JPWO2017170681A1 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The present invention relates to a polymer composition for producing a liquid crystal alignment film, specifically a horizontal alignment film capable of efficiently obtaining a high-quality liquid crystal alignment film by expanding the range of light irradiation amount in which the alignment control ability is stably generated. Provided is a composition for producing a liquid crystal alignment film for an electric field driven liquid crystal display device. Moreover, this invention provides the liquid crystal aligning agent and liquid crystal aligning film which are formed from this composition, the board | substrate and liquid crystal display element which have this liquid crystal aligning film. The present invention comprises (A) at least two polymers having a photoreactive structure and a liquid crystal structure; (B) at least one selected from a diisocyanate component and a tetracarboxylic acid derivative, and a diamine compound. And (C) an organic solvent. Among the at least two polymers, one polymer (A1) and the other polymer (A2) photoreact with each other. Polymer compositions differing in the amount of structures that exhibit properties are provided. [Selection figure] None

Description

  The present invention relates to a polymer composition for a liquid crystal aligning agent, in particular, a liquid crystal aligning agent for a lateral electric field drive type liquid crystal display element, consisting of the composition alone, consisting essentially of the composition or the composition. A liquid crystal aligning agent having liquid crystal, particularly a liquid crystal aligning agent for a horizontal electric field drive type liquid crystal display element, a liquid crystal alignment film formed from the liquid crystal aligning agent, particularly a liquid crystal alignment film for a horizontal 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 horizontal electric field drive type liquid crystal display element, and a liquid crystal display element having the substrate, in particular, a horizontal electric field drive type liquid crystal display element.

  The liquid crystal display element is known as a light, thin and low power consumption display device, and has been remarkably developed in recent years. The liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between 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 alignment state between the substrates.

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

In addition to the conventional rubbing method, a photo-alignment method is known as an alignment treatment method for a liquid crystal alignment film for imparting alignment control ability. Compared with the conventional rubbing method, the photo-alignment method eliminates the need for rubbing, does not cause the generation of dust and static electricity, and can perform the alignment treatment even on the substrate of the liquid crystal display element having the uneven surface. There is an advantage that you can.
There are various photo alignment methods. 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 aligned according to the anisotropy.

As the photo-alignment method, a decomposition-type photo-alignment method, a photo-crosslinking type or a photo-isomerization type photo-alignment method, and the like are known.
The decomposition type photo-alignment method is, for example, that a polyimide film is irradiated with polarized ultraviolet rays, and an anisotropic decomposition is generated by utilizing the polarization direction dependency of ultraviolet absorption of the molecular structure. This is a method of aligning the liquid crystal by the method (for example, see Patent Document 1).

  The photo-crosslinking type or photoisomerization type photo-alignment method uses, for example, polyvinyl cinnamate, irradiates polarized ultraviolet rays, and performs a dimerization reaction (cross-linking reaction) at the double bond portion of two side chains parallel to the polarized light. This is a method of generating and aligning the liquid crystal in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1). In addition, when a side chain polymer having azobenzene in the side chain is used, irradiation with polarized ultraviolet light causes an isomerization reaction at the azobenzene portion of the side chain parallel to the polarized light, and the liquid crystal is aligned in a direction perpendicular to the polarization direction. Align (see Non-Patent Document 2, for example). Further, Patent Document 3 discloses a liquid crystal alignment film obtained by using a photo-alignment method by photocrosslinking, photoisomerization or photo-fleece rearrangement.

Japanese Patent No. 3893659 JP-A-2-37324 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 photo-alignment method has a great advantage because it eliminates the rubbing process itself as compared with the rubbing method conventionally used industrially as an alignment treatment method for liquid crystal display elements. And compared with the rubbing method in which the alignment control ability becomes almost constant by rubbing, the photo alignment method can control the alignment control ability by changing the irradiation amount of polarized light.
However, if the alignment controllability of the main component used in the photo-alignment method is too sensitive to the amount of polarized light, the alignment may be incomplete in part or all of the liquid crystal alignment film, and stable liquid crystal alignment cannot be realized. Occurs.

Accordingly, an object of the present invention is to increase the range of light irradiation amount in which the alignment control ability is stably generated, and to efficiently obtain a high-quality liquid crystal alignment film, a polymer composition for producing a liquid crystal alignment film, specifically Specifically, it is to provide a composition for producing a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element.
In addition to or in addition to the above object, the object of the present invention is to provide a liquid crystal aligning agent having the composition, a liquid crystal aligning film produced using the liquid crystal aligning agent, and a substrate having the liquid crystal aligning film. An object of the present invention is to provide 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 inventors have found the following invention.
<1> (A) At least two polymers having a structure that exhibits photoreactivity and a structure that exhibits liquid crystallinity;
(B) a polymer produced using at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine compound;
And (C) an organic solvent;
A polymer composition for producing a liquid crystal alignment film, more particularly a composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element.
<2> In the above <1>, one of the polymers (A1) and the other polymer (A2) out of at least two types of the polymer (A) is different in the amount of the structure that exhibits photoreactivity. It is good.

  <3> In the above item <1> or <2>, at least two kinds of polymers as the component (A) preferably have a structure that exhibits photoreactivity and a structure that exhibits only liquid crystallinity. In this specification, “liquid crystallinity only” in “structure that expresses only liquid crystallinity” is a term used when considering “photoreactivity” and “liquid crystallinity”. The expression “only” means that “liquid crystallinity” is expressed but “liquidity” is not expressed.

<4> The structure exhibiting photoreactivity in the above <1> to <3>
Following formula (1)-(6)
(In the formula, A, B and D are each independently a 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 a hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —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, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 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 the same definition as Y ₁ ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
Cou represents coumarin-6-yl group or a coumarin-7-yl group, _-NO 2 are each a hydrogen atom bonded to them _{independently, -CN, -CH = C (CN} ) 2, -CH = CH- 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 each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q 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 l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof. )
The structure may be any one selected from the group consisting of:

<5> In the above <3> or <4>,
The structure that exhibits only liquid crystallinity is represented by the following formulas (21) to (31).
Wherein A and B have the same definition as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO ₂ , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
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, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer 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 heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z ₁ and Z ₂ may be any one structure selected from the group consisting of a single bond, —CO—, —CH ₂ O—, —CH═N—, and —CF ₂ —.

<6> In any one of the above items <2> to <5>, the amount of the structure that expresses the photoreactivity of the polymer (A1) expresses the liquid crystallinity and the structure that expresses the photoreactivity of the polymer (A1). 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 expressing the photoreactivity of the polymer (A2) is 0.95α mol% or less, assuming that the structure expressing the photoreactivity of the polymer (A2) and the structure expressing liquid crystal are 100 mol%, Preferably it is 0.1 (alpha) -0.8 (alpha) mol%, More preferably, it is 0.25 (alpha) -0.5 (alpha) mol%.
<7> In any one of the above items <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, More preferably, the weight average molecular weight of the polymer (A2) is 0.1β to 0.9β, preferably 0.2β to 0.8β, more preferably 0.3β to 0.7β. There should be.
<8> In any one of the above items <2> to <7>, when 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 60-80 wt%.

<9> In any one of the above items <1> to <8>, (M-1) a monomer (M1) having a structure in which at least two polymers exhibit photoreactivity and liquid crystallinity; and (M-2) And a monomer (M2) having a structure exhibiting only liquid crystallinity.
<10> In the above item <9>, the monomer (M1) may have a structure represented by any one of the above formulas (1) to (20).
<11> In the above item <9> or <10>, the monomer (M2) may have a structure represented by the above formulas (21) to (31).

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

<14> In any one of the above items <9> to <13>, when the total amount of the monomer (M1) and the monomer (M2) is 100 mol%, the polymer (A1) has a monomer (M1) of α mol% ( α is 15 or more, preferably 15-100, more preferably 20-80) and the remainder is 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 the remainder is monomer (M2 ) To be formed.

