TW201518361A - Polymer composition and liquid crystal alignment film for in-plane-switching-type liquid crystal display element - Google Patents

Abstract

The present invention addresses the problem of providing a novel polymer composition for obtaining a liquid crystal alignment film for an in-plane-switching-type liquid crystal display element, the polymer composition having excellent image persistence characteristics and imparting alignment control performance with high efficiency, and a liquid crystal alignment film for an in-plane-switching-type liquid crystal display element that uses the polymer composition. The present invention solves the abovementioned problem by a polymer composition containing (A) a photosensitive side-chain macromolecule exhibiting liquid crystal properties in a predetermined temperature range, (B) polyurea, and (C) an organic solvent.

Description

Polymer composition and liquid crystal alignment film for transverse electric field driven liquid crystal display element

The present invention relates to a novel polymer composition, a liquid crystal alignment film for a transverse electric field drive type liquid crystal display device using the same, and a method for producing a substrate having the alignment film. More specifically, it relates to a novel method for producing a liquid crystal display element excellent in baking characteristics.

A liquid crystal display element is known as a display device which is lightweight, thin, and low in power consumption, and has been remarkably developed in recent years for use in large-scale television applications. The liquid crystal display element is configured, for example, by holding one of the electrodes and holding the liquid crystal layer on the transparent substrate. Further, in the liquid crystal display device, the liquid crystal is applied between the substrates so as to have a desired alignment state, and the organic film composed of the organic material is used as the liquid crystal alignment film.

In other words, the constituent members of the liquid crystal alignment film-type liquid crystal display device are formed on a surface in contact with the liquid crystal of the substrate on which the liquid crystal is held, and the liquid crystal alignment is caused to function in a predetermined direction between the substrates. Further, in the liquid crystal alignment film, in addition to the parallel direction of the substrate, for example, the liquid crystal is aligned in a certain direction, and the pre-tilt angle of the liquid crystal is also sought to be controlled. use. In such a liquid crystal alignment film, the ability to modulate the alignment of the liquid crystal (hereinafter referred to as an alignment control function) can be imparted by performing an alignment treatment on the organic film constituting the liquid crystal alignment film.

As a method of aligning the liquid crystal alignment film for imparting an alignment control function, a rubbing method has been known from the past. The rubbing method is an organic film such as polyvinyl alcohol or polyamide or polyimide on a substrate, and the surface is wiped (frictionally) in a certain direction with a cloth such as cotton, nylon or polyester to make a liquid crystal. A method of aligning the rubbing direction (friction direction). This rubbing method is used in the manufacturing process of a conventional liquid crystal display element because it can realize the alignment state of a liquid crystal which is simple and relatively stable. In addition, as the organic film used for the liquid crystal alignment film, a polyimide-based organic film excellent in reliability or electrical properties such as heat resistance is selected.

However, the rubbing method of wiping the surface of the liquid crystal alignment film composed of polyimide or the like has a problem of generating dust or static electricity. Further, in recent years, in order to achieve high definition of the liquid crystal display element or unevenness of the switching active element for the electrode or liquid crystal driving on the substrate, the surface of the liquid crystal alignment film cannot be uniformly wiped with the cloth, and thus uniformity may not be achieved. The alignment of the liquid crystal.

Therefore, as another method of alignment treatment of a liquid crystal alignment film which does not rub, a photo-alignment method is being actively explored.

In the photo-alignment method, there are various methods for forming anisotropy in an organic film constituting a liquid crystal alignment film by linearly polarized or collimated light, and liquid crystal alignment is performed according to anisotropy thereof. .

As the main photo-alignment method, a decomposed photo-alignment is known. law. In this method, for example, the polarized ultraviolet ray is irradiated onto the polyimide film, and anisotropic decomposition is caused by the polarization direction dependence of the ultraviolet absorption of the molecular structure. In addition, the liquid crystal is aligned by the polyimine which remains without being decomposed (for example, see Patent Document 1).

Further, as another photo-alignment method, a photo-alignment type or a photo-isomerization type photo-alignment method is known. In the photocrosslinking type photo-alignment method, for example, polyethylene cinnamate is used, and polarized ultraviolet rays are irradiated to cause a dimerization reaction (crosslinking reaction) in the double bond portions of the two side chains parallel to the polarized light. Further, the liquid crystal is aligned in a direction perpendicular to the polarization direction (see, for example, Non-Patent Document 1). In the photo-alignment method of photoisomerization type, when azobenzene is used in a side chain having a side chain type polymer, the polarized ultraviolet ray is irradiated to cause anisotropic reaction of the azobenzene moiety in the side chain parallel to the polarized light. The liquid crystal is aligned in a direction perpendicular to the polarization direction (see, for example, Non-Patent Document 2).

As described above, the alignment treatment method of the liquid crystal alignment film by the photoalignment method does not require rubbing, so that there is no suspense of dust generation or static electricity. Further, even if the substrate of the liquid crystal display element having the uneven surface is subjected to the alignment treatment, it becomes an alignment treatment method suitable for the liquid crystal alignment film in the industrial production process.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent No. 3893659

[Non-patent literature]

[Non-Patent Document 1] M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992).

[Non-Patent Document 2] K. Ichimura et al., Chem. Rev. 100, 1847 (2000).

As described above, the photo-alignment method is an alignment treatment method for a liquid crystal display element, and has a large advantage since it is not required to be used in the industrial friction method. Further, in comparison with the rubbing method in which the alignment control function is almost constant by friction, the photo-alignment method can change the irradiation amount of the polarized light to regulate the alignment control function. However, in the photo-alignment method, when the alignment control function is the same as that in the case of the rubbing method, it is necessary to irradiate a large amount of the polarized light, and it is impossible to achieve the alignment of the liquid crystal which is stable.

For example, in the decomposition type photo-alignment method described in Patent Document 1, it is necessary to irradiate ultraviolet light from a high-pressure mercury lamp outputting 500 W to a polyimide film for 60 minutes, and therefore, it is necessary to irradiate a large amount of ultraviolet rays for a long period of time. Further, even in the case of the dimerization type or the photoisomerization type photo-alignment method, it is necessary to have a large amount of ultraviolet irradiation of several J (Joules) to several tens of J. Further, in the photo-crosslinking type or the photo-isomerization type photo-alignment method, thermal stability or optical stability of the alignment of the liquid crystal is deteriorated, and when it is a liquid crystal display element, there is a problem of alignment failure or display burning. In particular, in a liquid crystal display device of a lateral electric field drive type, since liquid crystal molecules are switched in-plane, it is easy to cause alignment misalignment of liquid crystal after liquid crystal driving, and display baking due to AC driving becomes a major problem.

As a result, in the light-aligning method, the liquid crystal alignment film or the liquid crystal alignment agent which can impart high alignment control function to the liquid crystal alignment film with high efficiency has been pursued for the realization of the high-efficiency or stable liquid crystal alignment of the alignment treatment.

The present invention provides a novel polymer composition which imparts an alignment control function with high efficiency and excellent in baking characteristics, and which is provided with a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element, and a transverse electric field drive type liquid crystal display element using the same. A liquid crystal alignment film, a substrate having the alignment film, and a lateral electric field drive type liquid crystal display device having the substrate are intended. Further, in the present invention, it is possible to provide a liquid crystal alignment film having an improved voltage holding ratio and a method for producing a substrate having the same, even if it is fired at a low temperature.

The inventors of the present invention have found the following inventions in order to achieve the above problems.

<1> A polymer composition comprising: (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a specific temperature range, (B) a polyurea, and (C) an organic solvent, particularly a transverse electric field A polymer composition for producing a liquid crystal alignment film for a driving type liquid crystal display device.

<2> In the above <1>, the component (A) is a photosensitive side chain which may cause photocrosslinking, photoisomerization, or photo Fries rearrangement.

<3> In the above <1> or <2>, the polyurea of the component (B) may be obtained by polymerizing a diisocyanate component and a diamine component.

<4> In the above <1> or <2>, the polyurea of the component (B) may be a diisocyanate component, a carboxylic acid derivative having two or more carboxylic acid moieties, and/or an anhydride thereof, and a diamine component. The polymerization reaction is carried out.

<5> In the above <3> or <4>, the diisocyanate component may be an aromatic diisocyanate and/or an aliphatic diisocyanate.

<6> The photosensitive component (A) may have any one of the selected ones selected from the group consisting of the following formulas (1) to (6), in any one of the above <1> to <5>. chain.

Wherein A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- Or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be substituted by a halogen group; T is a single bond or a carbon number of 1 to 12 An alkyl group, and the hydrogen atom bonded thereto may be substituted by a halogen group; Y ₁ represents a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms. The selected ring, or the same or different ring of 2 to 6 selected from the substituents, is bonded to the group bonded by the bonding group B, and the hydrogen atoms bonded to the bonding are independently capable of being - 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, and a carbon number 1 to 5 alkyl groups or 1 to 5 carbon alkyl groups; Y ₂ represents a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5-8 The group selected from the group consisting of alicyclic hydrocarbons and combinations thereof may be independently selected from -NO ₂ , -CN, -CH=C(CN) ₂ , -CH= CH-CN, halogen group, carbon number 1~5 Group, or an alkyl group having a carbon number of 1 to 5 (alkyloxy) substituted; R & lt represents a hydroxyl group, an alkoxy group having a carbon number (Alkoxy) 1 ~ 6 of, or Y ₁ represents the same as defined above; X represents a single bond, - COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, the number of X becomes At 2 o'clock, X may be the same or different from each other; Cou represents coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to these may be independently -NO ₂ , -CN, - CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; q1 and q2 are 1 and the other is 0; q3 is 0 or 1; P and Q are independently a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. The selected group of the group; however, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, the bond or the CH of the CH-CH side is an aromatic ring When the number of P is 2 or more, P may be the same or different from each other, and when the number of Q is 2 or more, Qs may be the same or different from each other; l1 is 0 or 1; l2 is an integer of 0 to 2; When both are 0, when A is a single bond, A also represents a single bond; when l1 is 1, when T is a single bond, B Also indicated is a single bond; H and I are each independently selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof.

<7> The photosensitive component of any one selected from the group consisting of the following formulas (7) to (10), wherein the component (A) has any one of the above-mentioned <1> to <5> chain.

In the formula, A, B, D, Y ₁ , X, Y ₂ , and R have the same definitions as above; l represents an integer from 1 to 12; m represents an integer from 0 to 2, and m1 and m2 represent integers from 1 to 3; ;n represents an integer from 0 to 12 (but B is a single bond when n=0).

<8> The photosensitive component (A) may have any one of the selected ones selected from the group consisting of the following formulas (11) to (13). chain.

In the formula, A, X, l, m, m1 and R have the same definitions as described above.

<9> The component (A) may have a photosensitive side chain represented by the following formula (14) or (15), as described in any one of <1> to <5>.

In the formula, A, Y ₁ , l, m1 and m2 have the same definitions as described above.

<10> As in any one of <1> to <5> above, the component (A) may have A photosensitive side chain represented by the following formula (16) or (17).

In the formula, A, X, l and m have the same definitions as described above.

<11> The component (A) may have a photosensitive side chain represented by the following formula (18) or (19), as described in any one of <1> to <5>.

In the formula, A, B, Y ₁ , q1, q2, m1, and m2 have the same definitions as described 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 alkyl group having 1 to 5 carbon atoms. Oxygen.

<12> The component (A) may be one having a photosensitive side chain represented by the following formula (20), in any one of the above <1> to <5>.

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

<13> The liquid crystal side of any one selected from the group consisting of the following formulas (21) to (31), wherein the component (A) is any one of the above-mentioned <1> to <12> chain.

Wherein A and B have the same definitions as defined above; Y ₃ is a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing hetero ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms; The groups selected from the group consisting of these groups may be independently selected from -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or a carbon number of 1 to 5, respectively. Substituted by an alkyloxy group; 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 combination a benzene ring, a furan ring, a nitrogen-containing hetero 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 side of the other 0; l represents an integer from 1 to 12, and m represents an integer from 0 to 2. However, in equations (23) to (24), the total of all m is 2 or more, and in equations (25) to (26), The total of all m is 1 or more, and 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, and a biphenyl ring. a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and an alkyl group or an alkyloxy group; Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-,- CF ₂ -.

<14> A method for producing a substrate having the liquid crystal alignment film, which is subjected to the steps of [I] to [III] to obtain an alignment control function The liquid crystal alignment film for a lateral electric field drive type liquid crystal display device, [I] The composition according to any one of the above <1> to <13> is applied to a substrate having a conductive film for driving a lateral electric field, a step of forming a coating film; [II] a step of irradiating the polarized ultraviolet ray to the coating film obtained in [I]; and [III] a step of heating the coating film obtained in [II].

<15> A substrate comprising a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device produced by the method of the above <14>.

<16> A transverse electric field drive type liquid crystal display element having the substrate of the above <15>.

<17> A method of producing a liquid crystal display device comprising: a step of preparing a substrate (first substrate) of the above <15>; obtaining a second substrate having a liquid crystal alignment film; and [IV] a step of obtaining a lateral electric field-driven liquid crystal display device, wherein the step of obtaining the second substrate having the liquid crystal alignment film is performed by the step of having [I'] to [III'], thereby obtaining a liquid crystal alignment imparting alignment control function a film; [I'] a polymer having (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a specific temperature range, (B) a polyurea, and (C) an organic solvent on the second substrate a step of coating to form a coating film; [II'] a step of irradiating the polarized ultraviolet ray to the coating film obtained by [I']; and [III'] heating the film obtained by [II']; [IV] the liquid crystal of the first and second substrates The alignment film has a step of arranging the first and second substrates facing each other to obtain a liquid crystal display element so that the liquid crystals are opposed to each other.

