KR20180132057A - Liquid crystal aligning 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 capable of efficiently obtaining a liquid crystal alignment film having a good quality by expanding a range of light irradiation amount in which alignment control ability stably occurs and more specifically to a liquid crystal composition for liquid crystal display A composition for preparing an alignment film is provided. The present invention also provides a liquid crystal aligning agent and a liquid crystal alignment film formed from the composition, a substrate having the liquid crystal alignment film, and a liquid crystal display element. (A) at least two polymers having a structure exhibiting photoreactivity and a structure exhibiting liquid crystallinity; (B) a polymer produced by using at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine compound, and (C) an organic solvent; (A1) and the other polymer (A2) among the at least two kinds of polymers provide a polymer composition which differs in the amount of the structure that exhibits photoreactivity with respect to each other.

Description

Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element

The present invention relates to a polymer composition for a liquid crystal aligning agent, particularly a liquid crystal aligning agent for a transverse electric field driving type liquid crystal display element, and a liquid crystal aligning agent consisting essentially of, or having, Liquid crystal alignment films for liquid crystal display devices, liquid crystal alignment films formed by the liquid crystal alignment agents, particularly liquid crystal alignment films for transverse electric field driven liquid crystal display devices, substrates having the liquid crystal alignment films, particularly substrates for transversely driven liquid crystal display devices, And more particularly to a liquid crystal display element having a substrate, in particular, a transversely-field-driven liquid crystal display element.

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

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

As a method of orienting a liquid crystal alignment film for imparting alignment control ability, in addition to the conventional rubbing method, a photo alignment method is known. Compared with the conventional rubbing method, the photo alignment method has an advantage in that it is possible to perform alignment treatment on a substrate of a liquid crystal display element which does not require rubbing and does not cause generation of oscillation or static electricity and has irregularities on its surface have.

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

As the photo-alignment method, a photo-alignment method of a decomposition type, a photo-alignment method of a photo-crosslinking type or a photo-isomerization type, and the like are known.

The decomposition type optical alignment method is a method in which, for example, polarized ultraviolet rays are irradiated to a polyimide film, anisotropic decomposition is generated by utilizing polarization direction dependency of ultraviolet absorption of the molecular structure, (See, for example, Patent Document 1).

The photo-crosslinking or photo-isomerization photo-alignment method can be carried out by, for example, using polyvinyl cinnamate, irradiating polarized ultraviolet light, and performing a diminution reaction (cross-linking reaction) in a double bond portion of two side chains parallel to polarized light ), And aligning the liquid crystal in a direction perpendicular to the polarization direction (see, for example, Non-Patent Document 1). When a side chain type polymer having azobenzene as a side chain is used, polarized ultraviolet light is irradiated to generate an isomerization reaction in the azobenzene moiety of the side chain parallel to the polarized light, and the liquid crystal is aligned in a direction orthogonal to the polarization direction See, for example, Non-Patent Document 2). Patent Document 3 discloses a liquid crystal alignment film obtained by photo-crosslinking, photo-isomerization, or photo alignment using optical-free potential.

Japanese Patent No. 3893659 Japanese Unexamined Patent Application Publication No. 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 does not require the rubbing process itself as compared with the conventionally used rubbing method as an alignment processing method of a liquid crystal display element. Compared to the rubbing method in which the alignment control ability is almost constant by rubbing, in the photo alignment method, the alignment control ability can be controlled by changing the irradiation amount of the polarized light.

However, if the orientation control ability of the main component used in the photo alignment method is excessively sensitive to the irradiation amount of the polarized light, the orientation of the liquid crystal alignment film may be incomplete in a part or the whole, and stable alignment of the liquid crystal may not be realized.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a polymer composition for producing a liquid crystal alignment film capable of efficiently obtaining a liquid crystal alignment film having a good quality by expanding the range of light irradiation amount in which alignment control ability stably occurs, And a composition for producing a liquid crystal alignment film for a display element.

It is another object of the present invention to provide a liquid crystal aligning agent having the composition in addition to or in addition to the above object, a liquid crystal alignment film produced using the liquid crystal aligning agent, a substrate having the liquid crystal alignment film, Or a liquid crystal display element having the substrate, in particular, a transverse electric field driven liquid crystal display element.

The present inventors have found the following inventions.

≪ 1 > A liquid crystal display comprising: (A) at least two polymers having a structure exhibiting photoreactivity and a structure exhibiting liquid crystallinity;

(B) a polymer prepared by using a diamine compound and at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative; And

(C) an organic solvent;

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

<2> It is preferable that the polymer (A1) and the other polymer (A2) of the at least two polymers as the component (A) in the above item <1> .

<3> In the above-mentioned <1> or <2>, at least two kinds of polymers as the component (A) each preferably have a structure that exhibits photoreactive properties and a structure that exhibits only liquid crystallinity. In the present specification, the term &quot; liquid crystal only &quot; in the &quot; structure expressing only liquid crystallinity &quot; is a word used when considering the &quot; photoreactivity &quot; and &quot; liquid crystalline property &quot; &Quot; is expressed by the word &quot; bay. &Quot;

&Lt; 4 > The structure for expressing the photoreactivity in the above < 1 > to < 3 &

The following formulas (1) to (6)

(Wherein, A, B, D are, each independently, a single _{bond, -O-, -CH 2 -, -COO-} , -OCO-, -CONH-, -NH-CO-, -CH = CH-CO -O-, or -O-CO-CH = CH-;

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

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

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

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

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

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

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

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

q3 is 0 or 1;

P and Q are each independently a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof; When X is -CH = CH-CO-O- or -O-CO-CH = CH-, P or Q on the side bonded to -CH = CH- is an aromatic ring, , The P groups may be the same or different, and when Q is 2 or more, the Q groups 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, when T is a single bond, A also represents a single bond;

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

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

Or a structure selected from the group consisting of

[Chemical Formula 1]

&Lt; 5 > The method according to < 3 > or < 4 &

The structures expressing only liquid crystallinity are represented by the following formulas (21) to (31)

(Wherein A and B have the same definitions as above;

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

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

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

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

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

Z ₁ and Z _{2 each} represent a single bond, -CO-, -CH ₂ O-, -CH═N-, or -CF ₂ -).

(2)

<6> In any one of the above items <2> to <5>, the amount of the structure that exhibits the photoreactivity of the polymer (A1) When the total amount is 100 mol%,? Mol% (? Is 15 or more, preferably 15 to 100, more preferably 20 to 80)

The amount of the structure that exhibits the photoreactivity of the polymer (A2) is 0.95? Mol% or less, preferably 0.1 (%) or less, to 0.8% by mole, and more preferably from 0.25 to 0.5% by mole.

<7> The method according to any one of <2> to <6>, wherein the weight average molecular weight of the polymer (A1) is β (β is 30,000 or more, preferably 30,000 to 300,000, And the polymer (A2) has a weight average molecular weight of 0.1? To 0.9?, Preferably 0.2? To 0.8?, More preferably 0.3? To 0.7? desirable.

<8> The polymer composition according to any one of <2> to <7>, wherein the total weight of the polymer (A1) and the polymer (A2) is 100 wt% Preferably 50 to 90 wt%, and more preferably 60 to 80 wt%.

<9> a monomer (M1) according to any one of <1> to <8>, wherein at least two kinds of polymers have a structure that exhibits (M-1) photoreactive and liquid crystalline properties; And (M-2) a monomer (M2) having a structure which expresses only liquid crystallinity; As shown in Fig.

<10> It is preferable that the monomer (M1) has the structure represented by any one of the formulas (1) to (20) in the above <9>.

<11> In the above-mentioned <9> or <10>, it is preferable that the monomer (M2) has a structure represented by the above formulas (21) to (31).

<12> The polymer according to any one of <9> to <11>, wherein the monomer (M1) has the following formulas: MA1, MA3, MA4, MA5, MA14, MA16 to MA23, MA25, MA28 to MA30, MA32, MA34, At least one selected from the group consisting of MA38 to MA42, MA44 and MA46.

<13> The polymer according to any one of <9> to <12>, wherein the monomer (M2) is a group consisting of MA2, MA9 to MA13, MA15, MA24, MA26, MA27, MA31, MA35, MA37, MA43 and MA45 Is preferably at least one selected from the group consisting of

(3)

[Chemical Formula 4]

[Chemical Formula 5]

<14> In any one of <9> to <13>, when the total amount of the monomer (M1) and the monomer (M2) is 100 mol%, the polymer (A1) (? is at least 15, preferably from 15 to 100, more preferably from 20 to 80) and the remainder is monomer (M2)

The polymer (A2) is formed so that the monomer (M1) accounts for 0.95 mol% or less, preferably 0.1 to 0.8 mol%, more preferably 0.25 to 0.5 mol%, and the remainder is the monomer (M2) .

<15> The polymer according to any one of <1> to <14>, wherein the component (B) is a polymer produced by using at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative and at least two diamine compounds , And a polymer having a structure represented by the formula (Y2-1) as a structure derived from a diamine.

[Chemical Formula 6]

Provided that 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 of Z ₃ and the benzene ring is a single bond, Bond, urea bond or amide bond.

<16> In the above-mentioned <1> to <15>, it is preferable that the polymer of component (B) is a polyurea obtained by polymerizing a diisocyanate component and a diamine component.

<17> It is preferable that the polymer of component (B) is a polyurea polyimide precursor obtained by polymerization reaction of a diisocyanate component, a tetracarboxylic acid derivative, and a diamine component in the above items <1> to <15> .