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

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

<16> In the above items <1> to <15>, the polymer of the component (B) may be a polyurea obtained by polymerizing a diisocyanate component and a diamine component.
<17> In the above items <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 items <1> to <15>, the polymer of the component (B) may be a polyimide precursor obtained by polymerizing a tetracarboxylic acid derivative and a diamine component.

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

<21> [I] A step of applying the polymer composition described in any one of the above <1> to <18> onto a substrate having a conductive film for driving a lateral 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, in which a liquid crystal alignment film, particularly a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element, to which alignment control ability is imparted is obtained.
<22> A substrate having the liquid crystal alignment film of <21> above, particularly a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element, particularly a substrate for a horizontal electric field drive type liquid crystal display element.
<23> [I] The process of apply | coating the polymer composition as described in any one of said <1>-<18> on the board | substrate which has a conductive film for a horizontal electric field drive, and forming 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 substrate having a liquid crystal alignment film, which obtains a liquid crystal alignment film, particularly a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element, to which alignment control ability is imparted.

<24> A liquid crystal display device having a substrate obtained in the above <23>, particularly a substrate for a horizontal electric field drive type liquid crystal display device, particularly a horizontal electric field drive type liquid crystal display device.
<25> A step of producing a substrate (first substrate) according to <23>above;
[I ′] A step of forming a coating film by applying the polymer composition described in any one of <1> to <18> on the second substrate;
[II ′] A step of irradiating the coating film obtained in [I ′] with polarized ultraviolet rays;
[III ′] a step of heating the coating film obtained in [II ′];
Obtaining a liquid crystal alignment film imparted with alignment control capability by having a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment of the first and second substrates via liquid crystal A step of obtaining a liquid crystal display element by arranging the first and second substrates to face each other so that the films face each other;
A method for producing a liquid crystal display element, comprising obtaining a liquid crystal display element, in particular, a lateral electric field drive type liquid crystal display element.

According to the present invention, a polymer composition for producing a liquid crystal alignment film, specifically a lateral liquid crystal alignment film capable of efficiently obtaining a high-quality liquid crystal alignment film by expanding the range of light irradiation amount in which the alignment control ability is stably generated. A composition for producing a liquid crystal alignment film for an electric field driven liquid crystal display element can be provided.
Further, according to the present invention, in addition to or in addition to the above effects, a liquid crystal alignment agent having the composition, a liquid crystal alignment film produced using the liquid crystal alignment agent, a substrate having the liquid crystal alignment film, A liquid crystal display element having a liquid crystal alignment film and / or the substrate, in particular, a lateral electric field drive type liquid crystal display element can be provided.

  The present application relates to a polymer composition for a liquid crystal aligning agent, in particular a liquid crystal aligning agent for a lateral electric field drive type liquid crystal display element, consisting of the composition alone, consisting essentially of the composition, or comprising the composition. Liquid crystal aligning agent, especially liquid crystal aligning agent for lateral electric field drive type liquid crystal display element, liquid crystal alignment film formed from the liquid crystal aligning agent, especially liquid crystal alignment film for lateral electric field drive type liquid crystal display element, and substrate having the liquid crystal alignment film In particular, a lateral electric field drive type liquid crystal display element substrate and a liquid crystal display element having the substrate, particularly a lateral electric field drive type liquid crystal display element are provided. Hereinafter, it explains in detail in order.

<Polymer composition>
The present application provides a polymer composition, particularly a polymer composition for a liquid crystal aligning agent, more particularly for a liquid crystal aligning agent for a lateral electric field drive type liquid crystal display element.
The polymer composition of the present application is
(A) manufactured using at least two polymers having a photoreactive structure and a liquid crystallinity structure; (B) at least one selected from a diisocyanate component and a tetracarboxylic acid derivative, and a diamine compound. And (C) an organic solvent.
In addition, among the 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.

  The (A) component at least two kinds of polymers each preferably have a structure that exhibits photoreactivity and liquid crystallinity, and a structure that exhibits only liquid crystallinity. In this specification, “liquid crystallinity only” in “structure that expresses only liquid crystallinity” is a term used when considering “photoreactivity” and “liquid crystallinity”. The expression “only” means that “liquid crystallinity” is expressed but “liquidity” is not expressed.

<(A) Polymer having photoreactive structure and liquid crystal structure>
In the present specification, the “structure that exhibits photoreactivity” refers to a structure that reacts with light in a certain wavelength range, particularly light in the wavelength range of 250 nm to 400 nm. For example, the structure is a polymer that is component (A). It is good to have in the side chain.

In the present specification, “photoreactivity” is not particularly limited, but means that it reacts with light to show a crosslinking reaction, an isomerization reaction, or a photo-Fries rearrangement, and preferably shows a crosslinking reaction. It is good. In the case of using a polymer having a “structure that exhibits photoreactivity”, the achieved orientation control ability can be stably maintained for a long period of time even when exposed to an external stress such as heat.
In the present specification, the “structure exhibiting liquid crystallinity” refers to a structure exhibiting liquid crystallinity in a certain temperature range, particularly a temperature range of 100 to 300 ° C., for example, a mesogenic group or a mesogenic component in a 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 alignment can be obtained when the polymer is used as a liquid crystal alignment film.

The polymer structure preferably has, for example, a main chain and a side chain bonded to the main chain, and the side chain has a “structure that exhibits photoreactivity” and a “structure that exhibits liquid crystallinity”. The “structure that exhibits photoreactivity” and the “structure that exhibits liquid crystallinity” may be included in the same side chain or in different side chains. Preferably, the polymer is provided with a structure that exhibits photoreactivity and liquid crystallinity in a certain side chain, and a structure that exhibits only liquid crystallinity in another side chain.
When the “structure that exhibits photoreactivity” and the “structure that exhibits liquid crystallinity” have the same side chain, a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, or an azobenzene group; When the side chain has a “structure that expresses photoreactivity” that is bonded to the tip and exhibits a crosslinking reaction or isomerization reaction in response to light, the side chain is a “structure that exhibits liquid crystallinity” In some cases, the structure is a mesogenic component and has a phenylbenzoate group that undergoes a photo-Fries rearrangement reaction, which is a “structure that exhibits photoreactivity”.

  Specific examples of the main chain of at least two kinds of polymers as the component (A) of the present invention are not particularly limited, but each independently includes hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α- It may be composed of at least one selected from the group consisting of radically polymerizable groups such as methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and siloxane.

<< Photoreactive structure >>
The structure that exhibits photoreactivity, particularly the structure that exhibits photoreactivity and liquid crystallinity, may be a structure represented by any one selected from the group consisting of 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 may be any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
In which A, B, D, Y ₁ , X, Y ₂ and R have the same definition as above;
l represents an integer of 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 of 0 to 12 (however, when n = 0, B is a single bond).

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

The side chain may be a photosensitive side chain represented by the following formula (14) or (15).
In the formula, A, Y ₁ , l, m1 and m2 have the same definition as above.

The side chain may be a photosensitive side chain represented by the following formula (16) or (17).
In the formula, A, X, l and m have the same definition 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 definition 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 group 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 definition as above.

<< Structure that exhibits only liquid crystallinity >>
The structure exhibiting only liquid crystallinity may be a structure represented by any one selected from the group consisting of formulas (21) to (31). In the formula, A, B, Y ₃ , R ₃ , q 1, q 2, l, m, m 1, m ₂ , m 3, R ₂ , Z ₁ , Z ₂ have the same definition as described above.