<18> A transverse electric field drive type liquid crystal display element manufactured by the method of <17> above.

Moreover, the second invention was found as another surface.

<P1> A method for producing a substrate having the liquid crystal alignment film, which comprises a step of [I] to [III], thereby obtaining a liquid crystal alignment film for a lateral electric field-driven liquid crystal display device which imparts an alignment control function, [ I] a polymer composition comprising: (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a specific temperature range, (B) a polyurea, and (C) an organic solvent, which is coated with a transverse electric field drive a step of forming a coating film on the substrate of the conductive film; [II] a step of irradiating the polarized ultraviolet ray to the coating film obtained in [I]; and [III] a step of heating the coating film obtained in [II].

<P2> In the above <P1>, the component (A) may have a photosensitive side chain which causes photocrosslinking, photoisomerization, or photofresh rearrangement.

<P3> In the above <P1> or <P2>, the polyurea of the component (B) can be obtained by polymerizing a diisocyanate component and a diamine component.

<P4> In the above <P3>, the diisocyanate component may be an aromatic diisocyanate and/or an aliphatic diisocyanate.

<P5> The photosensitive component of any one selected from the group consisting of the following formulas (1) to (6), as in any one of the above <P1> to <P4> chain.

Wherein A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- Or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be substituted by a halogen group; T is a single bond or a carbon number of 1 to 12 An alkyl group, and the hydrogen atom bonded thereto may be substituted by a halogen group; Y ₁ represents a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms. The selected ring, or the same or different ring of 2 to 6 selected from the substituents, is bonded to the group bonded by the bonding group B, and the hydrogen atoms bonded to the bonding are independently capable of being - 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, and a carbon number 1 to 5 alkyl groups or 1 to 5 carbon alkyl groups; Y ₂ represents a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5-8 The group selected from the group consisting of alicyclic hydrocarbons and combinations thereof may be independently selected from -NO ₂ , -CN, -CH=C(CN) ₂ , -CH= CH-CN, halogen group, carbon number 1~5 Group, or an alkyl group having a carbon number of 1 to 5 substituted; R & lt represents a hydroxyl group, an alkoxy group having a carbon number of 1 to 6, or Y ₁ represents the same as defined above; X represents a single bond, -COO -, - OCO- , -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-; Cou means coumarin-6-yl or The coumarin-7-yl group and the hydrogen atom bonded thereto may be independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, carbon number 1~ Substituted by an alkyl group of 5 or an alkyloxy group having 1 to 5 carbon atoms; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; and P and Q are each independently a single bond, a divalent benzene ring And a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of the combinations. However, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, the bond or the CH of the CH-CH side is an aromatic ring; H and I are independently 2 a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination selected from the group.

<P6> The component (A) may have a photosensitive side selected from any one of the groups consisting of the following formulas (7) to (10), as in any one of the above <P1> to <P4> chain.

In the formula, A, B, D, Y ₁ , X, Y ₂ , and R have the same definitions as above; l represents an integer from 1 to 12; m represents an integer from 0 to 2, and m1 and m2 represent integers from 1 to 3; ;n represents an integer from 0 to 12 (but B is a single bond when n=0).

<P7> As described in any of <P1>~<P4> above, (A) The fraction may have at least one photosensitive side chain selected from the group consisting of the following formulas (11) to (13).

In the formula, A, X, l, m, m2 and R have the same definitions as described above.

<P8> As the above <P1> to <P4>, the component (A) may have a photosensitive side chain represented by the following formula (14) or (15).

In the formula, A, Y ₁ , X, l, m1 and m2 have the same definitions as described above.

<P9> As the above <P1> to <P4>, the component (A) may have a photosensitive side chain represented by the following formula (16) or (17).

In the formula, A, X, l and m have the same definitions as described above.

<P10> As the above <P1> to <P4>, the component (A) may have a photosensitive side chain represented by the following formula (18) or (19).

In the formula, A, B, Y ₁ , q1, q2, m1, and m2 have the same definitions as described 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 alkyl group having 1 to 5 carbon atoms. Oxygen.

<P11> As the above <P1> to <P4>, the component (A) may be a photosensitive side chain represented by the following formula (20).

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

<P12> The liquid crystal side of any one selected from the group consisting of the following formulas (21) to (31), in any one of the above <P1> to <P11> chain.

In the formula, A, B, q1 and q2 have the same definitions as above; Y ₃ is a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing hetero ring, and an alicyclic ring having a carbon number of 5-8. The selected one of the group consisting of a hydrocarbon and a combination thereof may be independently selected from -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or a carbon number. Substituted by an alkyloxy group of 1 to 5; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a monovalent benzene ring, naphthalene a ring, a biphenyl ring, a furan ring, a nitrogen-containing hetero 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; and 1 represents 1 to 12 In the integers, m represents an integer from 0 to 2. However, in the formulas (25) to (26), the total of all m is 2 or more, and in the formulas (27) to (28), the total 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 hetero ring And an alicyclic hydrocarbon having 5 to 8 carbon atoms, and an alkyl group or an alkyloxy group; Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -.

<P13> A substrate having a structure as described above by <P1> The liquid crystal alignment film for a lateral electric field drive type liquid crystal display element manufactured by any one of <P12>.

<P14> A transverse electric field drive type liquid crystal display element having the substrate of the above <P13>.

<P15> A method for producing a liquid crystal display device comprising: a step of preparing a substrate (first substrate) of the above <P13>; a step of obtaining a second substrate having a liquid crystal alignment film; and [IV] a step of obtaining a lateral electric field-driven liquid crystal display device, wherein the step of obtaining the second substrate having the liquid crystal alignment film is performed by the step of having [I'] to [III'], thereby obtaining a liquid crystal imparting an alignment control function An alignment film; [I'] a polymer containing (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a specific temperature range, (B) polyurea, and (C) an organic solvent on the second substrate a step of coating a composition to form a coating film; [II'] a step of irradiating the polarized ultraviolet ray to the coating film obtained by [I']; and [III'] a step of heating the coating film obtained by [II']; [IV] The liquid crystal display element in which the liquid crystal display elements of the first and second substrates are aligned so that the liquid crystals are opposed to each other, and the first and second substrates are opposed to each other to obtain a liquid crystal display element.

<P16> A transverse electric field drive type liquid crystal display element manufactured by the above <P15>.

<P17> A composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device, which comprises (A) a photosensitive side chain type polymer which exhibits liquid crystallinity in a specific temperature range, (B) polyurea, and (C) Organic solvent.

<P18> In the above <P17>, the polyurea of the component (B) may be obtained by polymerizing a diisocyanate component and a diamine component.

<P19> In the above <P18>, the diisocyanate component may be an aromatic diisocyanate and/or an aliphatic diisocyanate.

According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device and a transverse electric field drive type liquid crystal display device having the substrate, which has an excellent alignment characteristic and is excellent in baking characteristics.

The lateral electric field drive type liquid crystal display element manufactured by the method of the present invention does not impair the display characteristics even if it is continuously driven for a long period of time in order to impart a high efficiency alignment control function.

Further, in the present invention, by providing the polyurea of the component (B) in the polymer composition, it is possible to provide a transverse electric field-driven liquid crystal element having excellent voltage holding ratio even when baked at a low temperature, and Liquid crystal alignment film of the component. That is, according to the present invention, even in the case of low-temperature baking, even a residual solvent (N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone of a high boiling point solvent) can be obtained. The alignment film has a higher voltage holding ratio.

figure 1

1‧‧‧Side chain polymer film

2, 2a‧‧‧ side chain

figure 2

3‧‧‧Side chain polymer film

4, 4a‧‧‧ side chain

image 3

5‧‧‧Side chain polymer film

6, 6a‧‧‧ side chain

Figure 4

7‧‧‧Side chain polymer film

8, 8a‧‧‧ side chain

FIG. 1 is a view schematically showing an example of an anisotropic introduction process of a method for producing a liquid crystal alignment film used in the present invention, in which a crosslinkable organic group is used for a photosensitive side chain, and is introduced. An anisotropic graph of hours.

FIG. 2 is a view schematically showing an example of an anisotropic introduction process of a method for producing a liquid crystal alignment film used in the present invention, in which a crosslinkable organic group is used for a photosensitive side chain, and is introduced. A graph when the anisotropy is large.

FIG. 3 is a view schematically showing an example of an anisotropic introduction process of a method for producing a liquid crystal alignment film used in the present invention, and an organic layer causing Freis rearrangement or anisotropy in a photosensitive side chain. Base, the anisotropy introduced is an hour chart.

[Fig. 4] is a view schematically showing an example of an anisotropic introduction process of a method for producing a liquid crystal alignment film used in the present invention, and an organic layer causing Freis rearrangement or heterogeneity in a photosensitive side chain is used. Base, the graph when the anisotropy introduced is large.

The inventors of the present invention conducted the research and obtained the following findings to complete the present invention.

The polymer composition used in the production method of the present invention has a side chain type polymer which can exhibit liquid crystallinity (hereinafter also referred to as a side) The chain-type polymer) is a film obtained by using the polymer composition, and is a film of a side chain type polymer which can exhibit liquid crystallinity. The coating film does not need to be subjected to rubbing treatment, but is subjected to alignment treatment by polarized light irradiation. Further, after the polarized light irradiation, the step of heating the side chain type polymer film is a coating film (hereinafter also referred to as a liquid crystal alignment film) which imparts an alignment control function. At this time, the slight anisotropy expressed by the polarized light irradiation is a driving force, and the liquid crystalline side chain type polymer itself can be realigned efficiently by self-organization. As a result, a high-efficiency alignment treatment as a liquid crystal alignment film can be realized, and a liquid crystal alignment film imparting a high alignment control function can be obtained.

Further, in the polymer composition of the present invention, polyurea is used as the component (B) in addition to the side chain type polymer of the component (A) and the organic solvent of the component (C). Thereby, even if the voltage holding ratio of the liquid crystal alignment film is greatly increased by low-temperature firing, this is unexpected. In particular, by using a specific person as a polyurea to increase its effect. The present inventors thought that the phenomenon of (A) component and (B) component interacted by the addition of the component (B), and the effect is expected to be drastically improved (still, these systems include The inventors' knowledge of the mechanism of the present invention is not inconsistent with the inventors).

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

<Method for Producing Substrate Having Liquid Crystal Alignment Film> and <Method for Manufacturing Liquid Crystal Display Element>

The method for manufacturing a substrate having a liquid crystal alignment film of the present invention has the steps of [I] to [III], [I] will contain (A) sensitivity to liquid crystallinity in a specific temperature range a polymer composition of a side chain type polymer, (B) polyurea, and (C) an organic solvent, which is applied onto a substrate having a conductive film for driving a transverse electric field to form a coating film; [II] irradiation a step of irradiating ultraviolet light to the coating film obtained in [I]; and [III] a step of heating the coating film obtained in [II].

According to the above steps, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device which imparts an alignment control function can be obtained, and the substrate having the liquid crystal alignment film can be obtained.

Further, in addition to the substrate (first substrate) obtained as described above, a lateral electric field drive type liquid crystal display element can be obtained by preparing the second substrate.

The second substrate is replaced with a substrate having a conductive film for driving a lateral electric field, and a substrate having no conductive film for driving a lateral electric field is used, and the above steps [I] to [III] are used (for use without lateral direction) For the sake of convenience, in the present invention, in the case of the steps [I'] to [III'], a second substrate having a liquid crystal alignment film imparting an alignment control function can be obtained.

The method for producing a lateral electric field drive type liquid crystal display device has the following steps: [IV] The first and second substrates obtained above, and the liquid crystal alignment films of the first and second substrates are opposed to each other through the liquid crystal, and are aligned. The steps of the liquid crystal display element. This allows a lateral electric field driven type Liquid crystal display element.

Hereinafter, each step of [I] to [III] and [IV] which are provided in the production method of the present invention will be described.

<Step [I]>

In the step [I], a polymer composition containing a photosensitive side chain type polymer, a polyurea, and an organic solvent which exhibits liquid crystallinity in a specific temperature range is applied onto a substrate having a conductive film for driving a transverse electric field. To form a coating film.

<Substrate>

The substrate is not particularly limited. However, when the liquid crystal display device to be produced is of a transmissive type, it is preferred to use a substrate having high transparency. In this case, it is not particularly limited, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.

Further, in consideration of the application to the reflective liquid crystal display device, an opaque substrate such as a germanium wafer may be used.

<Conductive film for driving a transverse electric field>

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

In the case where the liquid crystal display device is a transmissive type, the conductive film is ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide), but is not limited thereto.

Moreover, in the case of a reflective liquid crystal display element, as a conductive film, A material that reflects light such as aluminum or the like can be cited, but is not limited thereto.

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

<Polymer composition>

The polymer composition is coated on a substrate having a conductive film for driving a transverse electric field, particularly a conductive film.

The polymer composition used in the production method of the present invention contains (A) a photosensitive side chain type polymer which exhibits liquid crystallinity in a specific temperature range; (B) a polyurea; and (C) an organic solvent.