<18> In the above-mentioned <1> to <15>, it is preferable that the polymer of component (B) is a polyimide precursor obtained by polymerizing a tetracarboxylic acid derivative and a diamine component.

<19> A liquid crystal aligning agent containing a polymer composition according to any one of <1> to <18>, particularly a liquid crystal aligning agent for a transverse electric field driven liquid crystal display element.

<20> A liquid crystal alignment agent described in <19>, particularly a liquid crystal alignment film formed of a liquid crystal aligning agent for a transverse electric field driven liquid crystal display element, particularly a liquid crystal alignment film for a transverse electric field driven liquid crystal display element.

[21] [I] A process for forming a coating film by applying the polymer composition described in any one of the above items <1> to <18> on a substrate having a conductive film for transverse electric field drive;

[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; And

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

To obtain a liquid crystal alignment film for a liquid crystal alignment film, particularly a liquid crystal alignment film for a liquid crystal display device of a transverse electric field driving type.

<22> The liquid crystal alignment film of the above <21>, particularly a substrate having a liquid crystal alignment film for a transversal electric field type liquid crystal display device, particularly a substrate for a transversely driven liquid crystal display device.

[23] [I] A process for forming a coating film by applying the polymer composition described in any one of the above items <1> to <18> on a substrate having a conductive film for driving a transverse electric field;

[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; And

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

To obtain a liquid crystal alignment film for a liquid crystal alignment film for a liquid crystal display device, and particularly to a liquid crystal alignment film to which orientation control ability is imparted.

<24> A substrate obtained in the above <23>, particularly a liquid crystal display element having a substrate for a transversal electric field driving type liquid crystal display element, particularly a transversely driven liquid crystal display element.

<25> A method of manufacturing a semiconductor device, comprising the steps of: fabricating a substrate (first substrate) according to <23> above;

[I '] a step of applying a polymer composition described in any one of < 1 > to < 18 >

A step of irradiating the coating film obtained in [II '] [I'] with polarized ultraviolet light;

Heating the coating film obtained in [III '] [II'];

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

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

To obtain a liquid crystal display element, particularly a transversely-field driven liquid crystal display element.

According to the present invention, there is provided a polymer composition for producing a liquid crystal alignment film capable of efficiently obtaining a liquid crystal alignment film having a good quality by expanding the range of the light irradiation amount in which the alignment control ability is stably produced, specifically a polymer composition for a liquid crystal display A composition for producing a liquid crystal alignment film can be provided.

In addition to or in addition to the above effects, the present invention also provides a liquid crystal aligning agent having the composition, a liquid crystal alignment film produced using the liquid crystal aligning agent, a substrate having the liquid crystal alignment film, a liquid crystal alignment film thereof, and / It is possible to provide a liquid crystal display element having the substrate, in particular, a transverse electric field driven liquid crystal display element.

The present invention relates to a liquid crystal aligning agent for a liquid crystal aligning agent, particularly a liquid crystal aligning agent for a transverse electric field driving type liquid crystal display element, a liquid crystal aligning agent consisting solely of, or substantially containing, A liquid crystal alignment film for liquid crystal display elements, a liquid crystal alignment film for liquid crystal display elements, a liquid crystal alignment film for liquid crystal display elements, a liquid crystal alignment film for liquid crystal display elements, And a liquid crystal display element, in particular, a transverse electric field driving type liquid crystal display element. Hereinafter, they will be described in detail in order.

&Lt; Polymer composition >

The present invention provides polymer compositions, particularly polymer compositions for liquid crystal aligners, more particularly liquid crystal aligners for transverse electric field driven liquid crystal display devices.

The polymer composition of the present invention,

(A) at least two kinds of polymers having a structure exhibiting photoreactivity and a structure exhibiting liquid crystallinity; (B) a polymer produced by using at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine compound; And (C) an organic solvent.

It is preferable that the polymer (A1) and the polymer (A2) of one of the at least two polymers as the component (A) differ in the amount of the structure that exhibits photoreactivity.

At least two kinds of polymers as the component (A) each preferably have a structure which exhibits photoreactivity and liquid crystallinity and a structure which expresses only liquid crystallinity. In the present specification, the term &quot; liquid crystal only &quot; in the &quot; structure expressing only liquid crystallinity &quot; is a word used when considering the &quot; photoreactivity &quot; and &quot; liquid crystalline property &quot; &Quot; is expressed by the word &quot; bay. &Quot;

&Lt; (A) Polymer having a structure exhibiting photoreactivity and a structure exhibiting liquid crystallinity &

In the present specification, the term &quot; structure exhibiting photoreactivity &quot; refers to a structure that reacts in light of a wavelength range, particularly in a wavelength range of 250 nm to 400 nm. For example, It is preferable that the polymer has a side chain of the polymer.

In the present specification, the "photoreactivity" is not particularly limited, but refers to a crosslinking reaction, an isomerization reaction, or a photofrequency potential in response to light, preferably a crosslinking reaction. In the case of using a polymer having a &quot; structure exhibiting photoreactivity &quot;, even if it is exposed to external stress such as heat, the realized orientation control ability can be stably maintained for a long period of time.

As used herein, the term &quot; structure exhibiting liquid crystallinity &quot; refers to a structure exhibiting liquid crystallinity in a certain temperature range, particularly in a temperature range of 100 to 300 ° C. For example, a mesogen group or meso group It is preferable that it is a structure having a Gens component.

When a polymer having a &quot; structure exhibiting liquid crystallinity &quot; is used, a stable liquid crystal alignment can be obtained when the polymer is used as a liquid crystal alignment film.

It is preferable that the structure of the polymer has, for example, a main chain and a side chain which bonds to the main chain, and the side chain thereof has a structure expressing photoreactivity and a structure expressing liquid crystallinity. The &quot; structure exhibiting photoreactivity &quot; and &quot; the structure exhibiting liquid crystallinity &quot; may be on the same side chain or on different side chains. Preferably, the polymer is a polymer having a structure that exhibits photoreactive and liquid crystallinity in either side chain, and has a structure that expresses only liquid crystallinity in the other side chain.

When a structure exhibiting photoreactivity and a structure expressing liquid crystallinity are present in the same side chain, mesogen components such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group and an azobenzene group, Quot; structure exhibiting photoreactivity &quot; indicating a crosslinking reaction or an isomerization reaction in response to light coupled to the tip end of the side chain, may be a mesogen component whose side chain is &quot; a structure that exhibits liquid crystallinity &quot; And a structure having a phenyl benzoate group that undergoes a photoreactive reaction such as &quot; a structure that exhibits photoreactivity &quot;.

Specific examples of the main chains of the at least two kinds of polymers as the component (A) of the present invention are not particularly limited, but each independently may include hydrocarbons, (meth) acrylates, itaconates, fumarates, maleates, And at least one member selected from the group consisting of radically polymerizable groups such as methylene-gamma -butyrolactone, styrene, vinyl, maleimide and norbornene, and siloxane.

<< Structure to express photoreactivity >>

It is preferable that the structure exhibiting photoreactivity, particularly the structure exhibiting photoreactivity and liquid crystallinity, has a structure represented by any one of the formulas (1) to (6). In addition, the formula, A, the same definitions as B, D, S, Y _1, Y _2, R, X, Cou, q1 and q2, q3, P and Q, l1, l2, H, and I, the above-mentioned .

(7)

The side chain is preferably any one photosensitive side chain selected from the group consisting of the following formulas (7) to (10).

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

l represents an integer of 1 to 12;

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

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

[Chemical Formula 8]

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

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

[Chemical Formula 9]

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

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

[Chemical formula 10]

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

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

(11)

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

In the formula, A, B, Y1, q1, q2, m1 and m2 have the same definitions as above.

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

[Chemical Formula 12]

The side chain is preferably a photosensitive side chain represented by the following formula (20).

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

[Chemical Formula 13]

<< Structure that expresses liquidity only >>

The structure expressing only liquid crystallinity is preferably a structure represented by any one of the formulas (21) to (31). In addition, the formula, A, B, Y _3, R _3, q1, q2, l, m, m1, m2, m3, R _2, Z _1, Z ₂ is, has the same definition as described above.

[Chemical Formula 14]

<< Amount of structure that expresses photoreactivity of each of at least two kinds of polymers as component (A) >>

When the total of the structure exhibiting photoreactivity and the structure exhibiting only liquid crystallinity in each of at least two kinds of polymers as the component (A) is taken as 100 mol%

The amount of the structure that expresses the photoreactivity of the polymer (A1) is? Mol% (? Is 15 or more, preferably 15 to 100, more preferably 20 to 80)

The amount of the structure that expresses the photoreactivity of the polymer (A2) is preferably smaller than the amount of the structure that expresses the photoreactivity of the polymer (A1), specifically 0.95? Mol% or less, preferably 0.1? Mol%, more preferably 0.25? To 0.5? Mol%.

It is considered that the use of a polymer having a different amount of a photoreactive structure as a component (A) has the following effects. That is, the orientation property by ultraviolet irradiation is determined by the polymer (polymer (A1)) having a relatively large structure exhibiting photoreactivity. On the other hand, the polymer (polymer (A2)) having a relatively small structure exhibiting photoreactivity but having a relatively large structure exhibiting liquid crystallinity is oriented in accordance with the orientation determined by the polymer (A1). Of the at least two kinds of polymers, each polymer can share its action and effectively exert its action.