<< Amount of structure expressing photoreactivity of each of at least two kinds of polymers as component (A) >>
In each of at least two types of polymers as component (A), when the total of the structure that exhibits photoreactivity and the structure that exhibits only liquid crystallinity is 100 mol%,
The amount of the structure expressing 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 expressing the photoreactivity of the polymer (A2) should be less than the amount of the structure expressing the photoreactivity of the polymer (A1), specifically 0.95α mol% or less, preferably It is good to be 0.1α to 0.8α mol%, more preferably 0.25α to 0.5α mol%.
(A) It is thought that it has the following effect | actions by using the polymer from which the quantity of the structure which expresses photoreactivity differs as a component. That is, the orientation by ultraviolet irradiation is determined by the polymer (polymer (A1)) having a relatively large structure that exhibits photoreactivity. On the other hand, a polymer (polymer (A2)) having a relatively small structure that exhibits photoreactivity but a relatively large structure that exhibits liquid crystallinity (polymer (A2)) is aligned according to the alignment defined by the polymer (A1). Of the at least two types of polymers, each polymer can share the function of each and exhibit the function effectively.

<< Weight average molecular weight of each of at least two types of polymers as component (A) >>
Moreover, among the at least two types of polymers as the component (A), one of the weight average molecular weights is β (β is 30,000 or more, preferably 30,000 to 300,000, more preferably 40,000 to 200,000, more preferably 60,000 to 150,000),
The other weight average molecular weight is 0.1β to 0.9β, preferably 0.2β to 0.8β, and more preferably 0.3β to 0.7β.
In the present specification, unless otherwise specified, the weight average molecular weight is measured by GPC (Gel Permeation Chromatography) method.
In particular, the polymer (A1) having a relatively large amount of structure that exhibits 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 that exhibits photoreactivity has a weight average molecular weight of 0.1β to 0.9β, preferably 0.2β to 0.8β, 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. On the other hand, the polymer having a small weight average molecular weight tends to be formed in a relatively upper layer of the liquid crystal alignment film (a layer relatively far from the substrate). is there.
By having such a configuration, it is considered that the following effects are exhibited.
That is, the polymer (A1) having a relatively large structure that exhibits photoreactivity and a large weight average molecular weight is formed in a relatively lower layer (a layer relatively closer to the substrate) of the liquid crystal alignment film. On the other hand, the polymer (A2) having a relatively small structure that exhibits photoreactivity and a small weight average molecular weight is formed in a relatively upper layer (a layer far from the substrate) of the liquid crystal alignment film. In this situation, when irradiated with polarized ultraviolet rays, the polymer (A1) in the lower layer (layer relatively close to the substrate) is oriented according to the polarized ultraviolet rays. On the other hand, it is considered that the polymer (A2) of the upper layer (layer relatively far from the substrate) is oriented along the orientation of the polymer (A1).
When 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%. (A2) should be the remainder.

<Manufacturing method of at least two kinds of polymers as component (A)>
As long as at least 2 types of polymers which are (A) component of this invention have the above-mentioned structure, the manufacturing method will not be specifically limited. For example, at least two kinds of polymers as the component (A) of the present invention include (M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; and (M-2) only liquid crystallinity. And a monomer (M2) having a developing structure. In addition, it can copolymerize with another monomer in the range which does not impair photoreactive property and / or liquid crystallinity expression ability.
As described above, at least two types of polymers that are the component (A) of the present invention are formed having the monomer (M1) and the monomer (M2), and the total of the monomer (M1) and the monomer (M2) is calculated. In the case of 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). And it should be formed so that the remainder is monomer (M2).
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 remainder is monomer. It may be formed so as to be (M2).
In addition, it is preferable that the monomer (M1) and the monomer (M2) used in the polymer (A1) and the polymer (A2) are common to each other.

<< Monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity and its production method >>
At least two kinds of polymers as component (A) of the present invention are the above monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; and (M-2) monomer having a structure that exhibits only liquid crystallinity. (M2); and specifically, it may be obtained by copolymerization.

[Monomer (M1) having a structure exhibiting photoreactivity and liquid crystallinity]
The monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity may form a polymer having a structure that exhibits photoreactivity and liquid crystallinity at the side chain site of the polymer when the polymer is formed. It is a monomer that can be used.
As the structure that exhibits photoreactivity at the side chain site, the following structures and derivatives thereof are preferable.

  More specific examples of the monomer (M1) include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other radical polymerizable groups and siloxanes. A polymerizable group composed of at least one selected from the group consisting of: a structure that exhibits photoreactivity and liquid crystallinity composed of at least one of the above formulas (1) to (6), preferably, for example, A structure that exhibits photoreactivity and liquid crystallinity comprising at least one of the above formulas (7) to (10), and photoreactivity and liquid crystallinity that comprises at least one of the above formulas (11) to (13). Structure, structure expressing photoreactivity and liquid crystallinity expressed by the above formula (14) or (15), photoreactivity and liquid expressed by the above formula (16) or (17) Structure that exhibits crystallinity, structure that exhibits photoreactivity and liquid crystallinity represented by the above formula (18) or (19), structure that exhibits photoreactivity and liquid crystallinity represented by the above formula (20) It is preferable that the structure has

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 a functional 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 that it is at least one selected from compounds. In particular, the monomer (M1) may have (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 a synthesis method described in a patent document (WO2011-084546).
MA2 can be synthesized by a synthesis method described in a patent document (Japanese Patent Laid-Open No. 9-118717).
MA3 can be synthesized by a synthesis method described in non-patent literature (Macromolecules 2002, 35, 706-713).
MA4 can be synthesized by a synthesis method described in a patent document (WO2014 / 054785).
MA5 can be synthesized by a synthesis method described in a patent document (Japanese Patent Laid-Open No. 2010-18807).
MA6 to MA9 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).
As MA10, commercially available M6BC (manufactured by Midori Chemical Co., Ltd.) can be used.
MA11-13 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).

MA14-18 are commercially available, and M4CA, M4BA, M2CA, M3CA, and M5CA (all manufactured by Midori Chemical Co., Ltd.) can be used.
MA19-23 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).
MA24 can be synthesized by a synthesis method described in non-patent literature (Polymer Journal, Vol. 29, No. 4, pp 303-308 (1997)).
MA25 can be synthesized by a synthesis method described in a patent document (WO2014 / 054785).
MA26 and MA27 are the synthesis methods described in non-patent literature (Macromolecules (2012), 45 (21), 8547-8554) and non-patent literature (Liquid Crystals (1995), 19 (4), 433-40), respectively. Can be synthesized.
MA28 to 33 can be synthesized by a synthesis method described in a patent document (WO2014 / 054785).
MA34 to 39 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).
MA40 and 41 can be synthesized by a synthesis method described in a patent document (Japanese translations of PCT publication No. 2009-511431).
MA42 can be synthesized by a synthesis method described in a patent document (WO2014 / 054785).
MA43 can be synthesized by a synthesis method described in a patent document (WO2012-115129).
MA44 can be synthesized by the synthesis method described in the patent document (WO2013-1333078).
MA45 can be synthesized by a synthesis method described in a patent document (WO2008-072652).
MA46 can be synthesized by a synthesis method described in a patent document (WO2014 / 054785).

[Monomer (M2) having a structure exhibiting only liquid crystallinity and its production method]
The monomer (M2) having a structure that exhibits only liquid crystallinity is a monomer that allows a polymer derived from the monomer to exhibit liquid crystallinity and to form a mesogenic group at a side chain site.

  As a mesogenic group having a side chain, even if it is a group having a mesogen structure alone 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 mesogenic group of the side chain.

  More specific examples of the monomer (M2) having a structure exhibiting only liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, A structure having a structure composed of at least one selected from the group consisting of radically polymerizable groups such as norbornene and siloxane, and at least one of the above formulas (21) to (31). Is preferred.

  The monomer (M2) is a polymer 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 in these compounds. At least one selected from the group consisting of compounds in which the group is replaced by 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) may have (meth) acrylate as a polymerizable group, and preferably, for example, the end of the side chain is COOH.

