(In the formula, A, B, and D are independent, single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO. Represents -O- or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced 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 the same or selected from their substituents. It is a group consisting of 2 to 6 different rings bonded via a bonding group B, and the hydrogen atoms bonded to them are independently −COOR ₀ (in the formula, R ₀ is a hydrogen atom or 1 to 1 to carbon atoms. (Representing an alkyl group of 5), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. The hydrogen atoms bonded to are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group of;
R represents a hydroxy group, an alkoxy group having ₁ to 6 carbon atoms, or represents the same definition as Y1;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = Representing CH-, when the number of Xs is 2, the Xs 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 independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-. It may be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
One of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are independently selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. It is a group; however, when X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring. When the number of Ps is 2 or more, the Ps may be the same or different, and when the number of Qs is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
When both l1 and l2 are 0, A also represents a single bond when T is a single bond;
When l1 is 1, B also represents a single bond when T is a single bond;
H and I are groups independently selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof. )
It is one of the structures selected from the group consisting of
The structures expressing only the liquid crystal property are the following formulas (21) to (31).
(In the formula, A and B have the same definition as above;
_Y3 is a group selected from the group consisting of monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, nitrogen-containing heterocycles, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof. Yes, the hydrogen atoms attached to them 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 contains 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, and nitrogen. Represents a heterocycle, 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;
One of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, but in equations (23) to (24), the total of all m is 2 or more, and equations (25) to (26). ), The sum of all m is 1 or more, and m1, m2, and m3 independently represent integers of 1 to 3;
R ₂ is a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms. And represents an alkyl group or an alkyloxy group;
Z ₁ and Z ₂ are any one of the structures selected from the group consisting of single bond, -CO-, -CH ₂ O-, -CH = N-, -CF _2- ).
The amount of the structure expressing the photoreactivity of the polymer (A1) is α when the total of the structure expressing the photoreactivity of the polymer (A1) and the structure expressing only the liquid crystal property is 100 mol%. Mol% (α is 15 or more),
The amount of the structure that expresses the photoreactivity of the polymer (A2) is 0.95 α mol when the structure that expresses the photoreactivity of the polymer (A2) and the structure that expresses only liquid crystallinity are 100 mol%. % Or less,
A polymer composition having a weight average molecular weight of β (β is 30,000 or more) and a weight average molecular weight of the polymer (A2) of 0.1β to 0.9β.

Monomer (M1) in which the at least two polymers have a structure that expresses (M-1) photoreactivity and a structure that expresses only liquidity; and (M-2) a monomer having a structure that expresses only liquidity. The polymer composition according to claim 1, which is formed by having (M2) ;. When the total of the monomer (M1) and the monomer (M2) is 100 mol%,
The polymer (A1) is formed so that the monomer (M1) is α mol% (α is 15 or more) and the monomer (M2) is a residue.
The polymer composition according to claim 2, wherein the polymer (A2) is formed so that the monomer (M1) is 0.95 α mol% or less and the monomer (M2) is a residue. The component (B) is a polymer produced by using at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and two or more kinds of diamine compounds, and has the formula (Y2-1) as a structure derived from diamine. (In the formula, Z ₃ is an alkylene group having 1 to 20 carbon atoms which may be interrupted by a bond selected from an ether bond, an ester bond, an amide bond and a urea bond, and the bond portion between Z ₃ and the benzene ring is The polymer composition according to any one of claims 1 to 3, which is a polymer having a structure represented by a single bond, an ether bond, an ester bond, a urea bond or an amide bond).

The polymer composition according to any one of claims 1 to 4, wherein the polymer of the component (B) is a polyurea obtained by polymerizing a diisocyanate component and a diamine component. The weight according to any one of claims 1 to 4, wherein the polymer of the component (B) is a polyurea polyimide precursor obtained by polymerizing a diisocyanate component, a tetracarboxylic acid derivative, and a diamine component. Combined composition. The polymer composition according to any one of claims 1 to 4, wherein the polymer of the component (B) is a polyimide precursor obtained by polymerizing a tetracarboxylic acid derivative and a diamine component. A liquid crystal alignment agent containing the polymer composition according to any one of claims 1 to 7. A liquid crystal alignment film formed from the liquid crystal alignment agent according to claim 8. [I] A step of applying the polymer composition according to any one of claims 1 to 7 onto a substrate having a conductive film for driving a transverse electric field to form a coating film;
[II] A step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and a step of heating the coating film obtained in [III] [II];
A method for producing a liquid crystal alignment film, which obtains a liquid crystal alignment film to which an orientation control ability is imparted. The substrate having the liquid crystal alignment film according to claim 9. [I] A step of applying the polymer composition according to any one of claims 1 to 7 onto a substrate having a conductive film for driving a transverse electric field to form a coating film;
[II] A step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and a step of heating the coating film obtained in [III] [II];
A method for manufacturing a substrate having a liquid crystal alignment film, which obtains a liquid crystal alignment film to which an orientation control ability is imparted. A liquid crystal display element having the substrate according to claim 11. A step of manufacturing a substrate (first substrate) according to the manufacturing method according to claim 12.
[I'] A step of applying the polymer composition according to any one of claims 1 to 7 on a second substrate to form a coating film;
[II'] A step of irradiating the coating film obtained in [I'] with polarized ultraviolet rays;
[III'] The step of heating the coating film obtained in [II'];
A step of obtaining a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment of the first and second substrates via the liquid crystal. A step of arranging the first and second substrates so as to face each other so that the films face each other to obtain a liquid crystal display element;
A method for manufacturing a liquid crystal display element, which obtains a liquid crystal display element.