<< Weight average molecular weight of each of at least two kinds of polymers as component (A) >>

It is preferable that one of the at least two polymers as the component (A) has a weight average molecular weight of? (? Is 30,000 or more, preferably 30,000 to 300,000, more preferably 40,000 to 200,000, Is in the range of 60,000 to 150,000)

The weight average molecular weight of the other is preferably 0.1 beta to 0.9 beta, preferably 0.2 beta to 0.8 beta, more preferably 0.3 beta to 0.7 beta.

In the present specification, unless otherwise stated, the weight average molecular weight is measured by GPC (Gel Permeation Chromatography).

Particularly, the polymer (A1) having a relatively large amount of the photoreactive structure has a weight average molecular weight of? (? Is 30,000 or more, preferably 30,000 to 300,000, more preferably 40,000 to 20,000 , More preferably from 60,000 to 150,000)

The polymer (A2) having a relatively small amount of a structure exhibiting photoreactivity preferably has a weight average molecular weight of 0.1 beta to 0.9 beta, preferably 0.2 beta to 0.8 beta, more preferably 0.3 beta to 0.7 beta Do.

When the polymer is formed as a liquid crystal alignment film by using at least two kinds of polymers having different weight average molecular weights as the component (A), a polymer having a higher weight average molecular weight is used as a relatively lower layer of the liquid crystal alignment film ), While a polymer having a low weight average molecular weight tends to be formed in a relatively upper layer (relatively far from the substrate) of the liquid crystal alignment film.

By having such a configuration, it is considered that the following actions are exerted.

That is, the polymer (A1) having a relatively large structure exhibiting photoreactivity and having 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 exhibiting photoreactivity and having a low weight average molecular weight is formed in a relatively upper layer (relatively far from the substrate) of the liquid crystal alignment film. In this situation, when a polarized ultraviolet ray is irradiated, a polymer (A1) of a relatively lower layer (a layer relatively close to the substrate) is oriented in accordance with a polarized ultraviolet ray. On the other hand, it is considered that the polymer (A2) relatively in the upper layer (relatively far from the substrate) is oriented in accordance with the orientation of the polymer (A1).

When the total weight of the polymer (A1) and the polymer (A2) is 100 wt%, the proportion of the polymer (A1) is 20 to 95 wt%, preferably 50 to 90 wt%, more preferably 60 to 80 wt% , While the polymer (A2) is preferably a residue thereof.

&Lt; Process for producing each of at least two kinds of polymers as component (A) >

At least two kinds of polymers as the component (A) of the present invention are not particularly limited as long as they have the above-described constitution. For example, the at least two kinds of polymers as the component (A) of the present invention comprise a monomer (M1) having a structure that exhibits (M-1) photoreactive and liquid crystalline properties; And (M-2) a monomer (M2) having a structure which expresses only liquid crystallinity; As shown in Fig. In addition, it can be copolymerized with other monomers within a range that does not inhibit the photoreactive and / or liquid crystalline performance.

As described above, although at least two kinds of polymers as the component (A) of the present invention are formed with the monomer (M1) and the monomer (M2), the total amount of the monomer (M1) and the monomer (M2) , The polymer (A1) among the at least two kinds of polymers is a polymer in which the monomer (M1) accounts for? Mol% (? Is at least 15, preferably from 15 to 100, more preferably from 20 to 80) (M2).

The polymer (A2) is such that the monomer (M1) accounts for 0.95 mol% or less, preferably 0.1 to 0.8 mol%, more preferably 0.25 to 0.5 mol%, and the remainder is the monomer (M2) .

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 preparation method >>

The at least two polymers as the component (A) of the present invention comprise a monomer (M1) having a structure that exhibits the photoreactive and liquid crystallinity; And (M-2) a monomer (M2) having a structure which expresses only liquid crystallinity; , Specifically, by copolymerization.

[Monomer (M1) having a structure exhibiting photoreactive and liquid crystalline properties]

The monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity is a monomer capable of forming a polymer having a structure that exhibits photoreactivity and liquid crystallinity at the side chain portion of the polymer when the polymer is formed .

The following structures and derivatives thereof are preferable as a structure that exhibits photoreactive properties at the side chain sites.

[Chemical Formula 15]

More specific examples of the monomer (M1) include a hydrocarbon such as a hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate,? -Methylene-? -Butyrolactone, styrene, vinyl, maleimide and norbornene A radical polymerizable group, and a siloxane, and a structure that exhibits photoreactive and liquid crystallinity comprising at least one of the above-mentioned formulas (1) to (6), preferably a (7) to (10), a structure exhibiting photoreactivity and liquid crystallinity comprising at least one of the above-mentioned formulas (11) to (13) (14) or (15), a structure that exhibits photoreactive and liquid crystallinity represented by the formula (16) or (17), a structure that expresses the photoreactive and liquid crystalline properties represented by the formula (14) Or (19) A structure exhibiting reactivity and liquid crystallinity, and a structure exhibiting photoreactive and liquid crystallinity expressed by the formula (20).

The monomer (M1) is a monomer having a polymerizable group represented by the following formulas MA1, MA3, MA4, MA5, MA14, MA16 to MA23, MA25, MA28 to MA30, MA32, MA34, MA36, MA38 to MA42, MA44, Wherein the polymerizable group of the compound having a carboxyl group is selected from the group consisting of acrylate, itaconate, fumarate, maleate,? -Methylene-? -Butyrolactone, styrene, vinyl, maleimide, norbornene and siloxane And at least one member selected from compounds substituted with a polymerizable group. In particular, it is preferable that the monomer (M1) has (meth) acrylate as a polymerizable group, and preferably, for example, the end of the side chain is COOH.

MA1 to MA46 can be synthesized as follows.

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

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

MA3 can be synthesized by a synthesis method described in non-patent document (Macromolecules 2002, 35, 706-713).

MA4 can be synthesized by a synthesis method described in patent document (WO2014 / 054785).

MA5 can be synthesized by the synthetic method described in the patent document (Japanese Patent Application Laid-Open No. 2010-18807).

MA6 to MA9 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).

MA10 may be commercially available M6BC (manufactured by Midori Kagaku Co., Ltd.).

MA11 to 13 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).

MA14 to 18 are commercially available, respectively, M4CA, M4BA, M2CA, M3CA, and M5CA (all of which are manufactured by Midori Kagaku Co., Ltd.).

MA19 to 23 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).

The MA24 can be synthesized by a synthesis method described in Non-Patent Document (Polymer Journal, Vol.29, No.4, pp303-308 (1997)).

The MA25 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).

MA26 and MA27 were synthesized by the synthetic method described in non-patent documents (Macromolecules (2012), 45 (21), 8547-8554) and non-patent documents (Liquid Crystals (1995), 19 (4), 433-40) Synthesis can be carried out.

MA28 to 33 can be synthesized by a synthesis method described in Patent Document (WO2014 / 054785).

The MA34-39 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).

MA 40 and 41 can be synthesized by the synthesis method described in the patent document (Japanese Patent Application Laid-Open No. 2009-511431).

The MA42 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).

The MA43 can be synthesized by the synthesis method described in the patent document (WO2012-115129).

The MA44 can be synthesized by the synthesis method described in the patent document (WO2013-133078).

The MA45 can be synthesized by the synthesis method described in the patent document (WO2008-072652).

The MA46 can be synthesized by the synthesis method described in the patent document (WO2014 / 054785).

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Monomer (M2) having a structure exhibiting liquid crystallinity only and method for producing the same]

The monomer (M2) having a structure which expresses only liquid crystallinity refers to a monomer in which the polymer derived from the monomer exhibits liquid crystallinity and the polymer can form a mesogen group at a side chain site.

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

[Chemical Formula 19]

More specific examples of the monomer (M2) having a structure that expresses liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate,? -Methylene-? -Butyrolactone, styrene, (21) to (31), a polymerizable group composed of at least one kind selected from the group consisting of a radical polymerizable group such as maleimide and norbornene, and a siloxane, and a structure having at least one of the above-mentioned formulas Do.

The monomer (M2) is a polymer having a polymerizable group of a compound having a methacrylate as a polymerizable group in the above formulas MA2, MA9 to MA13, MA15, MA24, MA26, MA27, MA31, MA35, MA37, MA43 and MA45, A group consisting of a compound consisting of a compound substituted with a polymerizable group selected from the group consisting of maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, At least one kind selected from the group consisting of In particular, it is preferable that the monomer (M2) has a (meth) acrylate as a polymerizable group, and preferably, for example, the end of the side chain is COOH.

<< Monomer having crosslinkable group (M3) >>

The polymer (A1) and / or the polymer (A2) is a monomer having a crosslinkable group (M-3), specifically, a monomer represented by the following formulas (G-1), (G- 4), more specifically, a monomer having a structure represented by the following formula (0): &quot; (3) &quot; .

[Chemical Formula 20]

[Monomer having a structure represented by formula (0)

More specific examples of the monomer having the structure represented by the formula (0) include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate,? -Methylene-? -Butyrolactone, styrene, (0), and a polymerizable group composed of at least one kind selected from the group consisting of a radical polymerizable group such as amide, 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-hexene, 1,7-octadiene monoepoxide, and the like.

Specific examples of the monomer having thianthrene include those in which the epoxy structure of the monomer having an epoxy group is substituted with thyrenes.

Examples of the monomer having aziridine include, for example, those in which the epoxy structure of the monomer having an epoxy group is substituted with aziridine or 1-methyl aziridine.