<< Monomer having crosslinkable group (M3) >>
Polymer (A1) and / or polymer (A2) is (M-3) a monomer having a crosslinkable group, specifically, the following formulas (G-1), (G-2), (G-3) and ( And 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 structure represented by formula (0)]
More specific examples of the monomer having the structure represented by the above formula (0) include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, It preferably has a polymerizable group composed of at least one selected from the group consisting of radically polymerizable groups such as norbornene and siloxane, and a structure represented by the above formula (0).

  Among such monomers, specific examples of the monomer having an epoxy group include compounds such as glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and allyl glycidyl 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 and 1,7-octadiene monoepoxide.

Specific examples of the monomer having thiirane include those obtained by replacing the epoxy structure of the monomer having an epoxy group with thiirane.
Specific examples of the monomer having an aziridine include those in which the epoxy structure of the monomer having an epoxy group is replaced with aziridine or 1-methylaziridine.

  Examples of the monomer having an oxetane group include (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-oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3-ethyl-oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- ( Acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetane, 3- (acryloyloxymethyl) -2-phenyl-oxetane, 2- (methacryloyloxymethyl) oxetane, 2 -(Ac Royloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyloxymethyl) -4-trifluoromethyloxetane are preferred, and 3- (methacryloyloxymethyl) -3-ethyl- And oxetane, 3- (acryloyloxymethyl) -3-ethyl-oxetane, and the like.

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

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

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

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

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

Specifically, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, List triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thionoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, etc. Can do. Furthermore, the carbon atom of these nitrogen-containing aromatic heterocycles may have a substituent containing a heteroatom.
Of these, for example, a pyridine ring is preferred.

  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 has an ionicity. In order to reduce the elution of impurities and promote the cross-linking reaction of the cross-linkable group, more specifically, the cross-linking reaction of the group represented by the above formula (0), or a more durable liquid crystal alignment film Can be obtained. 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) is replaced with the monomer (M1) and the monomer (M2), and optionally with the monomer (M3). What is necessary is just to copolymerize.

  The monomer (M4) is selected from the group consisting of hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, radical polymerizable groups such as styrene, vinyl, maleimide, norbornene, and siloxane. It preferably has 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. NH in the amide group and urethane group may or may not be substituted. Examples of the substituent in the case where it may be substituted include an alkyl group, an amino-protecting group, and a benzyl group.

  Among such monomers, as a monomer having a nitrogen-containing aromatic heterocyclic group, specifically, for example, 2- (2-pyridylcarbonyloxy) ethyl (meth) acrylate, 2- (3-pyridylcarbonyloxy) Examples include ethyl (meth) acrylate, 2- (4-pyridylcarbonyloxy) ethyl (meth) acrylate, and the like.

  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 include N- (tertiary butyloxycarbonyl) piperidin-4-yl ester, 4- (6-methacryloyloxyhexyloxy) benzoic acid 2- (tertiary butyloxycarbonylamino) ethyl ester, and the like.

  (M-4) A 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 represented by the above formulas MA6 to MA8 and MA33, and Polymerizability in which the polymerizable group of the compound having a 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 may be at least one selected from the group consisting of compounds in which the group is replaced.

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

  Specific examples of the other monomer include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.

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

  Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, 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- Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and , Etc. 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, 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- Propyl-2-adamantyl methacrylate, 8-methyl 8 tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate.

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

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

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

  The radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxidation). Hydrogen, tert-butyl hydride peroxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxy cyclohexane) Etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclo Xanthate-tert-amyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2′-di (2-hydroxyethyl) And azobisisobutyronitrile). Such radical thermal polymerization initiators can be used singly or in combination of two or more.

  The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy 2-methylpropiophenone, 2-hydroxy-2-methyl-4′-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- N-di-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4′-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (2′-methoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)]-2, 6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -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-diethylamino) Coumarin), 2- (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bi (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 ′ -Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2 -Dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (5-2,4-cyclopentadi) N-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone 3,3 ′, 4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 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-methyl-3H-benzothiazol-2-ylidene) -1-naphthalen-2-yl-ethanone or 2- (3-methyl-1 3- benzothiazol -2 (3H) - ylidene) -1- (2-benzoyl) ethanone, and the like. These compounds may be used alone or in combination of two or more.

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

  The monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; and (M-2) the monomer (M2) having a structure that exhibits only liquid crystallinity are copolymerized to form at least two kinds of 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 is soluble. Specific examples are given below.

  N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , Γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethyl 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, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion , 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 organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the produced | generated polymer, you may mix and use the above-mentioned organic solvent in the range which the produced | generated polymer does not precipitate.
In radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction. Therefore, it is preferable to use an organic solvent that has been deaerated to the extent possible.

  The polymerization temperature during radical polymerization can be selected from 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 is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

  In the above-mentioned radical polymerization reaction, the molecular weight of the obtained polymer is decreased when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer is increased when the ratio is small, the ratio of the radical initiator is It is preferable that it is 0.1 mol%-10 mol% with respect to the monomer to superpose | polymerize. Further, various monomer components, solvents, initiators and the like can be added during the polymerization.

[Recovery of polymer]
When the produced polymer is recovered from the reaction solution obtained by the above-described reaction, the reaction solution may be poured into a poor solvent to precipitate these polymers. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection | recovery is re-dissolved in an organic solvent and the operation which carries out reprecipitation collection | recovery is repeated 2 to 10 times, the impurity in a polymer can be decreased. 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 purification efficiency is further improved.

<< (B) component >>
The polymer composition used for this invention has the polymer manufactured using the diamine compound and at least 1 type chosen from the diisocyanate component and the tetracarboxylic acid derivative as (B) component. The polymer of the component (B) includes a polyurea produced using a diisocyanate component and a diamine component, a polyimide precursor produced 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.

  In the second aspect of the present invention, the polymer composition used in the present invention comprises, as component (B), a polymerization reaction of a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound, and then imidization. It has polyurea polyimide manufactured by doing.

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

  Here, the aromatic diisocyanate refers to those in which the R group of the diisocyanate structure (O═C═N—R—N═C═O) includes a structure containing an aromatic ring. The aliphatic diisocyanate means that the R group of the isocyanate structure is composed of a cyclic or acyclic aliphatic structure.

  Specific examples of the aromatic diisocyanate include o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanates (for example, 2,4-diisocyanate tolylene), 1,4-diisocyanate-2-methoxybenzene. 2,5-diisocyanate xylenes, 2,2′-bis (phenyl diisocyanate) propane, 4,4′-diisocyanate diphenylmethane, 4,4′-diisocyanate diphenyl ether, 4,4′-diisocyanate Examples thereof include diphenyl sulfone, 3,3′-diisocyanate diphenyl sulfone, and 2,2′-diisocyanate benzophenone. The aromatic diisocyanate is preferably tolylene 2,4-diisocyanate.

  Specific examples of the aliphatic diisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, and tetramethylethylene diisocyanate. As the aliphatic diisocyanate, preferably, isophorone diisocyanate is used. Of these, isophorone diisocyanate and 2,4-diisocyanate tolylene are preferable from the viewpoint of polymerization reactivity and voltage holding ratio, and isophorone diisocyanate is more preferable from the viewpoint of availability, polymerization reactivity, and voltage holding ratio.

<< tetracarboxylic acid derivative >>
Examples of the tetracarboxylic acid derivative that is a raw material for the component (B) include the following tetracarboxylic dianhydrides.

Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,4,5-pentanetetracarboxylic Dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3 , 5-tricarboxycyclopentylacetic acid dianhydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, tricyclo [4.2.1. 0 ^2,5 ] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7,8-dianhydride, hexacyclo [6.6.0.1 ^2,7 . 0 ^3,6 . 1 ^9,14 . 0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid-4,5: 11,12-dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1 And naphthalene succinic dianhydride.