<<(A) Side chain type polymer>>

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

(A) The side chain type polymer may be subjected to a photoreaction in a wavelength range of from 250 nm to 400 nm, and may exhibit liquid crystallinity in a temperature range of from 100 ° C to 300 ° C.

The (A) side chain type polymer is preferably a photosensitive side chain in which light having a wavelength in the range of 250 nm to 400 nm has a reaction.

The (A) side chain type polymer preferably has a mesogenic group for exhibiting liquid crystallinity in a temperature range of from 100 ° C to 300 ° C.

(A) The side chain type polymer is a side chain having a photosensitive bond in a main chain bond, and can cause a cross-linking reaction, an anisotropy reaction, or a photo Fries rearrangement in the light. The structure of the photosensitive side chain is not particularly limited, but it is desirable to cause cross-linking induction of light. Should be, or the configuration of the light Frey rearrangement, more desirable to cause cross-linking reactions. In this case, even if it is exposed to external pressure such as heat, the alignment control function that is stably realized can be maintained for a long period of time. The structure of the side chain type polymer which can exhibit the liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a rigid mesogen component in the side chain structure. In this case, when the side chain type polymer is used as a liquid crystal alignment film, stable liquid crystal alignment can be obtained.

The structure of the polymer has, for example, a main chain and a side chain bonded thereto, and a side chain thereof has a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenyl benzoate group, an azobenzene group, or the like. a mesogen component and a structure of a photosensitive group bonded to a tip end to undergo a cross-linking reaction or an anisotropic reaction in which light is induced, or a side chain having a main chain and a bond thereto, and a side chain thereof The crystal component is a structure having a phenyl benzoate group which undergoes a light Fress rearrangement reaction.

More specific examples of the structure of the side chain type polymer which can exhibit liquid crystallinity are preferably composed of a hydrocarbon, a (meth) acrylate, an itaconate, a fumarate, a maleate, At least one selected from the group consisting of radically polymerizable groups such as α -methylene-γ-butyrolactone, styrene, vinyl, maleimide, and norbornene, and a group of siloxanes The structure of the main chain and the side chain composed of at least one of the following formulas (1) to (6).

Wherein A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- Or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be substituted by a halogen group; T is a single bond or a carbon number of 1 to 12 An alkyl group, and the hydrogen atom bonded thereto may be substituted by a halogen group; Y ₁ represents a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms. The selected ring, or the same or different ring of 2 to 6 selected from the substituents, is bonded to the group bonded by the bonding group B, and the hydrogen atoms bonded to the bonding are independently capable of being - 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, and a carbon number 1 to 5 alkyl groups or 1 to 5 carbon alkyl groups; Y ₂ represents a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5-8 The group selected from the group consisting of alicyclic hydrocarbons and combinations thereof may be independently selected from -NO ₂ , -CN, -CH=C(CN) ₂ , -CH= CH-CN, halogen group, carbon number 1~5 Group, or an alkyl group having a carbon number of 1 to 5 substituted; R & lt represents a hydroxyl group, an alkoxy group having a carbon number of 1 to 6, or Y ₁ represents the same as defined above; X represents a single bond, -COO -, - OCO- , -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, when the number of X becomes 2, X can be mutually Is the same or different; Cou represents coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to these independently can be independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; q1 and q2 are 1 and the other is 0; q3 is 0 or 1; P and Q are independently a group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof; The selected base; however, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, the bond or the CH on the CH-CH side is an aromatic ring, and the number of P becomes 2 In the above case, P may be the same or different from each other. When the number of Q becomes 2 or more, Qs may be the same or different from each other; l1 is 0 or 1; l2 is an integer of 0 to 2; and 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. I is independently by,,, a furan ring, a pyrrole ring, and combinations of such divalent and H of the benzene ring a naphthalene ring biphenyl ring of the selected group.

The side chain may be at least one photosensitive side chain selected from the group consisting of the following formulas (7) to (10).

In the formula, A, B, D, Y ₁ , X, Y ₂ , and R have the same definitions as above; l represents an integer from 1 to 12; m represents an integer from 0 to 2, and m1 and m2 represent integers from 1 to 3; ;n represents an integer from 0 to 12 (but B is a single bond when n=0).

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

In the formula, A, X, l, m, m1 and R have the same definitions as described above.

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

In the formula, A, Y ₁ , l, m1 and m2 have the same definitions as described above.

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

In the formula, A, X, l and m have the same definitions as described above.

Further, the side chain may be 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 described 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 alkyl group having 1 to 5 carbon atoms. Oxygen.

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

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

Further, the (A) side chain type polymer may have at least one liquid crystal side chain selected from the group consisting of the following formulas (21) to (31).

In the formula, A, B, q1 and q2 have the same definitions as above; Y ₃ is a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing hetero ring, and an alicyclic ring having a carbon number of 5-8. The selected one of the group consisting of a hydrocarbon and a combination thereof may be independently selected from -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or a carbon number. Substituted by an alkyloxy group of 1 to 5; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a monovalent benzene ring, naphthalene a ring, a biphenyl ring, a furan ring, a nitrogen-containing hetero 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; and 1 represents 1 to 12 In the integers, m represents an integer from 0 to 2. However, in the formulas (23) to (24), the total of all m is 2 or more, and in the formulas (25) to (26), the total 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 hetero ring And an alicyclic hydrocarbon having 5 to 8 carbon atoms, and an alkyl group or an alkyloxy group; Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -.

<<Method for producing photosensitive side chain type polymer>>

The above-mentioned side chain type polymer which can exhibit liquid crystallinity can be obtained by polymerizing a photoreactive side chain monomer having the above-mentioned photosensitive side chain and a liquid crystal side chain monomer.

[Photoreactive side chain monomer]

When a photoreactive side chain monomer is a polymer, a monomer having a polymer having a photosensitive side chain can be formed at a side chain portion of the polymer.

The photoreactive group which the side chain has is preferably the following structure and its derivative.

More specific examples of the photoreactive side chain monomer preferably have a hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α -methylene-γ- A polymerizable group composed of at least one selected from the group consisting of a radical polymerizable group such as butyrolactone, styrene, vinyl, maleimide, and decane, and a siloxane, and the above formula The photosensitive side chain formed of at least one of (1) to (6) is preferably a photosensitive side chain composed of at least one of the above formulas (7) to (10), and is represented by the above formula (11). a photosensitive side chain composed of at least one of the above-mentioned (13), a photosensitive side chain represented by the above formula (14) or (15), and a photosensitive side chain represented by the above formula (16) or (17) The photosensitive side chain represented by the above formula (18) or (19) and the structure of the photosensitive side chain represented by the above formula (20).

In the present invention, novel compounds (1) to (11) represented by the following formulas (1) to (11) are provided as photoreactive and/or liquid crystal side chain monomers.

Wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; R ¹⁰ represents Br or CN; S represents an alkylene group having 2 to 10 carbon atoms; and u represents 0 or 1; and Py Represents 2-pyridyl, 3-pyridyl or 4-pyridyl.

Further, in the present invention, as the photoreactive and/or liquid crystal side chain monomer, novel compounds (12) to (17) represented by the following formulas (12) to (17) are provided.

In the formulae (12) to (17), R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; v represents 1 or 2; and u represents 0 or 1 (except, in the formula (12), S represents an alkylene group having 2 to 9 carbon atoms, and in the formula (14), S represents an alkylene group having 1 to 10 carbon atoms.

[Liquid Crystal Side Chain Monomer]

The liquid crystal side chain monomer means a monomer which exhibits liquid crystallinity from a polymer of the monomer, and the polymer can form a mesogenic group at a side chain portion.

The mesogen group which is a side chain has a mesogenic structure, such as biphenyl or phenyl benzoate, and the like, such as benzoic acid, etc., may form a mesogen structure by hydrogen bonding of the side chains. The basis. The mesogenic group which is a side chain is preferably the following structure.

More specific examples of the liquid crystal side chain monomer preferably have a hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α -methylene-γ-butyl A polymerizable group composed of at least one selected from the group consisting of a radical polymerizable group such as a lactone, a styrene, a vinyl group, a maleidene, and a decane, and a siloxane, and the above formula ( The structure of the side chain formed by at least one of 21) to (31).

(A) a side chain type polymer can exhibit liquid crystal properties as described above It is obtained by polymerization of a photoreactive side chain monomer. Further, copolymerization of a photoreactive side chain monomer having no liquid crystallinity and a liquid crystal side chain monomer, or copolymerization of a photoreactive side chain monomer and a liquid crystal side chain monomer exhibiting liquid crystallinity can be achieved. And get it. Further, it is copolymerizable with other monomers within a range that does not impair the performance of liquid crystallinity.

Examples of the other monomer include monomers which are industrially obtainable by radical polymerization.

Specific examples of the other monomer include an unsaturated carboxylic acid, an acrylate compound, a methacrylate compound, a maleimide compound, acrylonitrile, maleic anhydride, a styrene compound, and a vinyl compound.

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

Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, decyl acrylate, decyl methyl acrylate, phenyl acrylate, 2, 2, 2-three. Ethyl fluoroacrylate, tert-butyl acrylate, cyclohexyl acrylate, isodecyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate, 2-ethoxyethyl acrylate, acrylic acid Tetrahydrofurfuryl ester, 3-methoxybutyl 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 methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, decyl methacrylate, and methyl propyl acrylate. Methyl decyl methyl ester, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, A 2-methoxyethyl acrylate, methoxy triethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate Ester, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and methacrylic acid 8 -ethyl-8-tricyclodecyl ester or the like. Glycidyl (meth) acrylate, (3-methyl-3-epoxypropenyl) methyl (meth) acrylate, and (3-ethyl-3- epoxypropenyl) A can also be used. A (meth) acrylate compound having a cyclic ether group such as a (meth) acrylate.

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 maleinimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The method for producing the side chain type polymer of the present embodiment is not particularly limited, and a general method for industrial treatment can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a liquid crystal side chain monomer or a photoreactive side chain monomer. Among these, from the viewpoint of the ease of reaction regulation, etc., Radical Polymerization.

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

The radical thermal polymerization initiator is a compound which generates a radical by heating above a decomposition temperature. Examples of such a radical thermal polymerization initiator include ketone peroxides (methylethyl ketone peroxide, cyclohexanone peroxide, etc.), and dioxins peroxide (peroxide, benzoyl peroxide). Etc.), hydrogen peroxide (hydrogen peroxide, tert-butyl hydroperoxide, anisidine hydrogen peroxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dioxygen peroxide) Propylene, dilaurate, etc., peroxy ketal (dibutylperoxycyclohexane, etc.), alkyl perester (perester) (peroxidic neodecanoate-tert-butyl ester, Peroxy pivalic acid-tert-butyl ester, 2-ethylcyclohexanecarboxylic acid-tert-pentyl ester, etc., persulfate (potassium persulfate, sodium persulfate, persulfate) ammonium, etc.), azo compound (azobisisobutyronitrile, and 2,2 '- bis (2-hydroxyethyl) azobisisobutyronitrile, etc.). One type of the radical thermal polymerization initiator 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 which is initiated by radical polymerization by light irradiation. As such a radical photopolymerization initiator, benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, ketone ketone, thioxanthene may be mentioned. Ketone, isopropyl ketone, 2,4-diethyl thioxanthone, 2-ethyl fluorene (Anthraquinone), acetophenone, 2-hydroxy-2-methylpropionylbenzene, 2-hydroxyl -2-methyl-4'-isopropylpropionylbenzene, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2 , 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzoxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane- 1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,4-dimethylaminobenzoic acid ethyl, 4-dimethyl Isoamyl benzoic acid, 4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tris(t-butylperoxycarbonyl)benzophenone , 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-three Pyrazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxy Styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s- Triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4-[pN,N-bis(ethoxycarbonylmethyl) -2,6-bis(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s- Pyrazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole , 2-(p-dimethylaminostyryl)benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin , 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2-chlorophenyl)-4, 4',5,5'-indole (4-ethoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4', 5,5'-tetraphenyl-1,2'-diimidazole, 2,2'bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2 '-Diimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 3-(2 -methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropanyl)-9-n- Dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole- 1-yl)-phenyl)titanium, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t-hexyl) Peroxycarbonyl)benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3,4'-di(A) Oxycarbonyl)-4,3'-bis(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-di(t-butyl Oxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazolyl-2-ylidene)-1-naphthalen-2-yl-ethanone, or 2-(3-methyl -1,3-Benzothiazole-2(3H)-ylidene-1-(2-benzylidene)ethanone. These compounds may be used singly or in combination of two or more.

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

The organic solvent used for the polymerization reaction of the side chain type polymer which can exhibit the liquid crystallinity is not particularly limited as long as it is a polymer which is formed by dissolution. Specific examples thereof are as follows.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, two Methyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ -butyrolactone, isopropyl alcohol methoxymethylpentanol, dipentene, ethyl amyl ketone , methyl mercapto ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl Cellulolytic acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, Dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate single Propyl ether, 3-methyl-3-methoxybutyl acetate, tripropyl Glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether , diisobutyl ketone, methyl cyclohexane, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, carbonic acid Vinyl ester, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxy Methyl propyl propionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropane Propyl acrylate, butyl 3-methoxypropionate, dimethyl dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropane decylamine 3-ethoxy-N,N-dimethylpropane decylamine, 3-butoxy-N,N-dimethylpropane decylamine, and the like.