Examples of the monomer having an oxetane group include a (meth) acrylate ester having an oxetane group and the like. Examples of such monomers include 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3-ethyl-oxetane , 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (acryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) (Acryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) oxetane, 2- 2- (acryloyloxymethyl) -4-trifluoromethyloxetane is preferable, and 3- (methacryloyloxymethyl) -4-trifluoromethyloxetane and 2- Methyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3-ethyl-oxetane, and the like.

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

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

Above all, a monomer having an epoxy group and an oxetane group are preferable from the viewpoint of availability and the like, and a monomer having an epoxy group is more preferable. Among them, glycidyl (meth) acrylate is preferable in terms of availability.

<< Monomer having nitrogen-containing aromatic heterocyclic group (M4) >>

The polymer (A1) and / or the polymer (A2) may contain, 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; .

The nitrogen-containing aromatic heterocyclic ring is preferably a structure selected from the group consisting of the following formulas [20a], [20b] and [20c] (wherein Z ₂ is a linear or branched alkyl group having 1 to 5 carbon atoms) Is preferably an aromatic cyclic hydrocarbon containing 1, preferably 1 to 4, carbon atoms.

[Chemical Formula 21]

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

Of these, for example, a pyridine ring is preferred.

By having the polymer (A1) or the polymer (A2) have a group selected from nitrogen-containing aromatic heterocyclic group, amide group and urethane group, it is possible to reduce elution of ionic impurities when the polymer composition of the present invention is used as a liquid crystal alignment film In addition, since the cross-linking reaction of the cross-linking group, more specifically, the cross-linking reaction of the group represented by the formula (0) is accelerated, a more durable liquid crystal alignment film can be obtained. In order to prepare a polymer having a group selected from a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group, a monomer (M4) may be copolymerized with the monomer (M1) and the monomer (M2) .

As the monomer (M4), a radical polymerizable group such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate,? -Methylene-? -Butyrolactone, styrene, vinyl, maleimide and norbornene and Siloxane, 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 be substituted or unsubstituted. Examples of the substituent which may be substituted include an alkyl group, a protecting group of an amino group, and a benzyl group.

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

Specific examples of the monomer having an amide group or a urethane group include 2- (4-methylpiperidin-1-ylcarbonylamino) ethyl (meth) acrylate, 4- (Tert-butyloxycarbonyl) piperidin-4-yl ester, 4- (6-methacryloyloxyhexyloxy) benzoic acid 2- (tert- butyloxycarbonyl) Amino) ethyl ester, and the like.

(M4) The monomer (M4) having at least one group selected from the group consisting of a nitrogen-containing aromatic heterocyclic group, an amide group and a urethane group can be obtained by reacting the above-mentioned formulas MA6 to MA8, MA33, The polymerizable group of the methacrylate-containing compound is selected from the group consisting of acrylate, itaconate, fumarate, maleate,? -Methylene-? -Butyrolactone, styrene, vinyl, maleimide, norbornene and siloxane And a compound substituted with a polymerizable group which is a polymerizable group.

As described above, it can be copolymerized with other monomers within a range that does not impair the photoreactive and / or liquid crystalline expression ability.

Other monomers include, for example, industrially available monomers capable of radical polymerization.

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

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

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

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate Butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl methacrylate, Methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- methoxyethyl methacrylate, 2-methoxybutyl methacrylate, 2- 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, and bromostyrene.

Examples of the maleimide compound 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 which is industrially handled can be used. Specifically, a monomer (M1) having a structure that exhibits the above-described photoreactive and liquid crystalline properties; And (M-2) cationic polymerization, radical polymerization, and anionic polymerization using a vinyl group of the monomer (M2) having a structure that expresses only liquid crystallinity. Of these, radical polymerization is particularly preferable from the viewpoints of ease of reaction control and the like.

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

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

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such a radical photo polymerization initiator include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2-methyl-4-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 1-hydroxycyclohexyl phenyl ketone, Benzoquinone, benzanthrone, 2-methyl-1- [4- (4-methylpiperidin-1-ylmethoxy) (Methylthio) phenyl] -2-morpholinopropane-1-one, ethyl 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Di (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 2,4 , 6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) - (Trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis Bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)] - Bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) (P-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- Mercapto benzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl- (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2, 2'-bis (2,4-dichloro Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4' -Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl- (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1 (3-methyl-2-morpholinopropionyl) carbazole, (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium , 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, Di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) Benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2- (3-methyl- 2-ylidene) -1-naphthalen-2-yl-ethanone, or 2- (3- -1,3-benzothiazol -2 (3H) - ylidene) -1- (2-benzoyl and the like) ethanone. These compounds may be used alone or in combination of two or more.

The radical polymerization method is not particularly limited, and examples thereof include an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, a bulk polymerization method and a solution polymerization method.

A monomer (M1) having a structure that exhibits photoreactivity and liquid crystallinity; And (M-2) the monomer (M2) having a structure which expresses only liquid crystallinity to obtain each of the at least two kinds of polymers of the present invention is not particularly limited as long as the resulting polymer dissolves It is not limited. Specific examples thereof are given below.

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, But are not limited to, pyridine, dimethyl sulfone, hexamethyl sulfoxide,? -Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, Ketones, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol mono Butyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol mono 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, An organic solvent such as methanol, ethanol, propanol, isopropanol, butanol, isopropanol, butanol, isobutanol, isobutanol, isobutanol, , Propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, Methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3- Methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylacetamide, propyl methoxypropionate, butyl 3-methoxypropionate, diglyme, Dimethyl propanamide, 3-butoxy-N, N-dimethylpropanamide, and the like.

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

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

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

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

[Recovery of Polymer]

When the produced polymer is recovered from the reaction solution obtained by the above-described reaction, the reaction solution may be put into a poor solvent and the polymer may be precipitated. Examples of the poor solvent used in the precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, . The polymer precipitated by charging into a poor solvent can be recovered by filtration and then dried at room temperature or under reduced pressure or under normal pressure. In addition, when the polymer precipitated and recovered is redissolved in an organic solvent and the operation of reprecipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and when three or more poor solvents selected from these are used, the purification efficiency is further improved, which is preferable.

<< Component (B) >>

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

In the second embodiment of the present invention, the polymer composition used in the present invention is obtained by polymerizing a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound as a component (B) Lt; RTI ID = 0.0 &gt; polyurea &lt; / RTI &gt; polyimide.

<<< Diisocyanate Ingredients >>>

Examples of the diisocyanate component as the raw material of the component (B) include aromatic diisocyanates and aliphatic diisocyanates. Preferred diisocyanate components are aromatic diisocyanates, aliphatic diisocyanates.

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

Specific examples of the aromatic diisocyanate include o-phenylenediisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, toluene diisocyanates (for example, 2,4-diisocyanate tolylene), 1,4 Diisocyanate-2-methoxybenzene, 2,5-diisocyanate xylene, 2,2'-bis (phenyl 4-diisocyanate) propane, 4,4'-diisocyanate diphenylmethane, 4 , 4'-diisocyanate diphenyl ether, 4,4'-diisocyanate 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, tetramethylethylene diisocyanate, and the like. The aliphatic diisocyanate is preferably isophorone diisocyanate. Among them, isophorone diisocyanate and tolylene 2,4-diisocyanate are preferred from the viewpoints of polymerization reactivity and voltage holding ratio, and isophorone diisocyanate is more preferable from the viewpoints of availability, polymerization reactivity, and voltage holding ratio .

<< Tetracarboxylic acid derivatives >>

As the tetracarboxylic acid derivative as a raw material of the component (B), for example, the following tetracarboxylic acid dianhydride can be mentioned.

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

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

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

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

Specific examples thereof are given below.

Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester , 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl Ester, 1,2,3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid Dicarboxy-1-cyclohexylsuccinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dialkyl ester, 1,2, 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, Ester, 3 , 3 ', 4,4'-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentyl acetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5-diene -1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 ^2,5 ] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7,8-di alkyl esters, cycloalkyl hexahydro ^{[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-naphthalenesuccinic dianhydride, and the like.

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

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

These tetracarboxylic acid dianhydrides, tetracarboxylic acid diesters and tetracarboxylic acid dicarboxylic acid diesters can be used either individually or in combination of two or more types, depending on the properties such as liquid crystal alignability, voltage holding characteristics, Type or more.

<<< Diamine Ingredients >>>

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

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

Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 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'-diaminostilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfide, 4,4'- Diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis Phenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,5-bis Bis (4-aminophenoxy) methyl] propane, 2,2-bis [4- (4-aminophenoxy) benzene, Bis [4- (4-aminophenoxy) phenyl] propane, bis [4- Bis (4-aminophenyl) phenyl] sulfone, 1,1-bis (4-aminophenyl) cyclohexane, 4-aminophenyl) fluorene, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- , 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrrene, 1,6-diamino Pyrene, 1,8-diaminopyrene, 2,7-diaminofluorene, 1,3-bis (4-aminophenyl) tetramethyldisiloxane, benzidine, 2,2'-dimethylbenzidine, (4-aminophenyl) ethane, 1,3-bis (4-amyl Bis (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) hexane, 1,7-bis (4-aminophenyl) decane, 1,8-bis (4-aminophenyl) octane, 1,9- Bis (4-aminophenoxy) butane, 1, 5-bis (4-aminophenoxy) Bis (4-aminophenoxy) pentane, 1,8-bis (4-aminophenoxy) pentane, (4-aminophenoxy) decane, di (4-aminophenyl) propane-1,3-dioate, di (4-aminophenoxy) decane, Di (4-aminophenyl) hexane-1,6-dioate, di (4-aminophenyl) Phenyl) heptane-1,7-dioate, di (4-aminophenyl) octane-1,8-dioate, di 1,1-dioate, 1,3-bis [4- (4-aminophenoxy) phenoxy] propane, 1,4 Bis [4- (4-aminophenoxy) phenoxy] pentane, 1,6-bis [4- (4-aminophenoxy) phenoxy] butane, Bis [4- (4-aminophenoxy) phenoxy] heptane, 1,8-bis [4- Bis [4- (4-aminophenoxy) phenoxy] decane, and 1,10-bis [4- (4-aminophenoxy) phenoxy] decane.