  As aromatic tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4′- Benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid A dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride etc. are mentioned.

  The tetracarboxylic dianhydride may be used alone or in combination of two or more depending on the liquid crystal alignment properties of the liquid crystal alignment film to be formed, such as voltage holding characteristics and accumulated charges.

Moreover, you may use tetracarboxylic-acid dialkyl ester and tetracarboxylic-acid dialkyl diester dichloride as a tetracarboxylic-acid component which is a raw material of (B) component. When the tetracarboxylic acid component contains such a tetracarboxylic acid dialkyl ester or tetracarboxylic acid dialkyl ester dichloride, the polymer becomes a polyamic acid ester that is a polyimide precursor. The tetracarboxylic acid dialkyl ester that can be used is not particularly limited, and examples thereof include aliphatic tetracarboxylic acid diesters and aromatic tetracarboxylic acid dialkyl esters.
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, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2 , 3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic 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 dialkyl ester, 2,3,5-tricarboxycyclopentyl acetate dialkyl Ester, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 ^2,5 ] nonane-3,4 , 7,8-tetracarboxylic acid-3,4: 7,8-dialkyl ester, hexacyclo [6.6.0.1 ^2,7 . 0 ^3,6 . 1 ^9,14 . 0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid-4,5: 11,12-dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene And succinic dianhydride.

  Specific examples of the aromatic tetracarboxylic acid dialkyl ester include pyromellitic acid dialkyl ester, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dialkyl ester, and 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-naphthalene tetracarboxylic acid dialkyl ester, 2 , 3,6,7-Naphthalenetetracarboxylic acid Alkyl esters thereof.

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

  These tetracarboxylic dianhydrides, tetracarboxylic acid diesters, tetracarboxylic acid diester dichlorides, etc. are each one or two depending on the properties such as liquid crystal alignment properties, voltage holding properties, accumulated charges, etc. when formed into a liquid crystal alignment film. More than one type can be used in combination.

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

  Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, and isophorone diamine. Etc.

  Examples of aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino- 2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-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'-diaminostilbene, 4,4'-diamino Tilben, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 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, bi [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,1-bis (4-aminophenyl) cyclohexane, α, α′-bis (4-amino Phenyl) -1,4-diisopropylbenzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexa Fluoropropane, 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) Nyl) 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) Cis) 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-dioate, 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) phenoxy] heptane, 1,8-bis [4- ( 4-aminophenoxy) phenoxy] octane, 1,9-bis [4- (4-aminophenoxy) phenoxy] nonane, 1,10-bis [4- (4-aminophenoxy) phenoxy] decane and the like.

  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 represents an alkylene group having 1 to 5 carbon atoms, and R ₂ represents a hydrogen atom or a methyl group.

  Specific examples of the aromatic-aliphatic diamine include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4 -Aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-methylaminopropyl) ) Aniline, 4- (3-methylaminopropyl) aniline, 3- (4-aminobutyl) aniline, 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- (4- Methylaminobutyl) aniline, 3- (5-aminopentyl) aniline, 4- (5-aminopenti) ) Aniline, 3- (5-methylaminopentyl) aniline, 4- (5-methylaminopentyl) aniline, 2- (6-aminonaphthyl) methylamine, 3- (6-aminonaphthyl) methylamine, 2- ( 6-aminonaphthyl) ethylamine, 3- (6-aminonaphthyl) ethylamine and the like.

  Examples of heterocyclic diamines include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 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 include 1,18-diaminooctadecane and 1,2-bis (3-aminopropoxy) ethane.

  Examples of urea bond-containing diamines include N, N′-bis (4-aminophenethyl) urea.

Furthermore, in the component (B), the diamine component that undergoes a polymerization reaction with the diisocyanate component may include a diamine having a vertical alignment side chain as long as the effects of the present invention are not impaired.
Moreover, the diamine component in (B) component may contain the following diamines.

  In the formula, m and n are each an integer from 1 to 11, m + n is an integer 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 holding ratio (also referred to as VHR) of a liquid crystal display element using a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention. These diamines are preferred from the viewpoint of excellent stored charge reduction effect of such liquid crystal display elements.

  In addition, examples of the diamine component in the component (B) include diaminosiloxanes represented by the following formula (wherein m is an integer of 1 to 10).

  When the diamine compound further has a nitrogen atom between two amino groups, the nitrogen atom present between the two amino groups is bonded to carbonyl or has two or more benzene rings and a single atom. 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 (B) component, the diamine which has a structure represented by a following formula (Y2-1) is mentioned, for example.

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 bonding part 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 lowered. A methyl group or an ethyl group is preferred.

From the viewpoint of liquid crystal alignment, Y ₂ is preferably formula (Y2-2), (Y2-3), or (Y2-5), and particularly preferably formula (Y2-2) or formula (Y2-5). .

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

  Such diamines include 4,4′-diaminodiphenylmethane, 1,2-bis (4-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 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) penta 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-dioate, 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) phenoxy] heptane, 1,8-bis [4- (4-aminophenoxy) Phenoxy] octane, 1,9-bis [4- (4-aminophenoxy) phenoxy] nonane, 1,10-bis [4- (4-aminophenoxy) phenoxy] decane, N, N′-bis (4-amino) And phenethyl) urea.

  (B) In the polymer of a component, the ratio in the case of containing the structure represented by the said Formula (Y2-1) is preferable 15-90 mol% with respect to all the structural units derived from diamine, and 40-85 mol % Is more preferable.

  These diamine components in the component (B) can be used singly or in combination of two or more depending on the properties such as liquid crystal alignment properties, voltage holding properties, and accumulated charges when the liquid crystal alignment film is formed. The mixing ratio is not limited.

  In addition, the molecular weight of the polymer of component (B) is measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained liquid crystal alignment film, the workability when 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, and more preferably 10,000 to 200,000.

  In obtaining the polymer of the component (B) by a polymerization reaction of at least one selected from the diisocyanate component and tetracarboxylic acid derivative of each raw material and a diamine component, a known synthesis method can be used. Generally, it is a method in which at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine component are reacted in an organic solvent. The reaction of at least one selected from a diisocyanate component and a tetracarboxylic acid derivative with a diamine component is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is generated.

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

  Examples of organic solvents that can be used here include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, and tetramethyl. Urea, pyridine, dimethylsulfone, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate , Ethyl cellosolve acetate, 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, tri Propylene 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, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropyl Pionic 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. These may be used alone or in combination. Further, even a solvent that does not dissolve polyurea may be used by mixing with the above solvent as long as the produced polymer of component (B) does not precipitate.

  In addition, since water in the organic solvent causes the polymerization reaction to be hindered, it is preferable to use a dehydrated and dried organic solvent as much as possible.

  When reacting at least one selected from a diisocyanate component and a tetracarboxylic acid derivative with a diamine component in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred to obtain a diisocyanate component and a tetracarboxylic acid derivative. A method of adding at least one selected from the above as it is or dispersed or dissolved in an organic solvent, and 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 And 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. In addition, when at least one kind selected from a diisocyanate component and a tetracarboxylic acid derivative or a diamine component consists of a plurality of kinds of compounds, they may be reacted in a premixed state, individually in order, or individually. The reacted low molecular weight substance may be mixed and reacted to obtain a high molecular weight substance.

  The polymerization temperature at that time can be selected from an arbitrary temperature of -20 ° C to 150 ° C, 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 is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is 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 stage of the reaction is 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. It is preferable. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polymer produced.

  When the produced polymer is recovered from the reaction solution of the polymer as the component (B), the reaction solution may be poured into a poor solvent and precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated in a poor solvent and collected by filtration can be dried at normal temperature or under reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection | recovery is re-dissolved in an organic solvent and the operation which carries out reprecipitation collection | recovery is repeated 2 to 10 times, the impurity in a polymer can be decreased. 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 purification efficiency is further improved.