These organic solvents may be used singly or in combination. Further, even a solvent which does not dissolve the formed polymer may be used in combination with the above-mentioned organic solvent in the range in which the polymer formed is not precipitated.

Further, in the radical polymerization, the oxygen in the organic solvent is a cause of hindering the polymerization reaction, and the organic solvent is preferably used for degassing to the extent possible.

The polymerization temperature during free radical polymerization can be selected from 30 ° C to 150 ° Any temperature of °C, but preferably in the range of 50 ° C to 100 ° C. Further, although the reaction can be carried out at any concentration, when the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid is too high, so that uniform stirring becomes difficult, and the monomer concentration is relatively high. Preferably, it is 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

In the above-mentioned radical polymerization reaction, when the ratio of the radical polymerization initiator is larger than that of the monomer, the molecular weight of the obtained polymer becomes small, and the molecular weight of the polymer obtained when the amount is small increases, so radicals The ratio of the initiator is preferably from 0.1 mol% to 10 mol% with respect to the monomer which is polymerized. Further, various monomer components, solvents, initiators, and the like may be added during the polymerization.

[Recovery of Polymers]

When the reaction solution of the side chain type polymer which can exhibit liquid crystallinity obtained by the above reaction is recovered, the reaction solution is poured into a weak solvent to precipitate the polymer. Examples of the weak solvent used for the precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and diethyl ether. , methyl ethyl ether, water, and the like. After the weak solvent is added and the precipitated polymer is recovered by filtration, it can be dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, the precipitated polymer is redissolved in an organic solvent and subjected to reprecipitation recovery, and the impurities in the polymer can be reduced by repeating from 2 to 10 times. As a weak solvent at this time, for example, When alcohols, ketones, hydrocarbons, and the like are used, when three or more kinds of weak solvents selected from the above are used, it is preferable because the efficiency of purification can be further improved.

The molecular weight of the (A) side chain type polymer of the present invention is a weight average measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, the handleability at the time of formation of a coating film, and the uniformity of a coating film. The molecular weight is preferably from 2,000 to 1,000,000, more preferably from 5,000 to 100,000.

[Modulation of polymer composition]

The polymer composition used in the present invention is preferably prepared as a coating liquid in such a manner as to be suitable for formation of a liquid crystal alignment film. In other words, the polymer composition used in the present invention is preferably prepared by dissolving a solution of a resin component for forming a resin film in an organic solvent. Here, the resin component is a resin component containing a side chain type polymer which exhibits liquid crystallinity which has been described. In this case, the content of the resin component is preferably from 1% by mass to 20% by mass, more preferably from 3% by mass to 15% by mass, even more preferably from 3% by mass to 10% by mass.

In the polymer composition of the present embodiment, all of the above-mentioned resin components may be the above-mentioned photosensitive side chain type polymer which can exhibit liquid crystallinity, but it does not impair the liquid crystal discovery ability and the photosensitive property. Other polymers than these may be mixed. In this case, the content of the other polymer in the resin component is from 0.5% by mass to 80% by mass, preferably from 1% by mass to 50% by mass.

Such other polymers, for example, poly(meth)acrylic acid It is composed of an ester, polyacrylic acid or polyimine, and is not a polymer of a side chain type polymer which can exhibit liquid crystallinity.

<<(B) component>>

The polymer composition used in the present invention has a polyurea as the component (B). Preferably, the component (B) is a polymer obtained by polymerizing a diisocyanate component and a diamine component.

<<<Diisocyanate component>>>

Examples of the diisocyanate component of the raw material of the component (B) include aromatic diisocyanate and aliphatic diisocyanate. The preferred diisocyanate component is an aromatic diisocyanate or an aliphatic diisocyanate.

Here, the aromatic diisocyanate means that the group of R in the diisocyanate structure (O=C=N-R-N=C=O) is a structure including an aromatic ring. Further, the aliphatic diisocyanate means that the group of R in the isocyanate structure is composed of a cyclic or non-cyclic aliphatic structure.

Specific examples of the aromatic diisocyanate include o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, and toluene diisocyanate (for example, 2,4-diisocyanate) Tolylene, 1,4-diisocyanate-2-methoxybenzene, 2,5-diisocyanate xylene, 2,2'-bis(4-diisocyanate phenyl)propane, 4,4 '-Diisocyanate diphenylmethane, 4,4'-diisocyanate diphenyl ether, 4,4'-diisocyanate diphenylanthracene, 3,3'-diisocyanate diphenylanthracene, 2,2'- Diisocyanate benzophenone and the like. As the aromatic diisocyanate, it is preferably listed 2,4-diisocyanate methylphenyl. Specific examples of the aliphatic diisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, and tetramethylethylene diisocyanate. As the aliphatic diisocyanate, isophorone diisocyanate is preferred. Among them, isophorone diisocyanate and 2,4-diisocyanate methylphenyl are preferred from the viewpoints of polymerization reactivity and voltage retention, and further, isophorone diisocyanate is obtainable and polymerizable. The viewpoint of voltage retention is better.

<<<Diamine composition>>>

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

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, and 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, and 2,5-diamino group. Toluene, 3,5-diaminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chloro Benzene, 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'-di Aminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminostilbene, 4,4'-diaminodi Styrene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diamine Diphenyl hydrazine, 3,3'-diaminodiphenyl fluorene, 4,4'-diaminobenzophenone, 1,3-bis(3-aminophenoxy)benzene, 1, 3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,5-bis(4-aminophenoxy)benzoic acid, 4,4 '-Bis(4-Aminophenoxy)bibenzyl, 2,2-bis[(4-aminophenoxy)methyl]propane, 2,2-bis[4-(4- Phenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl] Bismuth, bis[4-(4-aminophenoxy)phenyl]anthracene, 1,1-bis(4-aminophenyl)cyclohexane, α , α '-bis(4-aminophenyl) )-1,4-diisopropylbenzene, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-dual ( 4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-di Amino naphthalene, 1,5-diamino hydrazine, 1,3-diamino hydrazine, 1,6-diamino hydrazine, 1,8-diamino hydrazine, 2,7-diamino hydrazine, 1,3-bis(4-aminophenyl)tetramethyldioxane, benzidine, 2,2'-dimethylbenzidine, 1,2-bis(4-aminophenyl)ethane , 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,5-bis(4-aminophenyl)pentane, 1, 6-bis(4-aminophenyl)hexane, 1,7-bis(4-aminophenyl)heptane, 1,8-bis(4-aminophenyl)octane, 1,9- Bis(4-aminophenyl)decane, 1,10-bis(4-aminophenyl)decane, 1,3-bis(4-aminophenoxy)propane, 1,4-double ( 4-aminophenoxy)butane, 1,5-bis (4- Aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,8-bis (4) -aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,10-bis(4-aminophenoxy)decane, bis(4-amine Phenyl)propane-1,3-diester, bis(4-aminophenyl)butane-1,4-dicarboxylate, bis(4-aminophenyl)pentane-1,5-di Acid ester, bis(4-aminophenyl)hexane-1,6-diester, bis(4-aminophenyl)heptane-1,7-diester, bis(4-aminobenzene) Octane-1,8-diester, bis(4-aminophenyl)decane-1,9-diester, bis(4-aminophenyl)decane-1,10-di Acid ester, 1,3-bis[4-(4-aminophenoxy)phenoxy]propane, 1,4-bis[4-(4-aminophenoxy)phenoxy]butane, 1,5-bis[4-(4-aminophenoxy)phenoxy]pentane, 1,6-bis[4-(4-aminophenoxy)phenoxy]hexane, 1, 7-bis[4-(4-aminophenoxy)phenoxy]heptane, 1,8-bis[4-(4-aminophenoxy)phenoxy]octane, 1,9- Bis[4-(4-aminophenoxy)phenoxy]decane, 1,10-bis[4-(4-aminophenoxy)phenoxy]decane, and the like.

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

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

Specific examples of the aromatic-aliphatic diamine include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, and 4-amino-N-. Methylbenzylamine, 3-aminophenethylamine, 4-aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenylethylamine, 3- (3-aminopropyl)benzene Amine, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl)aniline, 4-(3-methylaminopropyl)aniline, 3-(4-aminobutyl) Aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4-(4-methylaminobutyl)aniline, 3-(5-amine Benido)aniline, 4-(5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline, 4-(5-methylaminopentyl)aniline, 2-(6 -aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2-(6-aminonaphthyl)ethylamine, 3-(6-aminonaphthyl)ethyl Amines, etc.

Examples of the heterocyclic diamine include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7- Diaminodibenzofuran, 3,6-diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis(4-amine Phenyl)-1,3,4-oxadiazole and the like.

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

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

Further, in the component (B), the diamine component which is subjected to a polymerization reaction with the diisocyanate component may contain a diamine having a side chain for vertical alignment within a range not impairing the effects of the present invention.

Further, the diamine component of the component (B) may further contain the following diamine.

(wherein, m and n are integers from 1 to 11, respectively, m+n is an integer from 2 to 12, h is an integer from 1 to 3, and j is an integer from 0 to 3.)

It is advantageous to further increase the voltage holding ratio (also referred to as VHR) of the liquid crystal display element using the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention by introducing such a diamine. These diamines are preferred from the viewpoint of excellent effect of reducing the cumulative charge of the liquid crystal display element.

In addition, as the diamine component of the component (B), a diamine siloxane such as the following formula may be mentioned.

(where m is an integer from 1 to 10)

The diamine component of the component (B) may be used alone or in combination of two or more kinds depending on the properties of the liquid crystal alignment property, the voltage retention property, and the cumulative charge. The ratio mixed at this time is not limited.

In addition, the molecular weight of the polyurea of the component (B) is the weight average measured by the GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained liquid crystal alignment film, the handleability at the time of formation of the liquid crystal alignment film, and the uniformity of the liquid crystal alignment film. The molecular weight is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 150,000.

In order to obtain the polymer of the above component (B) by a polymerization reaction of a diisocyanate component of a respective raw material with a diamine component, a well-known synthesis method can be used. In general, a method in which a diisocyanate component and a diamine component are reacted in an organic solvent is used. The reaction between the diisocyanate component and the diamine component is relatively easy to carry out in an organic solvent, and is advantageous in that no by-products are produced.

The organic solvent used for the reaction between the diisocyanate component and the diamine component is not particularly limited as long as it is dissolved.

Specific examples thereof are listed below.

Examples of the organic solvent which can be used herein include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone. , N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, γ -butyrolactone, isopropyl alcohol methoxymethylpentanol, dipentene, Ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve B Acid ester, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl Ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol Dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Monoacetate monopropyl ether, 3-methyl-3-methyl Butyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl Butyrate, butyl ether, diisobutyl ketone, methylcyclohexane, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl Ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, pyruvic acid Ethyl ester, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid , 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N - dimethylpropane decylamine, 3-ethoxy-N,N-dimethylpropane decylamine, 3-butoxy-N,N-dimethylpropane decylamine, and the like. These may be used alone or in combination. Further, even if it is a solvent in which the polyurea is not dissolved, it can be used in the above solvent in the range in which the produced polyurea is not precipitated.

Further, since the water in the organic solvent is a cause of hindering the polymerization reaction, it is preferred to use an organic solvent as far as possible to dehydrate it.

In the case where the diisocyanate component and the diamine component are reacted in an organic solvent, a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the diisocyanate component is directly or dispersed or dissolved in an organic solvent. In the method, a method in which a diamine component is added to a solution in which a diisocyanate component is dispersed or dissolved in an organic solvent, a method in which a diisocyanate component and a diamine component are alternately added, and the like may be used, and any of these may be used. Further, when the diisocyanate component or the diamine component is composed of a plurality of compounds, the reaction may be carried out in a state of being mixed in advance, or may be individually reacted in order, or may be separately reacted. A low molecular weight body is a mixture of high molecular weight bodies.

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

In the polymerization of polyurea, the total of diisocyanate components The molar ratio of the molar number and the total amount of the diamine component is preferably 0.8 to 1.2. As with the usual polycondensation reaction, the molecular weight of the polyurea formed by the closer the molar ratio is closer to 1.0 is larger.

When the produced polyurea is recovered from the reaction solution of polyurea, the reaction solution may be poured into a weak solvent to precipitate. Examples of the weak solvent used for the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer which has been precipitated by a weak solvent is recovered by filtration, and then dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, the precipitated polymer is redissolved in an organic solvent and subjected to reprecipitation recovery, and the impurities in the polymer can be reduced by repeating from 2 to 10 times. Examples of the weak solvent in this case include alcohols, ketones, and hydrocarbons. When three or more kinds of weak solvents are selected from among the above, it is preferable to further improve the purification efficiency.

Such a polyurea is, for example, a polymer having a repeating unit represented by the following formula [1].

(In the formula [1], A ₁ is a divalent organic group, A ₂ is a divalent organic group, and C ₁ and C ₂ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, which may be the same or different ).

In the above formula [1], each of A ₁ and A ₂ may be a polymer having the same repeating unit, and A ₁ or A ₂ may be a polymer having a plurality of repeating units of different structures.

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

According to a preferred embodiment of the present invention, as A ₁ , a group derived from the above-exemplified preferred diisocyanate component is preferred. Further, as A ₂ , a group derived from the above-exemplified preferred diamine component is preferred.