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

[Chemical Formula 22]

In the formula, Ar represents a benzene ring or a naphthalene ring, R ₁ is an alkylene group having 1 to 5 carbon atoms, and R ₂ is a hydrogen atom or a methyl group.

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

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

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

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

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

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

(23)

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

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

Further, as the diamine component in the component (B), a diaminosiloxane represented by the following formula (wherein m is an integer of 1 to 10) can be exemplified.

&Lt; EMI ID =

When the diamine compound further has a nitrogen atom in the middle of the two amino groups, the nitrogen atom present in the middle of the two amino groups may be bonded to carbonyl or may be bonded to two or more benzene rings as a single bond Is preferable because it can prevent salt formation with the component (A).

The preferred diamine component as a raw material for the component (B) is, for example, a diamine having a structure represented by the following formula (Y2-1).

(25)

Formula (Y2-1) of the, Z ₃ is an ether bond, a bond portion of the ester bond, an amide bond and a urea bond and an alkylene group of 1 to 20 carbon atoms which may be interrupted in the combination is selected from, Z ₃ and the benzene ring are single A 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).

(26)

In the formula (Y2-7) and (Y2-8), R ₁₃ is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, since the number of carbon atoms is too large to degrade the liquid crystal alignment property, a hydrogen atom, a methyl group or an ethyl group desirable.

In terms of liquid crystal alignment, roneun Y _2, formula (Y2-2), (Y2-3), (Y2-5) is preferable, and the formula (Y2-2), or a group represented by the formula (Y2-5) are particularly preferred .

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

Examples of such diamines include 4,4'-diaminodiphenylmethane, 1,2-bis (4-aminophenyl) ethane, 1,3-bis Bis (4-aminophenyl) hexane, 1,7-bis (4-aminophenyl) heptane, 1,8-bis 4-aminophenyl) octane, 1,9-bis (4-aminophenyl) Bis (4-aminophenoxy) pentane, 1, 1-bis (4-aminophenoxy) Bis (4-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) (4-aminophenyl) propane-1,3-dioate, di (4-aminophenyl) butane-1,4-dioate Di (4-aminophenyl) pentane-1,5-dioate, di (4-aminophenyl) hexane- Di (4-aminophenyl) heptane-1,7-dioate, di (4-aminophenyl) octane-1,8- (4-aminophenoxy) phenoxy] propane, 1,4-bis [4- (4-aminophenoxy) Phenoxy] pentane, 1,6-bis [4- (4-aminophenoxy) phenoxy] hexane, 1,7-bis Bis [4- (4-aminophenoxy) phenoxy] heptane, 1,8-bis [4- Phenoxy] decane, N, N'-bis (4-aminophenethyl) urea, and the like.

 (Y2-1) in the polymer of the component (B) is preferably from 15 to 90 mol%, more preferably from 40 to 85 mol%, based on the total structural units derived from the diamine More preferable.

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

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

A known synthetic method may be used to obtain the polymer of component (B) by polymerization reaction of at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative of each raw material with a diamine component. Generally, it is a method of reacting at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative with a diamine component in an organic solvent. The reaction of at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative with a diamine component is advantageous in that it proceeds comparatively easily in an organic solvent and does not produce any by-products.

The organic solvent used for the reaction of at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative with a diamine component is not particularly limited as long as the resulting polymer dissolves.

Specific examples thereof are given below.

Examples of the organic solvent usable herein include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N- Dimethyl sulfoxide, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone,? -Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, But are not limited to, methyl ethyl 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 monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethyl Diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethylisobutyl ether, diisobutylene Butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, Ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate , Propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3- Methoxypropyl methacrylate, propyl methoxy propionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3- -Dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, and the like. These may be used alone or in combination. The solvent may be a solvent that does not dissolve the polyurea, and may be used in combination with the solvent within the range that the produced polymer (B) is not precipitated.

In addition, since moisture in the organic solvent causes the polymerization reaction to be inhibited, it is preferable to use an organic solvent that is dehydrated and dried as much as possible.

In the reaction of at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative with a diamine component in an organic solvent, a solution prepared by dispersing or dissolving a diamine component in an organic solvent is stirred, and a diisocyanate component and a tetracarboxylic acid derivative Or a method of dispersing or dissolving at least one selected from the group consisting of a diisocyanate component and a tetracarboxylic acid derivative in an organic solvent or a method in which a diamine component is added 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 A method of adding at least one kind selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine component alternatively, and any of these methods may be used. When at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative or a diamine component is composed of a plurality of compounds, they may be reacted in a preliminarily mixed state, or they may be sequentially reacted individually, May be mixed and reacted to form a high molecular weight material.

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

In the polymerization of the polymer as the component (B), the ratio of the total number of moles of at least one member selected from the diisocyanate component and the tetracarboxylic acid derivative to the total number of moles of the diamine component is preferably 0.8 to 1.2. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polymer.

In the case of recovering the resulting polymer from the reaction solution of the polymer as the component (B), the reaction solution may be put into a poor solvent and precipitated. Examples of poor solvents to be used in the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by pouring into a poor solvent can be recovered by filtration and then dried at normal temperature or under reduced pressure or by heating. In addition, by repeating the operation of redissolving the polymer recovered and recovered in the organic solvent and re-precipitating and recovering the polymer solution 2 to 10 times, impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and when three or more poor solvents selected from these are used, the purification efficiency is further improved, which is preferable.

Among such polymers as the component (B), the polyurea is a compound represented by the following formula [1] wherein A ₁ is a divalent organic group, A ₂ is a divalent organic group, and C ₁ And C ₂ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, which may be the same or different)

Is a polymer having a repeating unit represented by the following formula

(27)

In the above formula [1], each of A ₁ and A ₂ may be a single kind and a polymer having the same repeating unit, or a polymer having repeating units having a structure in which plural kinds of A ₁ or A ₂ are highly different.

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 component exemplified above. As A ₂ , a group derived from the preferred diamine component exemplified above is preferable.

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

(28)

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; each of C ₁ to C ₂ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, And an alkynyl group having 2 to 10 carbon atoms.

Specific examples of the alkyl group for R ₁₁ include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s- . From the viewpoint of easiness 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 formula [1] and a repeating unit represented by the formula [2].

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

The polyurea polyimide is obtained by ring closure of the above polyurea polyamic acid or polyurea polyamic acid ester. The closed rate (also referred to as the imidization rate) of the amide acid group is not necessarily 100%, and can be arbitrarily adjusted depending on the purpose and purpose.

As a method of imidizing a polyurea polyamic acid or a polyurea polyamic acid ester, a method of imidizing a solution of a polyimide precursor as it is, or a catalyst in which a catalyst is added to a solution of a polyurea polyamic acid or a polyurea polyamic acid ester Imitation can be heard.

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

The catalyst imidation of a polyurea polyamic acid or a polyurea polyamic acid ester is carried out by adding a basic catalyst and an acid anhydride to a solution of a polyurea polyamic acid or a polyurea polyamic acid ester and heating the solution at a temperature of -20 DEG C to 250 DEG C, Deg.] C to 180 [deg.] C. The amount of the basic catalyst is 0.5 to 30 times, preferably 2 to 20 times the amount of the amide group, and the amount of the acid anhydride is 1 to 50 times, preferably 3 to 30 times the amount of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Of these, pyridine is preferred because it has an appropriate basicity for promoting the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Of these, the use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

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

According to a preferred embodiment of the present invention, in the polymer composition according to the present invention, the blending ratio (by mass) of the above-mentioned components (A) and (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 in the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent dissolving the resin component. Specific examples thereof are given below.

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

[Preparation of polymer composition]

The polymer composition used in the present invention is preferably prepared as a coating liquid so as to be suitable for forming a liquid crystal alignment film. That is, it is preferable that the polymer composition used in the present invention is prepared as a solution in which a resin component for forming a resin coating is dissolved in an organic solvent. Here, the resin component is at least one resin selected from the group consisting of (A) at least two kinds of polymers having a structure exhibiting photoreactivity and a structure exhibiting liquid crystallinity, and (B) a diisocyanate component and a tetracarboxylic acid derivative At least one of which is a resin component containing a polymer produced by using a diamine compound. At that time, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and particularly preferably 1% by mass to 10% by mass.

In the polymer composition of the present embodiment, all of the above-mentioned resin components may be the above-described components (A) and (B), but other polymers other than those described above may be added within the range that does not impair the liquid crystal- Or may be mixed. At that time, the content of the other polymer in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.

Such another polymer includes, for example, a polymer which is composed of poly (meth) acrylate or the like and does not exhibit a structure exhibiting photoreactivity and a structure exhibiting liquid crystallinity.