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

In the above formula [1], A ₁ and A ₂ may each be one kind and a polymer having the same repeating unit, or A ₁ and A ₂ may be plural kinds and a polymer having a repeating unit having a different structure. But you can.

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

According to a preferred embodiment of the present invention, A ₁ is preferably a group derived from the preferred diisocyanate components listed above. Further, as A ₂ are groups derived from the preferred diamine components listed above are preferred.

  A polyimide precursor is a polymer which has a repeating unit shown by following formula [2], for example.

In Formula [2], A ₃ is each independently a tetravalent organic group, and A ₂ is each independently a 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 each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms that may have a substituent, An alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms.

Specific examples of the 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. Etc. 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 and the diisocyanate in the polyurea polyimide precursor is preferably 99: 1 to 1:99 in terms of molar ratio.

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

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

  The temperature when the polyurea polyamic acid or polyurea polyamic acid ester is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., while removing water generated by the imidization reaction from the system. It is preferable to do this.

  The catalytic imidation 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 It can carry out by stirring at 180 degreeC. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times of the amic acid group, Preferably they are 3 mol times-30 mol times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and 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 poured into a solvent and precipitated. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated in the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection is re-dissolved in a solvent and the operation which carries out reprecipitation collection is repeated 2-10 times, the impurity in a polymer can be decreased. Examples of the solvent at this time include alcohols, ketones, and hydrocarbons, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further increased.

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

<< (C) Organic solvent >>
The organic solvent used for 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, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4 Methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, etc. Is mentioned. 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 solution 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 refers to (A) at least two polymers having a structure that exhibits photoreactivity and a structure that exhibits liquid crystallinity, and (B) a diisocyanate component and a tetracarboxylic acid derivative. It is a resin component comprising at least one selected and a polymer produced 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, the above-mentioned resin components may all be the above-described component (A) and component (B), but other than those as long as the liquid crystal expression ability and the photosensitive performance are not impaired. Other polymers may be mixed. In that case, content of the other polymer in a resin component is 0.5 mass%-80 mass%, Preferably it is 1 mass%-50 mass%.
Examples of such other polymers include poly (meth) acrylates and the like, and examples include polymers that are not polymers having a structure that exhibits photoreactivity and a structure that exhibits liquid crystallinity.

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

The following are mentioned as a specific example of the solvent (poor solvent) which improves the uniformity of film thickness and surface smoothness.
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 monoacetate 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, dipro Lenglycol 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, 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, methyl 3-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 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 Examples include solvents having surface tension.

  These poor solvents may be used alone or in combination. When using the solvent as described above, it is preferably 5% by mass to 80% by mass of the total solvent, 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 that improves film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Company), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done. The use ratio of these surfactants is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part with respect to 100 parts by mass of the resin component contained in the polymer composition. Part by mass.

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-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Examples thereof include propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane.

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

  Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentylglycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl-4 4'-diaminodiphenylmethane and the like.

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

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

As photosensitizers, aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino substituted Aromatic 2-hydroxyketone (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene)- 3-methylbenzothia Phosphorus, 2- (β-naphthoylmethylene) -3-methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene)- 3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α-naphthoylmethylene) ) -3-methylbenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthoxazoline, 2- (4-biphenoyl) Methylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β- Ftoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p -Methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol And 9-anthracenecarboxylic acid), benzopyran, azoindolizine, methylcoumarin and the like.
Aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferred.

  In the polymer composition, in addition to the above-described ones, a dielectric, a conductive substance, or the like for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film, as long as the effects of the present invention are not impaired. Furthermore, a crosslinkable compound may be added for the purpose of increasing the hardness and density of the liquid crystal alignment film.

<Liquid crystal aligning agent>
The present application has a polymer composition as described above, or consists essentially of the polymer composition as described above, or a liquid crystal aligning agent composed of only the polymer composition as described above, particularly for a liquid crystal display element, more particularly laterally. A liquid crystal aligning agent for an electric field driven liquid crystal display element is provided.

<Liquid crystal alignment film> or <Substrate having liquid crystal alignment film>
This application provides the liquid crystal aligning film formed from the above-mentioned liquid crystal aligning agent, especially the liquid crystal aligning film for liquid crystal display elements, and more especially for a horizontal electric field drive type liquid crystal display element.
In addition, the present application relates to a liquid crystal alignment film formed from the liquid crystal alignment agent described above, particularly a substrate having a liquid crystal alignment film for a liquid crystal display element, more particularly a lateral electric field drive type liquid crystal display element, particularly a liquid crystal display element. A substrate for a horizontal electric field drive type liquid crystal display element is provided.

<Method for manufacturing liquid crystal alignment film> or <Method for manufacturing substrate having liquid crystal alignment film>
The liquid crystal alignment film described above is
[I] The process of apply | coating the above-mentioned polymer composition or the above-mentioned liquid crystal aligning agent on a board | substrate, for example on the board | substrate which has a conductive film for a horizontal electric field drive, and forming 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];
Thus, a liquid crystal alignment film imparted with an alignment control ability, particularly a liquid crystal alignment film for a liquid crystal display element, more particularly a lateral electric field drive type liquid crystal display element, or a substrate having the liquid crystal alignment film can be obtained.

<< Board >>
Although it does not specifically limit about a board | substrate, When the liquid crystal display element manufactured is a transmission type, it is preferable that a highly transparent board | substrate is used. In that case, there is no particular limitation, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.
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 lateral electric field >>
The substrate has a conductive film for driving a horizontal electric field when used in a horizontal electric field drive type liquid crystal display element.
Examples of the conductive film include, but are not limited to, ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) when the liquid crystal display element is a transmission type.
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 are not limited thereto.
As a method for forming a conductive film on a substrate, a conventionally known method can be used.

<< Step [I] >>
In the step [I], on the substrate having the conductive film for driving the lateral electric field, the (A) structure exhibiting photoreactivity and the structure exhibiting liquid crystallinity of the present invention exhibit liquid crystallinity within a predetermined temperature range. (B) a polymer produced using 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 component (A) is a temperature at which at least two polymers of component (A) exhibit a liquid crystal phase as a whole.

The method for applying the polymer composition described above or the liquid crystal aligning agent described above onto a substrate having a conductive film for driving a lateral electric field is not particularly limited.
In general, the application method is generally performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), or a spray method, 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 heating means such as a hot plate, a thermal circulation type oven or an IR (infrared) type oven is used. Preferably, the solvent can be evaporated at 50 to 150 ° C. to obtain a coating film. 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 be lowered. Therefore, it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is.
In addition, it is also possible to provide the process of cooling the board | substrate with which the coating film was formed to room temperature after the [I] process and before the following [II] process.

<< Step [II] >>
In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When irradiating the surface of the coating film with polarized ultraviolet rays, the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction. As the ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used. 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 amount of irradiation is polarized ultraviolet light that realizes the maximum value of ΔA (hereinafter also referred to as ΔAmax), which is the difference between the ultraviolet light absorbance in a direction parallel to the polarization direction of polarized ultraviolet light and the ultraviolet light absorbance in a direction perpendicular to the polarization direction of the polarized ultraviolet light. The amount is preferably in the range of 1% to 70%, more preferably in the range of 1% to 50%.

<< Step [III] >>
In step [III], the ultraviolet-irradiated coating film polarized in step [II] is heated. An 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 crystallinity of the coating film used is developed.

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

  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. And a board | substrate with a liquid crystal aligning film can be manufactured highly efficiently.

<Liquid crystal display element> and <Method for manufacturing liquid crystal display element>
The present application provides a liquid crystal display element having a substrate having a liquid crystal alignment film obtained as described above, particularly a lateral electric field drive type liquid crystal display element.