Further, although the polyurea used in the present invention is preferably obtained from a diamine and a diisocyanate, it may be used in a small amount together with a diisocyanate such as a tetracarboxylic dianhydride, a tetracarboxylic acid derivative, or a tricarboxylic acid derivative. The compound obtained by reacting a compound having two or more amine groups with a diamine component, such as a dicarboxylic acid derivative, may be included in the present invention without departing from the effects of the present invention.

Here, the compound having a reaction point of two or more amine groups with a diamine component means a carboxylic acid derivative preferably having two or more carboxylic acid moieties which can generate a carboxyl group reactive with an amine group and/or Examples of the anhydride thereof include a tetracarboxylic acid derivative and/or an anhydride thereof, a tricarboxylic acid derivative and/or an anhydride thereof, a dicarboxylic acid derivative, and/or an anhydride thereof. In addition, the carboxylic acid derivative having two or more such carboxylic acid moieties and/or an anhydride thereof may be a carboxylic acid moiety, a carboxylic acid anhydride, a carboxylic acid ester or the like, and examples thereof include, for example, a tetracarboxylic acid Anhydride, a dialkyl tetracarboxylate, a dialkyl tetracarboxylate or the like. Here, when a compound having a reaction point of two or more amine groups with a diamine component is used, the ratio of the compound to the diisocyanate is preferably 99:1~0:100.

The amount of the compound having the reaction point of the amine group having two or more amine groups and the number of moles of the diamine is two or more and the compound of the amine group of the diamine component. The total ratio of the mole numbers of the isocyanate is from 0.8 to 1.2, preferably from about 0.9 to 1.1. As with the usual polycondensation reaction, the molecular weight of the polymer formed as the molar ratio is closer to 1.0 is larger.

Examples of the tetracarboxylic acid derivative and/or its anhydride include the following tetracarboxylic dianhydrides.

Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3. 4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,2 , 4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2, 4,5-pentanetetracarboxylic dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic acid Acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic acid Dihydride, tricyclo[4.2.1.0 ^2,5 ]decane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dianhydride,hexacyclo[6.6.0.1 ^2,7 .0 ^3,6 .1 ^9,14 .0 ^10,13 ]hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dianhydride, 3,4-dicarboxy-1, 2,3,4-hexahydro-1-naphthalene succinic dianhydride or the like.

As the aromatic tetracarboxylic dianhydride, pyromellitic acid Anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyl Tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, double (3, 4-Dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenium anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalene Tetracarboxylic dianhydride and the like.

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

Further, as the tetracarboxylic acid component of the raw material of the component (B), a dicarboxylic acid dialkyl ester or a tetracarboxylic acid dialkyl diester dichloride can be used. Further, when the tetracarboxylic acid component contains such a dialkyl tetracarboxylate or a dialkyl dicarboxylate dichloride, the polymer becomes a polyphthalamide of a polyimide precursor. The dicarboxylic acid dialkyl ester which can be used is not particularly limited, and examples thereof include an aliphatic tetracarboxylic acid diester and an aromatic tetracarboxylic acid dialkyl ester.

Specific examples thereof are listed below.

Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester and 1,2-dimethyl-1,2,3,4-cyclobutylene. Alkanedicarboxylic acid dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2, 3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentane tetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1, Dialkyl 2,4,5-cyclohexanetetracarboxylate, dialkyl 3,4-dicarboxy-1-cyclohexylsuccinate, 3,4-dicarboxy-1,2,3,4-hexahydro Dialkyl 1-naphthylsuccinate, dialkyl 1,2,3,4-butanetetracarboxylate, dialkyl 1,2,4,5-pentanetetracarboxylate, bicyclo[3.3.0] Octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3',4,4'-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentyl acetic acid Dialkyl ester, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.0 ^2,5 ]壬Alkane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dialkyl ester, hexacyclo[6.6.0.1 ^2,7 .0 ^3,6 .1 ^9,14 .0 ^10,13 Hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dialkyl ester, 3,4-dicarboxy-1,2,3,4-hexahydro-1-naphthalene Succinic dianhydride and the like.

Specific examples of the aromatic tetracarboxylic acid dialkyl ester include dialkyl pyromellitate, 3,3',4,4'-biphenyltetracarboxylic acid dialkyl ester, and 2,2',3,3. '-Biphenyltetracarboxylic acid dialkyl ester, 2,3,3',4'-biphenyltetracarboxylic acid dialkyl ester, 3,3',4,4'-benzophenone tetracarboxylic acid dialkyl ester , 2,3,3',4'-dibenzophenone tetracarboxylic acid dialkyl ester, bis(3,4-dicarboxyphenyl)ether dialkyl ester, bis(3,4-dicarboxyphenyl)fluorene Dialkyl ester, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl ester, and the like.

Examples of the tetracarboxylic acid diester dichloride include a diester dichloride in which a carboxyl group of the above-described tetracarboxylic acid dialkyl ester is converted into a chlorocarbonyl group by a known method.

Examples of the alicyclic dicarboxylic acid include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, and 1,2-cyclobutane. Dicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutane II Carboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentane Carboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4 - cyclohexanedicarboxylic acid, 1,4-(2-northene)dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo[2.2.2]octane- 1,4-Dicarboxylic acid, bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-dioxo-1,4-bicyclo[2.2.2]octanedicarboxylic acid, 1, 3-adamantane dicarboxylic acid, 4,8-dioxo-1,3-adamantane dicarboxylic acid, 2,6-spiro[3.3]heptane dicarboxylic acid, 1,3-adamantane diacetic acid, camphor Acid, etc.

Examples of the aromatic dicarboxylic acid include o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butyl isophthalic acid, and 5-amino group. Phthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-nonanedicarboxylic acid, 1,4-nonanedicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4 '-Biphenyldicarboxylic acid, 1,5-biphenylene dicarboxylic acid, 4,4"-terphenylene dicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-di Phenylethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 2,2-diphenylhexafluoropropane-4,4'-dicarboxylic acid, 4,4'-diphenyl ether Dicarboxylic acid, 4,4'-bibenzyldicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 4,4'-Ethynylene Dibenzoic acid, 4, 4'-carbonyl dibenzoic acid, 4,4'-diphenylphosphonium dicarboxylic acid, 4,4'-diphenyl sulfide dicarboxylic acid, p-phenylenediacetic acid, 3,3'-p- Phenyldipropionic acid, 4-carboxycinnamic acid, p-phenylene diacrylate, 3,3'-[4,4'-( Methyl di-p-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxadi-p-phenylphenyl)dipropionic acid, 4,4'-[4,4 '-(Oxygen di-p-phenylene)]dibutyric acid, dicarboxyl of (isopropylidene-p-phenylene dioxy)dibutyric acid, bis(p-carboxyphenyl)dimethylnonane acid.

Examples of the dicarboxylic acid containing a heterocyclic ring include 1,5-(9-oxo (Oxofluorene) dicarboxylic acid, 3,4-furandicarboxylic acid, and 4,5-thiazole dicarboxylic acid. Acid, 2-phenyl-4,5-thiazole dicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylate Acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5 Pyridine dicarboxylic acid and the like.

The various dicarboxylic acids described above may be acid dihalides or anhydrous builders. These dicarboxylic acids, in particular, dicarboxylic acids which can impart a linear structure of polyamine, are preferred because they maintain the alignment of the liquid crystal molecules. Among these, terephthalic acid, isoterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethane are preferably used. Dicarboxylic acid, 4,4'-diphenylethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 2,2- Bis(phenyl)propane dicarboxylic acid, 4,4 yttrium terphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,5-pyridinedicarboxylic acid or the like acid dihalides. Although such isomers are also present in such compounds, they may be mixtures containing such. Further, two or more kinds of compounds may be used in combination. Further, the dicarboxylic acids used in the present invention are not limited to the above-exemplified compounds.

Liquid crystal alignment and voltage retention characteristics of such tetracarboxylic dianhydride, tetracarboxylic acid diester, tetracarboxylic acid diester dichloride, dicarboxylic acid or dicarboxylic acid halide, etc., when used in a liquid crystal alignment film The characteristics of the accumulated electric charge and the like may be one type or two or more types in combination.

The tetracarboxylic dianhydride, the tetracarboxylic acid diester, the tetracarboxylic acid diester dichloride, the dicarboxylic acid or the dicarboxylic acid halide or the like is allowed to coexist with the isocyanate compound and reacted with the diamine component, in order to obtain the present invention. As the polymer of the component (B), a well-known synthetic method can be used. Tetracarboxylic dianhydride A method in which a derivative thereof or a diamine component is reacted in an organic solvent. The reaction between the tetracarboxylic dianhydride and the diamine component is relatively easy to carry out in an organic solvent, and it is advantageous in that no by-products are produced.

According to a preferred embodiment of the present invention, in the polymer composition of the present invention, the total ratio of the components (A) and (B) is the total ratio (mass basis) of the component (A) to the component (B). When it is set to 1, the component (A) is from 0.01 to 0.99, preferably from 0.1 to 0.9, more preferably from 0.2 to 0.5.

<<(C) Organic Solvents>>

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 in which the resin component is dissolved. Specific examples thereof are listed below.

These may, for example, be N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl Pyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethylurea, pyridine, dimethyl hydrazine, hexamethylarylene, γ -butyrolactone, 3-methoxy-N,N-dimethyl Propane amide, 3-ethoxy-N,N-dimethylpropane decylamine, 3-butoxy-N,N-dimethylpropane decylamine, 1,3-dimethyl-imidazolidinone Ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme (Diglyme), 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, Diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate single Ethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methyl Butyl acetate, tripropylene glycol methyl ether. These may be used alone or in combination.

The polymer composition used in the present invention may contain components other than the above components (A), (B) and (C). In the case of applying a polymer composition, a solvent or a compound which improves film thickness uniformity or surface smoothness, a compound which improves the adhesion between the liquid crystal alignment film and the substrate, and the like are not limited thereto. this.

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

Examples thereof include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate. Butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, Propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl Ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetic acid Ester monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl Butyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexane, propyl ether, dihexyl ether, 1-hexyl Alcohol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether , methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid , 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol , 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, Propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, lactate n- A solvent having a low surface tension, such as butyl ester or isoamyl lactate.

These weak solvents may be used singly or in combination of plural kinds. When the solvent is used as described above, the solubility of the entire solvent contained in the polymer composition is not significantly lowered, and it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass based on the total amount of the solvent. quality%.

Examples of the compound which improves the uniformity of the film thickness or the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.

More specifically, for example, Eftop (registered trademark) 301, EF303, EF352 (manufactured by Tohkem Products), MEGAFAC (registered trademark) F171, F173, R-30 (manufactured by DIC Corporation), Fluorad FC430, FC431 (Sumitomo 3M) , AashiGuard (registered trademark) AG710 (made by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimei Chemical Co., Ltd.) Wait. The use ratio of the surfactant is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass, per 100 parts by mass of the resin component contained in the polymer composition.

Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include the following compounds containing a functional decane.

Examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, and N. -(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureido Propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecyl-1,4,7-tri Naloxane, 10-triethoxydecyl-1,4,7-triazinane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-triethoxy Base alkyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethylene)-3-aminopropyltrimethoxy矽, N-bis(oxyethylene)-3-aminopropyl Triethoxy decane and the like.

Further, in addition to improving the adhesion between the substrate and the liquid crystal alignment film, in order to prevent deterioration of electrical characteristics caused by the backlight when the liquid crystal display element is formed, the polymer composition may contain, for example, the following A phenolic plastic (Phenoplast) or an additive containing an epoxy group-containing compound. The specific phenolic plastic additive is shown below, but the structure is not limited thereto.

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

When a compound which improves the adhesion to the substrate is used, the amount thereof is preferably 0.1 parts by mass to 30 parts by mass, more preferably 1 part by mass, per 100 parts by mass of the resin component contained in the polymer composition. 20 parts by mass. When the amount used is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and when it exceeds 30 parts by mass, the alignment of the liquid crystal may be deteriorated.

As the additive, a photosensitizer can also be used. Preferred are colorless sensitizers and triplet sensitizers.

As a photosensitizer, it is an aromatic nitro compound, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy 4-methylcoumarin), coumarinone, Carbonyl dicoumarin, aromatic 2-hydroxyketone, and amino substituted, aromatic 2-hydroxyketone (2-hydroxybenzophenone, mono- or di-p-(dimethylamino)-2 -hydroxybenzophenone), acetophenone, anthracene, xanthone, thioxanthone, benzoxanone, thiazoline (2-benzylidenemethylene-3-methyl-β-naphtho Thiazoline, 2-(β-naphthylmethylene)-3-methylbenzothiazoline, 2-(α-naphthylmethylene)-3-methylbenzothiazoline, 2-(4- Biphenoyl methylene)-3-methylbenzothiazoline, 2-(β-naphthylmethylene)-3-methyl-β-naphthylthiazoline, 2-(4-double Phenolic methylene)-3-methyl-β-naphthylthiazoline, 2-(p-fluorobenzhydrylmethylene)-3-methyl-β-naphthylthiazoline), oxazoline (2-Benzylmercaptomethyl-3-methyl-β-naphthyloxazoline, 2-(β-naphthylmethylene)-3-methylbenzoxazoline, 2-(α -naphthylmethylene)-3-methylbenzoxazoline, 2-(4-bisphenolylmethylene)-3-methylbenzoxazoline, 2-(β-naphthylylene Base)-3- Benzyl-β-naphthyloxazoline, 2-(4-bisphenolylmethylene)-3-methyl-β-naphthyloxazoline, 2-(p-fluorobenzhydrylmethylene) -3-methyl-β-naphthyloxazoline), Benzothiazole, Nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroguanidine Acenaphthene (5-nitroguanidine), (2-[(m-hydroxy-p-methoxy)styryl]benzothiazole, benzoin alkyl ether, N-alkylated hydrazine , acetophenone ketal (2,2-dimethoxyphenyl ethyl ketone), naphthalene, anthracene (2-naphthalene methanol, 2-naphthalenecarboxylic acid, 9-fluorene methanol, and 9-fluorene carboxylic acid), benzene Pyran and azoazine (Azoindolizine), furocoumarin (Furocoumarin), and the like.