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

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

Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl But are not limited to, carbitol acetate, carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, 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 monopro Methyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Propyl ether, dihexyl ether, 1-hexanol, n-pentane, n-pentane, n-octane, diethyl ether , Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, Methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-ethoxy-2-propanol, Propoxy Propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, And a solvent having a low surface tension such as 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, .

These poor solvents may be used alone or in combination. When the above-described solvent is used, it is preferably 5% by mass to 80% by mass, more preferably 20% by mass or less, of the entire solvent so as not to significantly decrease the solubility of the entire solvent contained in the polymer composition. To 60% by mass.

Examples of the compound that improves film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent.

More specifically, for example, EFTA (registered trademark) 301, EF303, EF352 (manufactured by Tohchem Products), Megapack (registered trademark) F171, F173, R-30 SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seiyaku Chemical Co., Ltd.), FC431 (manufactured by Sumitomo 3M Company), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Co., ) And the like. The use ratio of these surfactants is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass based on 100 parts by mass of the resin component contained in the polymer composition.

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

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, and the like.

In addition to the improvement of the adhesion between the substrate and the liquid crystal alignment film, in order to prevent deterioration of the electric characteristics due to the backlight when the liquid crystal display device is constituted, additives such as phenolplast or epoxy group- . Specific phenoplast-based additives are shown below, but are not limited to these structures.

[Chemical Formula 29]

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, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 Tetraglycidyl-2,4-hexanediol, N, N, N ', N', -tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N', -tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

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

As an additive, a photosensitizer may be used. Colorless sensitizer and triplet sensitizer are preferable.

Examples of the photosensitizer include an aromatic nitro compound, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscumarin, aromatic 2- Substituted aromatic 2-hydroxy ketones (2-hydroxybenzophenone, mono- or di- p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, (2-benzoylmethylene-3-methyl-? -Naphthothiazoline, 2- (? -Naphthoylmethylene) -3-methylbenzothiazoline, 2- 2- (4-biphenoylmethylene) -3-methylbenzothiazoline, 2- (? -Naphthoylmethylene) -3-methyl-? -Naphthothiazoline, 2- ) -3-methyl- beta -naphthothiazoline, 2- (p-fluorobenzoylmethylene) -3-methyl- beta -naphthothiazoline), oxazoline (2-benzoylmethylene- Oxazoline, 2- (? -Naphthoylmethylene) -3 2- (4-biphenoylmethylene) -3-methylbenzooxazoline, 2- (? -Naphthoylmethylene) -3-methylbenzooxazoline, 2- 3-methyl-β-naphthoxazoline, 2- (4-biphenoylmethylene) -3-methyl- Nitro-aniline, 2,4,6-trinitroaniline) or nitroascenaphthene (5-nitroceaphthene), (2 - [(m-hydroxy- Benzotriazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalene methanol, 2- 9-anthracene methanol, and 9-anthracenecarboxylic acid), benzopyran, azoindolizine, methylcoumarin, and the like.

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

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

<Liquid Crystal Aligner>

The present invention relates to a liquid crystal aligning agent having the above-mentioned polymer composition, or essentially consisting of the above-mentioned polymer composition, or comprising only the polymer composition described above, particularly for a liquid crystal display element, more particularly a transversely driven liquid crystal display element A liquid crystal aligning agent for a liquid crystal display device.

&Lt; Liquid crystal alignment film > < Substrate having liquid crystal alignment film &

The present invention provides a liquid crystal alignment film formed of the above-described liquid crystal aligning agent, particularly a liquid crystal alignment film for a liquid crystal display element, more particularly a liquid crystal alignment film for a transverse electric field driving type liquid crystal display element.

It is another object of the present invention to provide a liquid crystal alignment film formed by the above-described liquid crystal aligning agent, particularly a substrate having a liquid crystal alignment film for a liquid crystal display element, more particularly a liquid crystal display element of a transverse electric field driving type, Type liquid crystal display element.

&Lt; Process for producing liquid crystal alignment film > < Process for producing substrate having liquid crystal alignment film &

In the liquid crystal alignment film described above,

[I] a step of coating the above-mentioned polymer composition or the above-described liquid crystal aligning agent on a substrate, for example, a substrate having a conductive film for driving a transversal electric field to form a coated film;

[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; And

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

It is possible to obtain a liquid crystal alignment film having a controllability of orientation, particularly a liquid crystal alignment film for a liquid crystal display element, more particularly a liquid crystal display element of a transverse electric field driving type, or a substrate having the liquid crystal alignment film.

<< Substrate >>

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

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

<< Conductive film for driving a transverse electric field >>

When the substrate is used in a transverse electric field driving type liquid crystal display element, the substrate has a conductive film for driving the transverse electric field.

When the liquid crystal display element is a transmissive type, ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide) may be used as the conductive film, but the present invention is not limited thereto.

In the case of a reflective liquid crystal display element, the conductive film may be a material that reflects light such as aluminum, but is not limited thereto.

As a method of forming a conductive film on a substrate, conventionally known techniques may be used.

<< Process [I] >>

In the step (I), on a substrate having a conductive film for transversal electric field drive, a layer having a structure that exhibits liquid crystallinity in a predetermined temperature range, a structure that exhibits photoreactive properties of the present invention (A) At least two polymers; (B) a polymer produced by using at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative and a diamine compound; And (C) an organic solvent is applied to form a coating film. Here, the liquid crystal phase expression temperature of the polymer of the component (A) refers to the temperature at which at least two kinds of polymers of the component (A) express the liquid crystal phase as a whole.

The method of applying the above-described polymer composition or the above-mentioned liquid crystal aligning agent onto a substrate having a conductive film for transversal electric field driving is not particularly limited.

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

After the polymer composition or the liquid crystal aligning agent is applied onto the substrate having the conductive film for transversal electric field driving, it is heated at 50 to 200 占 폚 by heating means such as a hot plate, a heat circulation type oven or an IR 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.

The thickness of the coating film is disadvantageous from the viewpoint of the power consumption of the liquid crystal display element if it is too thick, and the reliability of the liquid crystal display element is deteriorated when it is excessively thin, and is preferably 5 nm to 300 nm, 150 nm.

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

<< Process [II] >>

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

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

<< Process [III] >>

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

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

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 the liquid crystal temperature). In the case of a thin film surface such as a coating film, it is expected that the liquid crystal-forming temperature at the surface of the coating film is lower than the liquid crystal-forming temperature when the polymer of the component (A) of the present invention is observed in bulk. For this reason, it is more preferable that the heating temperature is within the temperature range of the liquid crystal display temperature of the coating film surface. That is, the temperature range of the heating temperature after irradiation with the polarized ultraviolet light is set to a temperature lower by 10 ° C than the lower limit of the temperature range of the liquid crystal molding temperature of the chain polymer to be used as the lower limit and a temperature 10 ° C lower than the upper limit of the liquid crystal temperature range It is preferable that the temperature is in the range of the upper limit. If the heating temperature is lower than the above temperature range, the effect of amplifying the anisotropy due to heat in the coating film tends to become insufficient. If the heating temperature is too high than the above temperature range, the coating film is in an isotropic liquid state (isotropic phase) And in this case, it may become difficult to reorient in one direction by self-organization.

The liquid crystal display temperature is preferably at least the glass transition temperature (Tg) at which the polymer of the component (A) of the present invention or the coating film surface transitions from the solid phase to the liquid crystal phase, and the phase transition from the liquid crystal phase to the isotropic phase (Tiso) below the isotropic phase transition temperature (Tiso).

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

By the above process, the production method of the present invention can realize introduction of anisotropy into the coating film with high efficiency. Then, a substrate having a liquid crystal alignment film adhered thereto can be produced with high efficiency.

<Liquid crystal display element> and <Method of manufacturing liquid crystal display element>

The present invention provides a liquid crystal display element having a substrate having the liquid crystal alignment film obtained as described above, particularly a liquid crystal display element of a transverse electric field driving type.

Specifically, a transverse electric field driven liquid crystal display device can be obtained by preparing a second substrate in addition to the above-obtained substrate (first substrate) having a liquid crystal alignment film.

When a substrate having no conductive film for transversal field driving is used in place of the substrate having a conductive film for driving a transversal electric field, the second substrate is a substrate having a conductive film for driving a transversal electric field . It is preferable that the second substrate has a liquid crystal alignment film in the same manner as the first substrate.

A method of manufacturing a liquid crystal display element, in particular, a transversal electric field driven liquid crystal display element,

[IV] a step of arranging the first and second substrates obtained above so as to oppose each other so that the liquid crystal alignment layers of the first and second substrates are opposed to each other via the liquid crystal, thereby obtaining a liquid crystal display element;

Respectively. This makes it possible to obtain a liquid crystal display element, particularly a transverse electric field driven liquid crystal display element.

&Lt; Process [IV] >

[Step IV] is a step of forming a liquid crystal alignment film (first substrate) having a liquid crystal alignment film on a conductive film for driving a transverse electric field obtained in [III] (Second substrate) is disposed opposite to the liquid crystal alignment layers so that both liquid crystal alignment layers are opposed to each other with liquid crystal interposed therebetween, and a liquid crystal cell is manufactured by a known method to manufacture a transverse electric field driven liquid crystal display element. The steps [I '] to [III'] can be carried out 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 transversal electric field in the step [I]. Since the difference between the steps [I] to [III] and the steps [I '] to [III'] is only the existence of the conductive film described above, the description of the steps [I '] to [III'] is omitted.