Specifically, in addition to the substrate having the liquid crystal alignment film (first substrate) obtained above, a second substrate is prepared, whereby a lateral electric field drive type liquid crystal display element can be obtained.
When the second substrate uses a substrate having no lateral electric field driving conductive film instead of the substrate having the lateral electric field driving conductive film, the second electric field driving conductive film as in the first substrate is used. In some cases, a substrate having In addition, the second substrate preferably has a liquid crystal alignment film as in the first substrate.

A method for manufacturing a liquid crystal display element, particularly a lateral electric field drive type liquid crystal display element,
[IV] A step of obtaining a liquid crystal display element by arranging the first and second substrates obtained above so that the liquid crystal alignment films of the first and second substrates face each other with liquid crystal interposed therebetween;
Have Thereby, a liquid crystal display element, especially a horizontal electric field drive type liquid crystal display element can be obtained.

<Process [IV]>
The step [IV] is performed in the same manner as the above [I ′] to [III ′] in the same manner as the substrate (first substrate) obtained in [III] and having a liquid crystal alignment film on the conductive film for driving a horizontal electric field. The obtained liquid crystal alignment film-attached substrate (second substrate) is arranged to face each other with the liquid crystal alignment film facing each other through the liquid crystal, and a liquid crystal cell is manufactured by a known method. This is a step of manufacturing a drive type liquid crystal display element. The steps [I ′] to [III ′] can be performed in the same manner as the steps [I] to [III] except for the difference in the presence or absence of the conductive film for driving the lateral electric field in the step [I]. Since the difference between the steps [I] to [III] and the steps [I ′] to [III ′] is only the presence or absence of the conductive film, the description of the steps [I ′] to [III ′] is omitted. To do.

To give an example of the production of a liquid crystal cell or a liquid crystal display element, the first and second substrates described above are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, 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, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed. , Etc. can be illustrated. At this time, when a lateral electric field driving type liquid crystal display element is manufactured, it is preferable to use a substrate having electrodes having a structure like a comb for driving an electric field 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 aligning agent of the present invention, the liquid crystal alignment film formed using the composition or the liquid crystal aligning agent, the substrate having the alignment film, and the liquid crystal alignment film or substrate are provided. The liquid crystal display element formed in this manner has excellent reliability and can be suitably used for a large-screen and high-definition liquid crystal television.

MA1 as a monomer having a photoreactive group used in Examples, MA2 as a monomer having a liquid crystal group, HBAGE as a monomer having a crosslinking group, and A1 as a monomer having an amide group are shown below.
MA1 and MA2 were synthesized as follows. That is, MA1 was synthesized by a synthesis method described in a patent document (WO2011-084546). MA2 was synthesized by a synthesis method described in a patent document (Japanese Patent Laid-Open No. 9-118717). A polymer formed using MA1 as a monomer has photoreactivity and liquid crystallinity, and a polymer formed using MA2 as a monomer has only liquid crystallinity.
The monomer A1 to be copolymerized was synthesized by the synthesis method described in WO2014 / 054785 pamphlet.
As HBAGE (hydroxybutyl acrylate glycidyl ether), a commercially available product was used.

<Diisocyanate component>
ISPDA: Isophorone 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 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 cellosolve (polymerization initiator)
AIBN: 2,2′-azobisisobutyronitrile

<Photo-alignment polymer synthesis example P1>
MA1 (1.66 g: 0.1 mol%) and MA2 (13.79 g: 0.9 mol%) were dissolved in THF (146.42 g), and after deaeration with a diaphragm pump, AIBN (0.82 g ) And deaerated again. Thereafter, the mixture was reacted 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. This precipitate was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P1.

<Photoalignment polymer synthesis examples P2 to P3>
The methacrylate polymer powders P2 to P3 were synthesized using the same method as in the photoalignment polymer synthesis example P1 except that the composition shown in Table 1 was used.

<Polymer synthesis example L1>
As tetracarboxylic dianhydride component, 4.85 g of TDA, 3.67 g of ISPDA as diisocyanate component, 5.89 g of DDM, 0.35 g of Me-DADPA, 0.25 of Me-4APhA as diamine component The resulting solution was reacted in 85.06 g of NMP at room temperature for 18 hours to obtain a polyamic acid (L1) solution having a 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 are used in 86.67 g of NMP. The solution was reacted at room temperature for 18 hours to obtain a polyurea (L2) solution having a concentration of 15 wt%.

<Polymer synthesis example L3>
As the diisocyanate component, 7.11 g of ISPDA, 6.45 g of DA-2MG and 1.41 g of Me-DADPA as the diamine component were used and reacted in NMP84.84 g at room temperature for 18 hours at a polyurea (L3) concentration of 15 wt%. Solution was obtained.

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

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

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

<Control 1>
The methacrylate polymer powder P2 (0.36 g) obtained in the photoalignment polymer synthesis example P2 was added to NMP (8.04 g), and the mixture was dissolved by stirring at room temperature for 1 hour. To this solution, the polyamic acid solution L1 (5.6 g) obtained in Polymer Synthesis Example L1 and BCS (6.0 g) were added 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 the photoalignment polymer synthesis example P2 was added to NMP (8.04 g), and the mixture was dissolved by stirring at room temperature for 1 hour. To this solution, the polyurea solution L2 (5.6 g) obtained in Polymer Synthesis Example L2 and BCS (6.0 g) were added 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 the photoalignment polymer synthesis example P2 was added to NMP (8.04 g), and the mixture was dissolved by stirring at room temperature for 1 hour. To this solution, the polyurea solution L3 (5.6 g) obtained in Polymer Synthesis Example L3 and BCS (6.0 g) were added 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 the photoalignment polymer synthesis example P3 was added to NMP (8.04 g), and the mixture was dissolved by stirring at room temperature for 1 hour. To this solution, the polyamic acid solution L1 (5.6 g) obtained in Polymer Synthesis Example L1 and BCS (6.0 g) were added and stirred to obtain a polymer solution CT4. This polymer solution CT4 was used as a liquid crystal aligning agent for forming a liquid crystal alignment film as it was.

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

<Control 6>
The methacrylate polymer powder P3 (0.36 g) obtained in the photoalignment polymer synthesis example P3 was added to NMP (8.04 g), and the mixture was dissolved by stirring at room temperature for 1 hour. To this solution, the polyurea solution L3 (5.6 g) obtained in Polymer Synthesis Example L3 and BCS (6.0 g) were added 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 photoalignment polymer synthesis example P1 and the methacrylate polymer powder P2 (0.84 g) obtained in the photoalignment polymer synthesis example P2 are added to NMP (12.8 g). In addition, the mixture was dissolved by stirring at room temperature for 1 hour. By adding BCS (6.0 g) and stirring, a polymer solution CT7 was obtained. 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 aligning agents T1 to 3 of Examples 1 to 3 and the liquid crystal aligning agents CT1 to CT6 of Controls 1 to 6, the polymer species used and their wt%, and two photoalignment polymers are used for the examples. Is the amount of the photoreactive group in each photo-alignment polymer, the “photoreactive group” in each photo-alignment polymer, the monomer species from which the “liquid crystalline group” is derived and the “amount of photoreactive group” in the monomer In addition, the “total photoreactive group amount” in the liquid crystal aligning agent derived therefrom is summarized in Table 2 below.
The “photoreactive group amount in each photo-alignment polymer” and “total photoreactive group amount” in Table 2 can be determined, for example, as follows.

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

<Production of liquid crystal cell>
The liquid crystal aligning agent (T1) obtained in Example 1 was 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 a film thickness of 100 nm. A liquid crystal alignment film was formed. Next, the coating film surface was irradiated with 5 to 50 mJ / cm ² of 313 nm ultraviolet rays 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 substrates with such a liquid crystal alignment film are prepared, a 6 μm spacer is set on the liquid crystal alignment film surface of one substrate, and the two substrates are combined so that the rubbing directions are parallel to each other. The periphery was sealed, and an empty cell with a cell gap of 4 μm was produced. Liquid crystal MLC-3019 (manufactured by Merck & Co., 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 liquid crystals were aligned in parallel.
Similarly, a liquid crystal cell was prepared using the liquid crystal aligning agents T2 and T3 obtained in Examples 2 and 3 and the liquid crystal aligning agents CT1 to 7 obtained in Controls 1 to 7.