Preferred are aromatic 2-hydroxyketone (benzophenone), coumarin, coumarinone, carbonyl dicoumarin, acetophenone, anthracene, xanthone, thioxanthone, and acetophenone. Ketal.

In the polymer composition, in addition to the above, in order to prevent the effects of the present invention from being affected, the dielectric characteristics of the liquid crystal alignment film, such as dielectric constant or conductivity, are changed for the purpose of improving the dielectric or conductive substance. Further, for the purpose of improving the hardness or density of the film when the liquid crystal alignment film is formed, a crosslinkable compound can be added.

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

The coating method is generally a method which is industrially carried out by screen printing, lithography, flexographic printing or ink jet printing. As another coating method, there are a dipping method, a roll coating method, a slit coating method, a spinning method (rotary coating method), a spray coating method, and the like, and these can be used depending on the purpose.

After coating the polymer composition on the substrate having the conductive film for driving the transverse electric field, it may be heated at 50 to 200 ° C by a heating means such as a hot plate, a heat cycle type oven or an IR (infrared) type oven, preferably The solvent was 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 of the side chain type polymer.

When the thickness of the coating film is too thick, the power consuming surface of the liquid crystal display element becomes unfavorable. When the film thickness is too thin, the reliability of the liquid crystal display element is lowered. Therefore, it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. .

Further, after the step [I], the step of cooling the substrate on which the coating film is formed to room temperature may be provided before the step [II] is continued.

<Step [II]>

In the step [II], the polarized ultraviolet ray is irradiated to the coating film obtained in the step [I]. When the polarized ultraviolet light is irradiated onto the film surface of the coating film, the polarized ultraviolet light is irradiated to the substrate through the polarizing plate in a certain direction. As the ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. It is preferred to select the most appropriate wavelength by a filter or the like by the type of the coating film to be used. Further, for example, in the form of selectively inducing a photocrosslinking reaction, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selected. As the ultraviolet light, for example, light emitted from a high pressure mercury lamp can be used.

The amount of ultraviolet light irradiated by the polarized light depends on the coating film used. In the coating film, the maximum value (hereinafter also referred to as ΔAmax) of the difference ΔA between the ultraviolet light absorbance in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet light absorbance in the vertical direction is preferably obtained. The amount of ultraviolet rays is in the range of 1% to 70%, more preferably in the range of 1% to 50%.

<Step [III]>

In the step [III], the coating film of the polarized ultraviolet rays is heated in the step [II]. By heating, an alignment control function can be imparted to the coating film.

Heating can be performed by heating means such as a hot plate, a heat cycle type oven or an IR (infrared) type oven. The heating temperature can be considered to make the liquid crystal of the coating film used. The temperature of sexual performance is determined.

The heating temperature is preferably within a temperature range in which the side chain type polymer indicates the temperature of liquid crystallinity (hereinafter referred to as liquid crystallinity expression temperature). When the surface of the film of the coating film is used, the liquid crystallinity of the surface of the coating film exhibits a temperature, and it is expected that the liquid crystal display temperature is lower when the side chain type polymer which exhibits liquid crystallinity is observed in a large amount (Bulk). Therefore, the heating temperature is more preferably in the temperature range of the liquid crystal display temperature of the surface of the coating film. In other words, the temperature range of the heating temperature after the polarized ultraviolet ray irradiation is preferably a lower limit of a temperature lower than a lower limit of a temperature range of the liquid crystalline property of the side chain type polymer to be used, which is 10 ° C. The upper limit of the temperature range is lower than the temperature of 10 ° C as the temperature of the upper limit. When the heating temperature is lower than the above temperature range, the effect of increasing the anisotropy of the heat of the coating film becomes insufficient, and when the heating temperature is higher than the above temperature range, the state of the coating film becomes close. The tendency of an isotropic liquid state (isotropic phase). In this case, by self-organization, it is sometimes difficult to reorient one direction.

Further, the liquid crystal display temperature means a glass transition temperature (Tg) of a side chain type polymer or a surface of a coating film from a solid phase to a liquid crystal phase, and a liquid crystal phase to an isotropic phase (isotropic phase). The temperature below the isotropic phase transfer temperature (Tiso) that causes the phase transition.

By the above steps, in the production method of the present invention, high efficiency and introduction of anisotropy of the coating film can be achieved. Moreover, the substrate with the liquid crystal alignment film can be manufactured with high efficiency.

<Step [IV]>

[IV] The step of the substrate (the first substrate) having the liquid crystal alignment film on the conductive film for driving the transverse electric field obtained in [III], and the same as the above [I'] to [III'] The liquid crystal alignment film is attached to the substrate (second substrate) of the liquid crystal alignment film, and the liquid crystal alignment film is disposed to face each other so that the liquid crystal alignment film is opposed to each other, and the liquid crystal cell is produced by a known method to produce a lateral electric field drive type liquid crystal display element. The steps. Further, the steps [I'] to [III'] are in the step [I], except that the substrate having the conductive film for driving the transverse electric field is replaced, and the substrate having the conductive film for driving the transverse electric field is used instead. The same procedure as in the steps [I] to [III] was carried out. The difference between the steps [I] to [III] and the steps [I'] to [III'] is only the presence or absence of the above-mentioned conductive film, and the description of the steps [I'] to [III'] is omitted.

In the example of the liquid crystal cell or the liquid crystal display device, the first and second substrates are prepared, and the spacer is spread on the liquid crystal alignment film of the one-side substrate, and the liquid crystal alignment film surface is formed inside. The substrate on the other side is a method of injecting a liquid crystal and sealing it under reduced pressure, or a method of sealing the liquid crystal on the liquid crystal alignment film surface of the spread pad, and bonding the substrate to perform sealing. In this case, it is preferable to use a substrate having an electrode having a comb-like structure for driving a lateral electric field in a substrate on one side. The diameter of the spacer at this time is preferably from 1 μm to 30 μm, more preferably from 2 μm to 10 μm. The spacer diameter holds the distance between one of the liquid crystal layers and the substrate, that is, the thickness of the liquid crystal layer.

The method for producing a coated substrate according to the present invention is to apply a polymer composition on a substrate and form a coating film, and then irradiate the polarized ultraviolet light. line. Then, by heating, the high-efficiency anisotropy of the side chain type polymer film is introduced, and a substrate with a liquid crystal alignment film having a liquid crystal alignment control function is produced.

In the coating film used in the present invention, the high-efficiency anisotropy of the coating film is introduced by utilizing the principle of induced molecular reorientation based on the photoreaction of the side chain and the self-organization of the liquid crystal. In the production method of the present invention, when the side chain type polymer has a photocrosslinkable group as a photoreactive group, the side chain type polymer is used to form a coating film on the substrate, and then the polarized ultraviolet light is irradiated, and then, After heating, a liquid crystal display element is formed.

In the following, an embodiment in which a side chain type polymer having a photocrosslinkable group is used as a photoreactive group is referred to as a first embodiment, and a group having a light Fress rearrangement or anisotropy is used as light. The embodiment of the side chain type polymer having a structure of a reactive group will be described as a second embodiment.

In the first aspect of the present invention, an anisotropic introduction process for producing a liquid crystal alignment film of a side chain type polymer having a photocrosslinkable group as a photoreactive group is schematically described. A diagram of an example. Fig. 1(a) is a view schematically showing a state of a side chain type polymer film before polarized light irradiation, and Fig. 1(b) is a view schematically showing a state of a side chain type polymer film after polarized light irradiation, and Fig. 1(c) The graph schematically shows the state of the side chain type polymer film after heating, and in particular, when the anisotropy introduced is small, that is, in the first aspect of the present invention, the ultraviolet irradiation amount in the step [II] is Δ. A pattern diagram when A is within the range of 1% to 15% of the maximum ultraviolet irradiation amount.

In the first aspect of the present invention, an anisotropic introduction treatment for a method for producing a liquid crystal alignment film of a side chain type polymer having a photocrosslinkable group as a photoreactive group is schematically described. A diagram of an example. Fig. 2(a) is a view schematically showing a state of a side chain type polymer film before polarized light irradiation, and Fig. 2(b) is a view schematically showing a state of a side chain type polymer film after polarized light irradiation, and Fig. 2(c) The graph schematically shows the state of the side chain type polymer film after heating, and in particular, when the anisotropy introduced is large, that is, in the first aspect of the present invention, the ultraviolet irradiation amount in the step [II] will be A pattern diagram when ΔA is within the range of 15% to 70% of the maximum ultraviolet irradiation amount.

3 is a side chain type polymer which uses a structure having a photoisomerization group or a light Freis rearrangement group represented by the above formula (18) as a second embodiment of the present invention. An example of an anisotropic introduction process of a photoreactive group in a method for producing a liquid crystal alignment film. Fig. 3 (a) is a view schematically showing a state of a side chain type polymer film before polarized light irradiation, and Fig. 3 (b) is a view schematically showing a state of a side chain type polymer film after polarized light irradiation, and Fig. 3 (c) It is a diagram schematically showing the state of the side chain type polymer film after heating, in particular, when the anisotropy introduced is small, that is, in the second aspect of the present invention, the ultraviolet irradiation amount of the step [II] will be A pattern diagram when ΔA is in the range of 1% to 70% of the maximum ultraviolet irradiation amount.

Fig. 4 is a view showing a liquid crystal alignment of a side chain type polymer using a structure in which a photoreactive group having a photorefractive group represented by the above formula (19) is used as a photoreactive group in the second embodiment of the present invention. A diagram showing an example of an anisotropic introduction process of a method for producing a film. Figure 4 (a) is a schematic representation FIG. 4(b) is a view schematically showing a state of a side chain type polymer film after polarized light irradiation, and FIG. 4(c) is a view schematically showing a side after heating. In the state of the chain type polymer film, especially when the anisotropy introduced is large, that is, in the second aspect of the present invention, the ultraviolet irradiation amount in the step [II] is the maximum ultraviolet irradiation of ΔA. A pattern diagram of the range of 1% to 70% of the amount.

In the first aspect of the present invention, when the anion treatment of the coating film is performed, and the amount of ultraviolet irradiation in the step [II] is ΔA within a range of 1% to 15% of the maximum ultraviolet irradiation amount, first A coating film 1 is formed on the substrate. As shown in Fig. 1(a), the coating film 1 formed on the substrate has a structure in which the side chain 2 has a random arrangement. According to the random arrangement of the side chain 2 of the coating film 1, the mesogenic component and the photosensitive group of the side chain 2 are also randomly aligned, and the coating film 1 is isotropic.

In the first aspect of the present invention, when the anion treatment of the coating film is performed, and the amount of ultraviolet irradiation in the step [II] is ΔA within a range of 15% to 70% of the maximum ultraviolet irradiation amount, first A coating film 3 is formed on the substrate. As shown in Fig. 2(a), the coating film 3 formed on the substrate has a structure in which the side chains 4 have a random arrangement. According to the random arrangement of the side chains 4 of the coating film 3, the mesogenic components and the photosensitive groups of the side chains 4 are also randomly aligned, and the coating film 2 is isotropic.

In the second aspect of the present invention, when the liquid crystal alignment film is used in the introduction treatment of the anisotropy of the coating film, the light having the photoisomerization group or the above formula (18) is used. The side chain type polymer of Freis rearrangement structure, the ultraviolet irradiation amount of [II] step will be △A into When it is in the range of 1% to 70% of the maximum ultraviolet irradiation amount, first, the coating film 5 is formed on the substrate. As shown in FIG. 3(a), the coating film 5 formed on the substrate has a structure in which the side chains 6 have a random arrangement. According to the random arrangement of the side chains 6 of the coating film 5, the mesogenic components and the photosensitive groups of the side chains 6 are also randomly aligned, and the side chain type polymer film 5 is isotropic.

In the second aspect of the present invention, in the case where the liquid crystal alignment film is used for the anisotropic introduction treatment of the coating film, the light Freyes rearrangement group having the above formula (19) is used. In the side chain type polymer of the structure, when the ultraviolet irradiation amount in the step [II] is such that ΔA is in the range of 1% to 70% of the maximum ultraviolet irradiation amount, first, the coating film 7 is formed on the substrate. As shown in FIG. 4(a), the coating film 7 formed on the substrate has a structure in which the side chains 8 have a random arrangement. According to the random arrangement of the side chains 8 of the coating film 7, the mesogenic components and the photosensitive groups of the side chains 8 are also randomly aligned, and the coating film 7 is isotropic.