In order to prepare a liquid crystal cell or a liquid crystal display device, the first and second substrates described above are prepared, the spacer is scattered on the liquid crystal alignment film of the substrate of the single chamber, the liquid crystal alignment film surface is inward, A method in which a liquid crystal is dropped on the surface of a liquid crystal alignment film on which a spacer is dispersed and a method in which a substrate is bonded and sealed by a method of bonding a substrate of a single- For example. At this time, in the case of manufacturing a transverse electric field driving type liquid crystal display element, it is preferable to use a substrate having electrodes having the same structure as a comb for driving a transverse electric field on one side substrate.

The diameter of the spacer is preferably 1 탆 to 30 탆, more preferably 2 탆 to 10 탆. This spacer diameter determines the distance between a pair of substrates sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.

As described above, the liquid crystal alignment film formed using the polymer composition or the liquid crystal aligning agent, the composition thereof, or the liquid crystal aligning agent of the present invention or the substrate having the alignment film, and the liquid crystal display element formed with the liquid crystal alignment film or substrate, Can be advantageously used for a liquid crystal television having a large screen and a high definition.

Example

MA1 as a monomer having a photoreactive group, MA2 as a monomer having a liquid crystalline 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 the synthetic method described in patent document (WO2011-084546). MA2 was synthesized by the synthetic method described in the patent document (Japanese Patent Application Laid-Open No. 9-118717). In addition, the polymer formed from MA1 as a monomer has photoreactive and liquid crystalline properties, and the polymer formed with MA2 as a monomer has only liquid crystallinity.

The monomer A1 to be copolymerized was synthesized by the synthetic method described in the pamphlet of WO2014 / 054785.

HBAGE (hydroxybutyl acrylate glycidyl ether), which is commercially available, was used.

(30)

<Diisocyanate Component>

ISPDA: Isophorone diisocyanate

&Lt; 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

&Lt; Tetracarboxylic acid dianhydride >

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

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

(Organic solvent)

THF: tetrahydrofuran

NMP: N-ethyl-2-pyrrolidone

BCS: butyl cellosolve

(Polymerization initiator)

AIBN: 2,2'-azobisisobutyronitrile

&Lt; Optical alignment polymer Synthesis Example P1 >

After MA1 (1.66 g: 0.1 mol%) and MA2 (13.79 g: 0.9 mol%) were dissolved in THF (146.42 g) and degassed by diaphragm pump, AIBN (0.82 g) was added and degassed again Respectively. Thereafter, the reaction was carried out at 60 DEG C for 8 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (300 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure to obtain a methacrylate polymer powder P1.

&Lt; Photoinduced polymer synthesis examples P2 to P3 >

Methacrylate polymer powders P2 to P3 were synthesized by the same method as in Photo-alignment Polymer Synthesis Example P1 except that the composition shown in Table 1 was used.

<Polymer Synthesis Example L1>

4.85 g of TDA as a tetracarboxylic acid dianhydride component, 3.67 g of ISPDA as a diisocyanate component, 5.89 g of DDM as a diamine component, 0.35 g of Me-DADPA and 0.25 of Me-4APhA were used, and NMP 85.06 g for 18 hours at room temperature to obtain a solution having a concentration of polyamic acid (L1) of 15 wt%.

&Lt; Polymer Synthesis Example L2 >

4.47 g of TDA as a tetracarboxylic acid dianhydride component, 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, For 18 hours to obtain a solution having a concentration of polyurea (L2) of 15 wt%.

&Lt; Polymer Synthesis Example L3 &

As a diisocyanate component, 7.11 g of ISPDA, 6.45 g of DA-2MG and 1.41 g of Me-DADPA were reacted in 84.84 g of NMP at room temperature for 18 hours to obtain a polyurea (L3) concentration of 15 wt % Solution.

&Lt; Example 1 >

The methacrylate polymer powder P1 (0.11 g) obtained in the photo alignment polymer Synthesis Example P1 and the methacrylate polymer powder P2 (0.25 g) obtained in the photo-alignment polymer Synthesis Example P2 were added to NMP (8.04 g) And dissolved by stirring 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 T1. This polymer solution T1 was used as a liquid crystal aligning agent for forming a liquid crystal alignment film.

&Lt; Example 2 >

The methacrylate polymer powder P1 (0.11 g) obtained in the photo alignment polymer Synthesis Example P1 and the methacrylate polymer powder P2 (0.25 g) obtained in the photo-alignment polymer Synthesis Example P2 were added to NMP (8.04 g) And dissolved by stirring 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. The polymer solution T2 was prepared as a liquid crystal aligning agent for forming a liquid crystal alignment film.

&Lt; Example 3 >

The methacrylate polymer powder P1 (0.11 g) obtained in the photo alignment polymer Synthesis Example P1 and the methacrylate polymer powder P2 (0.25 g) obtained in the photo-alignment polymer Synthesis Example P2 were added to NMP (8.04 g) And dissolved by stirring 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 prepared as a liquid crystal aligning agent for forming a liquid crystal alignment film.

<Control 1>

The methacrylate polymer powder P2 (0.36 g) obtained in Photo-alignment Polymer Synthesis Example P2 was added to NMP (8.04 g) and 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 a liquid crystal aligning agent for forming a liquid crystal alignment film as it is.

<Control 2>

The methacrylate polymer powder P2 (0.36 g) obtained in Photo-alignment Polymer Synthesis Example P2 was added to NMP (8.04 g) and 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 prepared as a liquid crystal aligning agent for forming a liquid crystal alignment film.

<Control 3>

The methacrylate polymer powder P2 (0.36 g) obtained in Photo-alignment Polymer Synthesis Example P2 was added to NMP (8.04 g) and 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 aligning agent for forming a liquid crystal alignment film as it is.

<Control 4>

To methacrylate polymer powder P3 (0.36 g) obtained in Photo-alignment Polymer Synthesis Example P3 was added to NMP (8.04 g) and 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 prepared as a liquid crystal aligning agent for forming a liquid crystal alignment film.

<Control 5>

To methacrylate polymer powder P3 (0.36 g) obtained in Photo-alignment Polymer Synthesis Example P3 was added to NMP (8.04 g) and 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. The polymer solution CT5 was prepared as a liquid crystal aligning agent for forming a liquid crystal alignment film.

<Control 6>

To methacrylate polymer powder P3 (0.36 g) obtained in Photo-alignment Polymer Synthesis Example P3 was added to NMP (8.04 g) and 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 aligning agent for forming a liquid crystal alignment film as it is.

<Control 7>

The methacrylate polymer powder P1 (0.36 g) obtained in the photo alignment polymer Synthesis Example P1 and the methacrylate polymer powder P2 (0.84 g) obtained in the photo-alignment polymer Synthesis Example P2 were added to NMP (12.8 g) And dissolved by stirring for 1 hour. BCS (6.0 g) was added and stirred to obtain a polymer solution CT7. This polymer solution CT7 was used as a liquid crystal aligning agent for forming a liquid crystal alignment film as it is.

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 the wt% thereof, and two kinds of photo alignment polymers for the examples were used The amount of the photo-reactive group in each photo-alignment polymer, the number of the monomer species derived from the "photo-reactive group" and the "liquid-crystalline group" in each photo-alignment polymer and the amount of the photo-reactive group in the monomer, Quot; total photoreactive group amount &quot; in the following Table 2.

The amounts of the "photoreactive groups in each of the photo-alignment polymers" and "total photoreactive groups" in Table 2 can be obtained, for example, as follows.

That is, in the liquid crystal aligning agent T1 of Example 1, the light orienting polymer species P1 and P2 were used, and P1 and P2 were used in an amount of 30 wt% and 70 wt%, respectively. The monomer derived from the &quot; photoreactive group &quot; in the light-orienting polymer species P1 is MA1 as described above. MA2 has only &quot; liquid crystalline phase &quot;. The "amount of photoreactive groups in each photo alignment polymer" is a value in mol% of "photoreactive group" when the sum of "liquid crystalline group" and "photoreactive group" is 100 mol% The amount of the photoreactive group is 100 x {0.1 / (0.1 + 0.9)}, which is 10 mol%. Likewise, the &quot; amount of photo reactive group &quot; in the photo-aligned polymer species P2 is 20 mol%.

The &quot; total photoreactive group amount &quot; in the photo alignment polymer is calculated from the weight ratio of the photo aligned polymer species P1 and P2 and the &quot; photoreactive group amount &quot; in the above photo-aligned polymer species P1 and P2, 0.17 mol% is obtained from + 0.2 mol% x 0.7 (derived from 70 wt% of P2 paper) derived from 30 wt% of paper.

&Lt; Production of liquid crystal cell &

The liquid crystal aligning agent (T1) obtained in Example 1 was filtered with a 0.45 占 퐉 filter, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 70 占 폚 for 90 seconds, Thereby forming a liquid crystal alignment film. Subsequently, ultraviolet rays of 313 nm were irradiated with 5 to 50 mJ / cm 2 through a polarizing plate on the coated film surface, and then heated on a hot plate at 150 캜 for 10 minutes to obtain a substrate with a liquid crystal alignment film attached. Two such substrates having liquid crystal alignment films were prepared, spacers having a size of 6 mu m were provided on the liquid crystal alignment film surface of one of the substrates, and the two substrates were combined in such a manner that their rubbing directions became parallel. Was sealed to prepare an empty cell having a cell gap of 4 탆. A liquid crystal MLC-3019 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a low pressure injection method and the injection port was sealed to obtain a liquid crystal cell in which the liquid crystal was aligned in parallel.