<Orientation evaluation>
The liquid crystal cells prepared in Examples 1 to 3 and Controls 1 to 7 were placed between two polarizing plates arranged so that their polarization axes were orthogonal to each other, and the backlight was turned on with no voltage applied, and transmitted. The arrangement angle of the liquid crystal cell was adjusted so that the luminance of light was minimized. Visually check the liquid crystal cell. When this liquid crystal cell was well aligned and no fluid alignment was confirmed, “◯” was indicated, when the aligned one was confirmed “Δ”, and when it was not aligned, “X” was indicated.

<Evaluation of voltage holding ratio (VHR)>
Using the liquid crystal cell produced above, a voltage of 5 V was applied for 60 μs at a temperature of 70 ° C., a voltage after 16.67 ms was measured, and how much the voltage could be held was calculated as a voltage holding ratio (VHR). . The voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technica.
The results of VHR 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 photoalignment polymer component.

From Table 2, in Examples 1 to 3, two kinds of photo-alignment polymers having different photoreactive group amounts were used, and blending with a polyamic acid or polyurea solution resulted in good alignment in a wide range of UV irradiation doses. And good VHR.
Specifically, when Examples 1 to 3 and Controls 1 to 3 are compared, the total photoreactive group amount is 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 in both of them, and VHR shows almost the same value. However, in both, in Example 1, two types (P1 and P2) are used as the polymer type, while in Control 1, only one type (P2) is used as the polymer type. This difference, while the excellent orientation to UV irradiation dose 30 mJ / cm ² in Example 1 is confirmed, a non-oriented in UV dose 30 mJ / cm ² in the control 1 found the following Example 1, Control Compared with 1, it can be seen that a good orientation is exhibited in a wide range of UV irradiation doses.
When Examples 1-3 are compared with Controls 4-6, they have the same total photoreactive group amount (Examples 1-3: 0.17; Controls 4-6: 0.17). While two types (P1 and P2) are used as the alignment polymer species, in Control 3, only one type (P3) is used as the photo-alignment polymer species. This difference, Examples 1-3 In While excellent orientation to UV irradiation dose 30 mJ / cm ² is confirmed, the flow orientation in the control 1 UV dose 30 mJ / cm ² is confirmed, Examples 1-3 It can be seen that this shows better orientation in a wide range of UV irradiation doses compared to Controls 4-6. Moreover, it turns out that Examples 1-3 are improving VHR compared with the control 7. FIG.

Claims (20)

(A) at least two types of polymers having a structure that exhibits photoreactivity and a structure that exhibits liquid crystallinity;
(B) a polymer produced using at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine compound;
And (C) an organic solvent;
A polymer composition containing   2. The polymer composition according to claim 1, wherein among the (A) at least two kinds of polymers, one polymer (A1) and the other polymer (A2) are different in the amount of structures that express photoreactivity with each other.   The composition according to claim 1 or 2, wherein each of the (A) at least two polymers has a structure that exhibits photoreactivity and a structure that exhibits only liquid crystallinity. The structure expressing the photoreactivity is
Following formula (1)-(6)
(In the formula, A, B and D are each independently a 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 a hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —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, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 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 the same definition as Y ₁ ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
Cou represents coumarin-6-yl group or a coumarin-7-yl group, _-NO 2 are each a hydrogen atom bonded to them _{independently, -CN, -CH = C (CN} ) 2, -CH = CH- 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 each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q 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 l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof. )
The polymer composition according to any one of claims 1 to 3, which has any one structure selected from the group consisting of:

The structure exhibiting only the liquid crystallinity has the following formulas (21) to (31).
Wherein A and B have the same definition as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO ₂ , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
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, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer 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 heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
4. Z ₁ and Z ₂ each represent one type of structure selected from the group consisting of a single bond, —CO—, —CH ₂ O—, —CH═N—, and —CF ₂ —. Or 5. The polymer composition according to 4.

The amount of the structure that exhibits photoreactivity of the polymer (A1) is α mol when the total of the structure that exhibits photoreactivity and the structure that exhibits liquid crystallinity of the polymer (A1) is 100 mol%. % (Α is 15 or more),
The amount of the structure expressing the photoreactivity of the polymer (A2) is 0.95α mol% when the structure expressing the photoreactivity of the polymer (A2) and the structure exhibiting liquid crystallinity are 100 mol%. It is the following, The polymer composition of any one of Claims 2-5.   The weight average molecular weight of the polymer (A1) is β (β is 30,000 or more), and the weight average molecular weight of the polymer (A2) is 0.1β to 0.9β. The polymer composition described in 1.   (M-1) a monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity, and (M-2) a monomer (M2) having a structure that exhibits only liquid crystallinity. The polymer composition according to any one of claims 1 to 7, wherein the polymer composition is formed. When the total of the monomer (M1) and the monomer (M2) is 100 mol%,
The polymer (A1) is formed such that the monomer (M1) is α mol% (α is 15 or more) and the monomer (M2) is a residue,
The polymer according to any one of claims 6 to 8, wherein the polymer (A2) is formed such that the monomer (M1) is 0.95α mol% or less and the monomer (M2) is a residue. Composition. The component (B) is a polymer produced using at least one selected from a diisocyanate component and a tetracarboxylic acid derivative and two or more diamine compounds, and the structure derived from the diamine is represented by the formula (Y2-1). (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 bonding portion between Z ₃ and the benzene ring is The polymer composition according to any one of claims 1 to 9, 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 10, wherein the polymer of the component (B) is a polyurea obtained by polymerizing a diisocyanate component and a diamine component.   The polymer of (B) component is a polyurea polyimide precursor obtained by polymerizing a diisocyanate component, a tetracarboxylic acid derivative, and a diamine component, The heavy as described in any one of Claims 1-10. Combined composition.   The polymer composition according to any one of claims 1 to 10, wherein the polymer of the component (B) is a polyimide precursor obtained by polymerizing a tetracarboxylic acid derivative and a diamine component.   The liquid crystal aligning agent containing the polymer composition of any one of Claims 1-13.   The liquid crystal aligning film formed from the liquid crystal aligning agent of Claim 14. [I] The process of apply | coating the polymer composition of any one of Claims 1-13 on the board | substrate which has a conductive film for a horizontal electric field drive, and forming 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 obtains a liquid crystal alignment film imparted with an alignment control ability.   A substrate having the liquid crystal alignment film according to claim 16. [I] The process of apply | coating the polymer composition of any one of Claims 1-13 on the board | substrate which has a conductive film for a horizontal electric field drive, and forming 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];
The manufacturing method of the board | substrate which has a liquid crystal aligning film which obtains the liquid crystal aligning film by which alignment control ability was provided by having.   The liquid crystal display element which has a board | substrate obtained with the manufacturing method of Claim 18. A step of manufacturing a substrate (first substrate) according to claim 18;
[I '] The process of apply | coating the polymer composition of any one of Claims 1-13 on a 2nd board | substrate, and forming a coating film;
[II ′] A step of irradiating the coating film obtained in [I ′] with polarized ultraviolet rays;
[III ′] a step of heating the coating film obtained in [II ′];
Obtaining a liquid crystal alignment film imparted with alignment control capability by having a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment of the first and second substrates via liquid crystal A step of obtaining a liquid crystal display element by arranging the first and second substrates to face each other so that the films face each other;
A method for producing a liquid crystal display element, comprising obtaining a liquid crystal display element.