In the first embodiment of the present invention, when the amount of ultraviolet irradiation in the step [II] is in the range of 1% to 15% of the maximum ultraviolet irradiation amount, the coating film 1 is coated with the isotropic film. Polarized ultraviolet light. As shown in FIG. 1(b), among the side chains 2 arranged in a direction parallel to the direction in which the ultraviolet light is polarized, the photosensitive group having the photosensitive group side chain 2a preferentially causes light such as a dimerization reaction. reaction. As a result, the density of the side chain 2a for photoreaction is only slightly increased in the direction of polarization of the ultraviolet ray, and as a result, only the coating film 1 is imparted with very small anisotropy.

In the first aspect of the present embodiment, the ultraviolet irradiation amount in the step [II] is in the range of 15% to 70% of the maximum ultraviolet irradiation amount of ΔA. In the case of this isotropic coating film 3, the polarized ultraviolet rays are irradiated. As shown in FIG. 2(b), among the side chains 4 arranged in the direction parallel to the polarization direction of the ultraviolet light, the photosensitive group having the photosensitive group side chain 4a preferentially causes light such as a dimerization reaction. reaction. As a result, the density of the side chain 4a in which the photoreaction is performed is increased in the direction in which the ultraviolet light is irradiated, and as a result, the coating film 3 is given a small anisotropy.

In the second aspect of the present invention, a liquid crystal alignment film is used, and a side chain type polymer having a photoisomerization group or a light Freis rearrangement group represented by the above formula (18) is used, [II When the amount of ultraviolet irradiation in the step is such that ΔA is within the range of 1% to 70% of the maximum ultraviolet irradiation amount, the isotropic coating film 5 is irradiated with the polarized ultraviolet rays. As a result, as shown in FIG. 3(b), the photosensitive group of the side chain 6a having the photosensitive group among the side chains 6 arranged in the direction parallel to the polarization direction of the ultraviolet light preferentially causes the light Fres rearrangement or the like. The light reacts. As a result, the density of the side chain 6a for photoreaction is only slightly increased in the direction of polarization of the ultraviolet ray, and as a result, only the coating film 5 is given a very small anisotropy.

In the second embodiment of the present invention, a coating film is used, and a side chain type polymer having a structure of a light Freis rearrangement group represented by the above formula (19) is used, and the ultraviolet irradiation amount in the step [II] will be When ΔA is in the range of 1% to 70% of the maximum ultraviolet irradiation amount, the isotropic coating film 7 is irradiated with polarized ultraviolet rays. As a result, as shown in FIG. 4(b), the photosensitive group of the side chain 8a having the photosensitive group among the side chains 8 arranged in the direction parallel to the polarization direction of the ultraviolet light preferentially causes rearrangement of the light Fryes, etc. The light reacts. As a result, the density of the side chain 8a of the photoreaction is performed. The degree of polarization of the ultraviolet ray is increased, and as a result, the coating film 7 is given a small anisotropy.

In the first embodiment of the present invention, when the ultraviolet irradiation amount in the step [II] is within a range of 1% to 15% of the maximum ultraviolet irradiation amount, the coating film 1 after the polarized light irradiation is heated. Become a liquid crystal state. As a result, as shown in FIG. 1(c), in the coating film 1, the amount of crosslinking reaction generated differs between the direction parallel to the direction in which the ultraviolet light is irradiated and the direction perpendicular thereto. In this case, since the amount of the crosslinking reaction generated in the direction parallel to the direction in which the ultraviolet light is irradiated is extremely small, the crosslinking reaction site is operated as a plasticizer. Therefore, the liquid crystallinity in the direction perpendicular to the polarization direction of the ultraviolet ray is higher than that in the parallel direction, and is included in the direction parallel to the direction in which the ultraviolet ray is polarized, and the side chain 2 of the mesogenic component which is self-organized is realigned. As a result, the very small anisotropy of the coating film 1 induced by the photocrosslinking reaction is increased by heat, and the coating film 1 becomes more anisotropic.

In the first embodiment of the present invention, when the ultraviolet irradiation amount in the step [II] is in the range of 15% to 70% of the maximum ultraviolet irradiation amount, the coating film 3 after the polarized light irradiation is heated to become a liquid crystal. status. As a result, as shown in FIG. 2(c), in the side chain type polymer film 3, the amount of crosslinking reaction generated differs between the direction parallel to the direction in which the ultraviolet rays are irradiated and the direction perpendicular thereto. Therefore, the side chain 4 contained in the mesogenic component which is self-organized in the direction parallel to the direction in which the ultraviolet light is irradiated is realigned. As a result, the very small anisotropy of the coating film 3 induced by the photocrosslinking reaction is increased by heat, and the coating film 3 is imparted thereto. Greater anisotropy.

In the second embodiment of the present invention, a coating film is used, and a side chain type polymer having a photoisomerization group or a light Freis rearrangement group represented by the above formula (18) is used, [II In the case where the amount of ultraviolet irradiation in the step is within the range of 1% to 70% of the maximum ultraviolet irradiation amount, the coating film 5 after the polarized light irradiation is heated to be in a liquid crystal state. As a result, as shown in FIG. 3(c), in the coating film 5, the amount of the light Fres rearrangement reaction is different between the direction parallel to the direction in which the ultraviolet rays are irradiated and the direction perpendicular thereto. In this case, the liquid crystal alignment force of the Fress rearrangement body generated in the direction perpendicular to the polarization direction of the ultraviolet ray is stronger than the liquid crystal alignment force of the side chain before the reaction, and is included in the direction of the polarization of the ultraviolet ray. In the direction, the side chain 6 of the self-organized mesogenic component is realigned. As a result, the extremely small anisotropy of the coating film 5 induced by the photocrosslinking reaction is increased by heat, and the coating film 5 becomes more anisotropic.

Similarly, in the second embodiment of the present embodiment, a side chain type polymer having a structure of the Freunds rearrangement group represented by the above formula (19) is used, and the ultraviolet irradiation amount in the step [II] will be used. When ΔA is in the range of 1% to 70% of the maximum ultraviolet irradiation amount, the coating film 7 after the polarized light irradiation is heated to be in a liquid crystal state. As a result, as shown in FIG. 4(c), in the side chain type polymer film 7, the amount of the light Fres rearrangement reaction is generated between the direction parallel to the direction in which the ultraviolet rays are irradiated and the direction perpendicular thereto. different. Since the anchoring force of the light Fryce rearrangement body 8(a) is stronger than the side chain 8 before the transposition, a certain amount of light Frys rearrangement is generated, which is included in The side chain 8 of the self-organized mesogenic component is realigned in a direction parallel to the direction in which the ultraviolet light is irradiated. As a result, the very small anisotropy of the coating film 7 induced by the light Frey's rearrangement reaction is increased by heat, and the coating film 7 becomes more anisotropic.

According to the coating film used in the method of the present invention, the polarized ultraviolet light is irradiated and heat-treated in order, and the anisotropy is introduced with high efficiency, and the liquid crystal alignment film having excellent alignment control function can be obtained.

Further, in the coating film used in the method of the present invention, the amount of the polarized ultraviolet light applied to the coating film and the heating temperature in the heat treatment are optimized. Thereby, high efficiency and introduction of anisotropy of the coating film can be achieved.

The irradiation amount of the most suitable polarizing ultraviolet ray is introduced into the coating film with high efficiency anisotropy used in the present invention, and in the coating film, the photosensitive group is subjected to photocrosslinking reaction or photoisomerization reaction, or light Fryce The amount of rearrangement reaction corresponds to the most suitable amount of polarized ultraviolet light to be irradiated. When the coating film used in the present invention is irradiated with the polarized ultraviolet light, when the photocrosslinking reaction or the photoisomerization reaction or the photosensitive chain of the side chain of the photofraction rearrangement reaction is small, the coating film cannot be obtained. A sufficient amount of light response. In this case, sufficient self-organization is not performed even after heating. Further, in the coating film used in the present invention, as a result of irradiating the polarized ultraviolet light to the structure having a photocrosslinkable group, when the photosensitive group of the side chain in which the crosslinking reaction is carried out becomes excessive, the side chain is interposed. The cross-linking reaction becomes excessive. In this case, the obtained film becomes rigid, and the subsequent heating may become an obstacle to self-organization. Moreover, in the coating film used in the present invention, the result of irradiating the polarized ultraviolet light to the structure having the light Freis rearrangement base is performed. When the photosensitive group of the side chain of the light Fres rearrangement reaction becomes excessive, the liquid crystal property of the coating film is excessively lowered. In this case, the liquid crystallinity of the obtained film also decreases, and the subsequent heating may hinder the progress of self-organization. Further, when the polarized ultraviolet light is irradiated to the structure having the light Freis rearrangement base, when the amount of ultraviolet light irradiation is too large, the side chain type polymer is photodecomposed, and the subsequent heating may hinder self-organization. Going on.

According to this, in the coating film used in the present invention, the photosensitive group of the side chain is subjected to a photocrosslinking reaction, a photoisomerization reaction, or a light Fries rearrangement reaction in an optimum amount by irradiation with polarized ultraviolet rays. It is preferably 0.1 mol% to 40 mol%, more preferably 0.1 mol% to 20 mol%, of the photosensitive group of the side chain type polymer film. By setting the amount of the photosensitive group of the side chain of the photoreaction in such a range, the self-organization efficiency of the subsequent heat treatment proceeds well, and formation of high-efficiency anisotropy in the film becomes possible.

The coating film used in the method of the present invention optimizes the photocrosslinking reaction or photoisomerization of the photosensitive group in the side chain of the side chain type polymer film by optimizing the irradiation amount of the polarized ultraviolet light. The amount of reaction, or light Fres rearrangement reaction. Further, the heat treatment after the combination achieves high efficiency and introduction of anisotropy of the coating film used in the present invention. In this case, the amount of suitable polarized ultraviolet rays can be measured according to the ultraviolet absorption evaluation of the coating film used in the present invention.

In other words, in the coating film used in the present invention, ultraviolet light absorption in the direction parallel to the polarization direction of the polarized ultraviolet light and ultraviolet absorption in the vertical direction after the polarized ultraviolet light irradiation are measured. From ultraviolet As a result of the measurement of the absorption, the difference ΔA between the ultraviolet light absorbance in the direction parallel to the polarized light direction of the polarized light and the ultraviolet light absorbance in the vertical direction was evaluated. Further, the maximum value (ΔAmax) of ΔA achieved in the coating film used in the present invention and the amount of irradiation of the polarized ultraviolet ray thereof were obtained. In the production method of the present invention, the amount of polarized ultraviolet light which is irradiated in the liquid crystal alignment film can be determined by using the amount of polarized ultraviolet radiation of ΔAmax as a standard.

In the production method of the present invention, it is preferred that the amount of the polarized ultraviolet light applied to the coating film used in the present invention is in the range of 1% to 70% of the amount of the polarized ultraviolet light which achieves ΔAmax, more preferably 1 Within the range of %~50%. In the coating film used in the present invention, the amount of polarized ultraviolet light in the range of 1% to 50% of the amount of polarized ultraviolet light of ΔAmax is equivalent to the photosensitive base of the side chain type polymer film. 0.1 mol% to 20 mol% The amount of polarized ultraviolet light for photocrosslinking reaction.

As described above, in the production method of the present invention, the introduction of the anisotropy of the high efficiency of the coating film is carried out, and the suitable heating temperature may be determined based on the liquid crystal temperature range of the side chain type polymer. Accordingly, for example, when the liquid crystal temperature range of the side chain type polymer used in the present invention is from 100 ° C to 200 ° C, the temperature of the heating after the polarized ultraviolet light irradiation is desirably from 90 ° C to 190 ° C. By doing so, the coating film used in the present invention can impart greater anisotropy.

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

As described above, the cross-section manufactured by the method of the present invention The substrate for an electric field-driven liquid crystal display element or a lateral electric field-driven liquid crystal display device having the same is excellent in reliability, and is suitable for use in a large-screen, high-definition liquid crystal television or the like.

Hereinafter, the present invention will be described using examples, but the present invention is not limited to the examples.

[Examples]

The abbreviations used in the examples are as follows.

<methacrylic monomer>

MA1 is synthesized according to the synthesis method described in the patent document (WO2011-084546).

MA2 is synthesized by a synthesis method described in the patent document (Japanese Patent Laid-Open No. Hei 9-118717).

<Diisocyanate component>

ISO1: methyl phenyl 2,4-diisocyanate

ISO2: isophorone diisocyanate

<Diamine component>

Me-4APhA: N-methyl-2-(4-aminophenyl)ethylamine

DA-1MG: bis(4-aminophenoxy)methane

DA-2MG: 1,2-bis(4-aminophenoxy)ethane

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

BAPU: 1,3-bis[2-(4-aminophenyl)ethyl]urea

p-PDA: p-phenylenediamine

DDM: 4,4'-diaminodiphenylmethane

3AMPDA: 3,5-Diamino-N-(pyridin-3-ylmethyl)benzoate decylamine

DADPA: 4,4'-diaminodiphenylamine

Me-DADPA: 4,4'-diaminodiphenyl(N-methyl)amine

<tetracarboxylic dianhydride>

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

PMDA: pyromellitic dianhydride

TDA: 3,4-dicarboxy-1,2,3,4-hexahydro-1-naphthalene succinic dianhydride

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

BDAM: 1,2,4,5-pentane tetracarboxylic dianhydride:

BDA: 1,2,3,4-butane tetracarboxylic dianhydride

<organic solvent>

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

<Polymerization initiator>

AIBN: 2,2'-azobisisobutyronitrile

<Synthesis Example 1: Methacrylate Polymer Solution>

MA1 (2.99 g, 9.0 mmol) and MA2 (1.83 g, 6.0 mmol) were dissolved in THF (44.57 g), degassed by a Diaphragm pump, and then AIBN (0.12 g, 0.5 mmol) was added again. Degas. Thereafter, the mixture was reacted at 50 ° C for 30 hours to obtain a methacrylate polymer solution. This polymer solution was added dropwise to diethyl ether (500 ml), and the resulting precipitate was filtered. The precipitate was washed with diethyl ether and baked at 40 ° C. The inside of the box was dried under reduced pressure to obtain a methacrylate polymer powder.