Similarly, liquid crystal aligning agents T2 and T3 obtained in Examples 2 and 3 and liquid crystal aligning agents CT1 to CT7 obtained in Controls 1 to 7 were used to prepare liquid crystal cells.

<Orientation Evaluation>

The liquid crystal cells prepared in Examples 1 to 3 and Controls 1 to 7 were installed between two polarizers arranged so that the polarization axes thereof were orthogonal to each other and the backlight was turned on in a voltage unapplied state so that the brightness of transmitted light was minimized. Was adjusted. The liquid crystal cell is visually confirmed. When the liquid crystal cell was satisfactorily oriented and the flow orientation was not confirmed, it was determined as &quot;? &Quot;, while when the flow orientation was confirmed, it was &quot; DELTA &quot;

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

Using the liquid crystal cell prepared above, a voltage of 5 V was applied for 60 seconds at a temperature of 70 DEG C, and a voltage after 16.67 milliseconds was measured. The degree of voltage maintenance was calculated as a voltage holding ratio (VHR). For the measurement of the voltage holding ratio, a voltage holding ratio measuring apparatus VHR-1 manufactured by Toyo Technica Co., Ltd. was used.

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 "total photoreactive group amount" in the photo-alignment polymer component.

From Table 2, it can be seen that, in Examples 1 to 3, two types of photo-alignment polymers differing in the amount of photoreactive groups are used, and blend with a polyamic acid or a polyurea solution exhibits good alignment properties in a wide range of UV irradiation amount It also shows good VHR.

Specifically, when Examples 1 to 3 and Controls 1 to 3 were compared, it was found that the amounts of both photoreactive groups were almost the same (Examples 1 to 3: 0.17; Control 1 to 3: 0.20) (Derived from HBAGE) and a polymer having a nitrogen-containing aromatic heterocyclic group are used, whereby VHR exhibits values of approximately the same degree. In both cases, however, two kinds (P1 and P2) are used as the polymer species in Example 1, and only one species (P2) is used as the polymer species in Control 1. By this difference, in Example 1, good alignment was observed up to a UV irradiation amount of 30 mJ / cm 2, whereas in Control 1, no alignment was observed at a UV irradiation amount of 30 mJ / cm 2. It can be seen that it exhibits good orientation in the amount of UV irradiation.

(Examples 1 to 3: 0.17; Control 4 to 6: 0.17), but the two kinds of photo-alignment polymer species (P1 and (P3) is used as the photo-alignment polymer species in the control 3. By this difference, in Examples 1 to 3, good alignment properties were confirmed up to a UV irradiation dose of 30 mJ / cm 2, while in Control 1, flow orientation was confirmed at a UV irradiation dose of 30 mJ / cm 2, 4 to 6, it can be seen that it exhibits a good alignment property at a wide range of UV irradiation amount. It can also be seen that the VHR is improved in Examples 1 to 3 as compared with Control 7.

Claims (20)

(A) at least two kinds of polymers having a structure exhibiting photoreactivity and a structure exhibiting liquid crystallinity;
(B) a polymer prepared by using a diamine compound and at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative; And
(C) an organic solvent;
&Lt; / RTI &gt; The method according to claim 1,
Wherein the polymer (A1) of one polymer and the polymer (A2) of the other polymer (A) differ in the amount of the structure that exhibits photoreactivity with respect to each other. 3. The method according to claim 1 or 2,
Wherein each of the at least two polymers (A) has a structure that exhibits photoreactivity and a structure that expresses only liquid crystallinity. 4. The method according to any one of claims 1 to 3,
The structure for expressing the photoreactivity,
The following formulas (1) to (6)
(Wherein, A, B, D are, each independently, a single _{bond, -O-, -CH 2 -, -COO-} , -OCO-, -CONH-, -NH-CO-, -CH = CH-CO -O-, or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;
T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;
Y ₁ represents a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings and alicyclic hydrocarbons having 5 to 8 carbon atoms, or the same or different 2 to 6 And the hydrogen atoms bonded to them are each independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
Y ₂ is a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, Each independently may be substituted with -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or has the same definition as Y ₁ ;
X is a single bond, -COO-, -OCO-, -N═N-, -CH═CH-, -C≡C-, -CH═CH-CO-O-, or -O-CO- CH- and when the number of X's is 2, X's may be the same or different;
Cou is a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonding to them are each independently -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH- A halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
q1 and q2 are one in one and zero in the other;
q3 is 0 or 1;
P and Q are each independently a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof; When X is -CH = CH-CO-O- or -O-CO-CH = CH-, P or Q on the side bonded to -CH = CH- is an aromatic ring, , The P groups may be the same or different, and when Q is 2 or more, the Q groups may be the same or different;
l1 is 0 or 1;
l2 is an integer of 0 to 2;
when l1 and l2 are both 0, when T is a single bond, A also represents a single bond;
When l1 is 1, when T is a single bond, B also represents a single bond;
H and I are each independently selected from divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, and combinations thereof)
Wherein the polymer is at least one of the following structures:
[Chemical Formula 1]

The method according to claim 3 or 4,
The structure expressing only the liquid crystallinity is represented by the following formulas (21) to (31)
(Wherein A and B have the same definitions as above;
Y ₃ is a group selected from the group consisting of monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, nitrogen containing heterocyclic rings, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, Each hydrogen atom may be independently substituted with -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
q1 and q2 are one in one and zero in the other;
m represents an integer of 0 to 2, provided that the sum of all m in the formulas (23) to (24) is 2 or more and the formulas (25) to (26) , The sum of all m is 1 or more, m1, m2 and m3 each independently represent an integer of 1 to 3;
R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, Or an alkyloxy group;
Z ₁ and Z _{2 each} represent a single bond, -CO-, -CH ₂ O-, -CH═N-, or -CF ₂ -).
(2)

6. The method according to any one of claims 2 to 5,
The amount of the structure that exhibits the photoreactivity of the polymer (A1) is preferably in the range of? Mol% (where? Is the molar amount of the polymer (A1)) when the sum of the structure that expresses the photoreactivity and the structure that expresses liquid crystallinity of the polymer 15 or more)
The amount of the structure that exhibits the photoreactivity of the polymer (A2) is preferably in the range of 0.95? Mol% or less when the structure exhibiting the photoreactivity of the polymer (A2) and the structure exhibiting liquid crystallinity are taken as 100 mol% . 7. The method according to any one of claims 2 to 6,
Wherein the weight average molecular weight of the polymer (A1) is? (? Is 30,000 or more) and the weight average molecular weight of the polymer (A2) is 0.1? To 0.9 ?. 8. The method according to any one of claims 1 to 7,
A monomer (M1) having a structure in which at least two kinds of polymers exhibit (M-1) photoreactive and liquid crystalline properties; And (M-2) a monomer (M2) having a structure which expresses only liquid crystallinity; &Lt; / RTI &gt; 9. The method according to any one of claims 6 to 8,
When the total amount of the monomer (M1) and the monomer (M2) is 100 mol%
Wherein the polymer (A1) is formed such that the monomer (M1) is? Mol% (? Is not less than 15) and the monomer (M2)
Wherein the polymer (A2) is formed such that the monomer (M1) is 0.95? Mol% or less and the monomer (M2) remains. 10. The method according to any one of claims 1 to 9,
(B) is a polymer prepared by using at least one member selected from a diisocyanate component and a tetracarboxylic acid derivative and at least two diamine compounds, , 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 of Z ₃ and the benzene ring is a single bond, an ether bond, an ester A bond, a urea bond or an amide bond.
(3)

11. The method according to any one of claims 1 to 10,
Wherein the polymer of component (B) is a polyurea obtained by polymerizing a diisocyanate component and a diamine component. 11. The method according to any one of claims 1 to 10,
Wherein the polymer of component (B) is a polyurea polyimide precursor obtained by polymerizing a diisocyanate component, a tetracarboxylic acid derivative, and a diamine component. 11. The method according to any one of claims 1 to 10,
Wherein the polymer of component (B) is a polyimide precursor obtained by polymerizing a tetracarboxylic acid derivative and a diamine component. A liquid crystal aligning agent containing the polymer composition according to any one of claims 1 to 13. A liquid crystal alignment film formed by the liquid crystal aligning agent according to claim 14. [I] a step of coating the polymer composition according to any one of claims 1 to 13 on a substrate having a conductive film for driving a transverse electric field to form a coated film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; And
[III] a step of heating the coating film obtained in [II];
To obtain a liquid crystal alignment film having an alignment control ability. A substrate having the liquid crystal alignment film according to claim 16. [I] a step of coating the polymer composition according to any one of claims 1 to 13 on a substrate having a conductive film for driving a transverse electric field to form a coated film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; And
[III] a step of heating the coating film obtained in [II];
To obtain a liquid crystal alignment film to which alignment control ability is imparted. A liquid crystal display element having a substrate obtained by the manufacturing method according to claim 18. A step of manufacturing a substrate (first substrate) according to claim 18;
[I '] a step of applying a polymer composition according to any one of claims 1 to 13 on a second substrate to form a coating film;
A step of irradiating the coating film obtained in [II '] [I'] with polarized ultraviolet light;
Heating the coating film obtained in [III '] [II'];
To obtain a liquid crystal alignment film having the alignment control ability, thereby obtaining a second substrate having the liquid crystal alignment film; And
[IV] a step of arranging the first and second substrates so that the liquid crystal alignment layers of the first and second substrates are opposed to each other with the liquid crystal interposed therebetween to obtain a liquid crystal display element;
To obtain a liquid crystal display element.