4.0 g of the obtained powder was added to 36.0 g of NMP, and stirred at room temperature for 3 hours. A methacrylate polymer solution (M1) having a solid content concentration of 10.0% by weight was obtained. The polymer was completely dissolved at the end of the agitation.

<Synthesis Example 2: Polyurea>

1.50 g of Me-4APhA was dissolved in NMP 12.77 g as a diamine component, and 1.68 g of ISO1 was added as a diisocyanate component at room temperature, and reacted at 60 degrees for 18 hours to obtain a polyurea (PU-1) concentration. 20 wt% solution.

<Synthesis Example 3 to 10: Polyurea>

The polyurea solutions of Synthesis Examples 3 to 10 were synthesized in the same manner as in the above Synthesis Example 2 (polyurea) in the compositions shown in Table 1.

<Synthesis Example 11: Polylysine>

Using CBDA 1.88 g as a tetracarboxylic dianhydride component, using BAPU 2.98 g as a diamine component, and reacting NMP 19.4 g at room temperature for 18 hours to obtain a solution having a polyamine acid (PAA-1) concentration of 20% by weight. .

Table 1:

<Synthesis Example 12: Polyurea. Polylysine>

1.99 g of DADPA was dissolved in 16.55 g of NMP as a diamine component, and 1.55 g of ISO 2 was added as a diisocyanate component at room temperature, and after stirring for 1 hour, 0.59 g of PMDA was added as an acid dianhydride component, and further The reaction was allowed to proceed for 6 hours at room temperature to obtain a polyurea. A solution of valeric acid (PUA-1) at a concentration of 20% by weight.

<Synthesis Examples 13 to 21: Polyurea. Polylysine >

The composition shown in Table 2, used with the above polyurea. Proline synthesis example 12 The same method was used to synthesize the polyurea of Synthesis Example 13~. Proline solution.

(Example 1)

In 3.0 g of the methacrylate polymer solution (M1) obtained in the above Synthesis Example 1, 3.0 g of a polyurea solution (PU-1) was added and stirred at room temperature for 1 hour. Further, BCS 4.0 g and NMP 5.0 g were added to the solution, and the mixture was stirred at room temperature for 1 hour to obtain a polymer solution (A1) having a solid content concentration of 6.0% by weight. This polymer solution directly becomes a liquid crystal alignment agent for forming a liquid crystal alignment film.

(Examples 2 to 9 and Comparative Examples 1 to 2)

The polymer solutions of Examples 2 to 9 were obtained in the same manner as in Example 1 in the compositions shown in Table 3. Further, Comparative Examples 1 and 2 were also adjusted in the same manner.

(Embodiment 10)

In the above methacrylic acid synthesis example 1, the methacrylate polymer solution (M1) 3.0 g, 3.5 g of polyurea was added. Proline solution (PUA-1) Stir at room temperature for 1 hour. Further, BCS 6.7 g and NMP 3.5 g were added to the solution, and the mixture was stirred at room temperature for 1 hour to obtain a polymer solution (A10) having a solid content concentration of 6.0% by weight. This polymer solution directly becomes a liquid crystal alignment agent for forming a liquid crystal alignment film.

(Examples 11 to 19)

The polymer solutions of Examples 11 to 20 were obtained in the same manner as in Example 10 using the compositions shown in Table 4.

[Production of Liquid Crystal Cell]

Using the liquid crystal alignment agent (A1) obtained in Example 1, the liquid crystal cell was produced in the order shown below. The substrate was a glass substrate having a thickness of 30 mm × 40 mm and a thickness of 0.7 mm, and a comb-shaped pixel electrode formed by patterning an ITO film was used. The pixel electrode has a comb-tooth shape in which a central portion is provided with a plurality of electrode elements to be bent in a zigzag shape. The width of each electrode element in the lateral direction was 10 μm, and the interval between the electrode elements was 20 μm. Since the pixel electrode forming each pixel is composed of a plurality of electrode elements having a curved shape in the center portion, the shape of each pixel is not rectangular, but is curved in the same manner as the electrode element in the central portion, and is similar to a bold type. The shape of the word. Further, each pixel is divided into upper and lower sides by a curved portion at the center thereof, and has a first region on the upper side of the curved portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the direction in which the electrode elements constituting the pixel electrodes are formed is different. In other words, when the alignment direction of the liquid crystal alignment film to be described later is used as a reference, the electrode elements of the pixel electrode are formed at an angle of +15° (clockwise) in the first region of the pixel, and the second pixel is formed. In the region, the electrode elements of the pixel electrode are formed at an angle of -15° (clockwise). In other words, in the first region and the second region of each pixel, the voltage between the pixel electrode and the counter electrode is applied to the direction of the rotation of the liquid crystal in the substrate surface (in-plane switching). They are constructed in opposite directions to each other.

The liquid crystal alignment agent (A1) obtained in Example 1 was spin-coated on the substrate to which the above electrode was prepared. Next, it was dried on a hot plate at 70 ° C for 90 seconds to form a liquid crystal alignment film having a film thickness of 100 nm. Next, the 313 nm ultraviolet light of 5 mJ/cm ² was irradiated through the polarizing plate through a polarizing plate, and then heated by a hot plate at 140 ° C for 10 minutes to obtain a substrate with a liquid crystal alignment film. Further, as the counter substrate, even a glass substrate having a columnar spacer having a height of 4 μm in which no electrode was formed was formed into a coating film, and an alignment treatment was performed. A printing sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was placed on the liquid crystal alignment film of the substrate on one side. Next, the substrate on the other side is bonded to the direction in which the alignment direction of the liquid crystal alignment film surface is 0°, and then the sealant is thermally cured to form an empty cell. In this empty cell, liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell having a configuration of an IPS (In-Planes Switching) mode liquid crystal display element.

Even in the liquid crystal alignment agents (A2 to A19) obtained in Examples 2 to 19, a liquid crystal cell was produced in the same manner as in A1.

(voltage retention rate (VHR) evaluation)

The VHR was evaluated in the obtained liquid crystal cell, and a voltage of 5 V was applied for 60 μs at a temperature of 70 ° C, and the voltage after 1667 ms was measured, and how much voltage was held as a voltage holding ratio was calculated.

Further, the voltage holding ratio was measured by using a voltage holding ratio measuring device VHR-1 manufactured by Dongyang Technica Co., Ltd.

Using the liquid crystal alignment agent (B1) obtained in Comparative Example 1, the liquid crystal cell was produced in the same manner as in the case of using the above liquid crystal alignment agent (A1), and VHR was evaluated in the same manner.

The results are shown in Tables 5 and 6 below.

As shown in Tables 5 and 6, it was judged that Comparative Examples 1 to 19 in which the components of Examples 1 to 19 of the present invention were common and contained no component (B) were compared. In comparison, the voltage holding ratio (VHR) is increased.

1‧‧‧Side chain polymer film

2, 2a‧‧‧ side chain

Claims (18)

A polymer composition comprising: (A) a photosensitive side chain type polymer which exhibits liquid crystallinity in a specific temperature range, (B) a polyurea, and (C) an organic solvent. The composition of claim 1, wherein the component (A) has a photosensitive side chain which causes photocrosslinking, photoisomerization, or photo Fries rearrangement. The composition of claim 1 or 2, wherein the polyurea of the component (B) is obtained by polymerizing a diisocyanate component and a diamine component. The composition of claim 1 or 2, wherein the polyurea of the component (B) is polymerized by reacting a diisocyanate component with a carboxylic acid derivative having 2 or more carboxylic acid moieties and/or an anhydride thereof and a diamine component. The reaction is obtained. The composition of claim 3 or 4, wherein the diisocyanate component is an aromatic diisocyanate and/or an aliphatic diisocyanate. The composition of any one of the items 1 to 5, wherein the component (A) has at least one photosensitive side chain selected from the group consisting of the following formulas (1) to (6), (wherein A, B, and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O -, or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be substituted by a halogen group; T is a single bond or a carbon number of 1 to 12 An alkyl group, and the hydrogen atom bonded thereto may be substituted by a halogen group; Y ₁ represents an alicyclic ring having a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5-8. The ring selected by the hydrocarbon, or the ring of the same or different ring selected from the substituents of 2 to 6 bonded through the bonding group B, and independently bonded to the hydrogen atoms of the bonding -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, carbon Substituted by an alkyl group of 1 to 5 or an alkyloxy group having 1 to 5 carbon atoms; Y ₂ represents a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5 to 8. Alicyclic hydrocarbons and groups thereof Group in the group consisting of the selected, with the hydrogen atom bonded to each of these may independently be _{-NO 2, -CN, -CH = C} (CN) 2, -CH = CH-CN, a halogen group, carbon atoms Substituted by an alkyl group of 1 to 5 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 the same definition as Y ₁ ; X represents a single bond, -COO -, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, the number of X becomes 2 When X is the same or different from each other; Cou represents coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to these may be independently -NO ₂ , -CN, -CH =C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; q1 and q2 are 1 and the other is 0. ; q3 is 0 or 1; P and Q are each independently a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. a group selected from the group consisting of; wherein, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, the bond or the CH of the CH-CH-side is an aromatic ring. When the number of P is 2 or more, P may be the same or different from each other, and when the number of Q is 2 or more, Q is mutually Is the same or different; l1 is 0 or 1; l2 is an integer of 0~2; when l1 and 12 are both 0, A also represents a single bond when T is a single bond; when l1 is 1, when T is a single bond, B Also means a single bond; H and I are independently selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof; The composition of any one of the items 1 to 5, wherein the component (A) has a photosensitive side chain selected from any one of the group consisting of the following formulas (7) to (10), (wherein A, B, and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O -, or -O-CO-CH=CH-; Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms. Or the same or different ring selected from the substituents, wherein the ring of 2~6 is bonded through the bond B, and the hydrogen atoms bonded to the bond are independently -COOR ₀ (formula) 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, and a carbon number of 1 to 5; Substituted by an alkyl group or an alkyloxy group having 1 to 5 carbon atoms; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH =CH-CO-O-, or -O-CO-CH=CH-, when X is 2, X may be the same or different; l represents an integer from 1 to 12; m represents an integer from 0 to 2. , m1, m2 represents an integer of 1 to 3; n-represents an integer (provided that when n = 0 B is a single bond) of 0 to 12; the Y ₂ represents a divalent benzene of a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of, respectively, independently of the bonded hydrogen atoms. Substituted by -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 the same definition as Y ₁ ) The composition of any one of the items 1 to 5, wherein the component (A) has a photosensitive side chain selected from any one of the group consisting of the following formulas (11) to (13), (wherein A represents independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or - O-CO-CH=CH-; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, Or -O-CO-CH=CH-, when X is 2, X may be the same or different; l represents an integer from 1 to 12, m represents an integer from 0 to 2, and m2 represents an integer from 1 to 3. ; R represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same one selected from the substituents; Or a heterogeneous ring of 2 to 6 bonded through a bond B, and the hydrogen atoms bonded to the bond may be independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or a carbon number of 1 to 5) Alkyl), -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 Substituted, or a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms) The composition according to any one of claims 1 to 5, wherein the component (A) has a photosensitive side chain represented by the following formula (14) or (15), wherein A represents independently a bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-; Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same one selected from the substituents. Or a heterogeneous ring of 2 to 6 bonded through a bond B, and the hydrogen atoms bonded to the bond may be independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or a carbon number of 1 to 5) Alkyl), -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 Substituted; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO -CH=CH-, when X is 2, X can be the same or different; l means an integer from 1 to 12, and m1 and m2 are integers from 1 to 3. The composition according to any one of claims 1 to 5, wherein the component (A) has a photosensitive side chain represented by the following formula (16) or (17), wherein A represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-; X represents Single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, When the number of X becomes 2, X may be the same or different from each other; l represents an integer from 1 to 12, and m represents an integer from 0 to 2) The composition according to any one of claims 1 to 5, wherein the component (A) has a photosensitive side chain represented by the following formula (18) or (19), wherein (in the formula, A and B are each independently Represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH -; Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or is selected from the substituents. The same or different ring of 2~6 is bonded through the bond B, and the hydrogen atoms bonded to the bond can be independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or a carbon number of 1) ~5 alkyl), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or alkyl group having 1 to 5 carbon atoms Substituted by a baseoxy group; q1 and q2 are 1 and the other is 0; l represents an integer from 1 to 12, m1 and m2 represent an integer from 1 to 3; and R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH =C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or alkyloxy group having 1 to 5 carbon atoms) The composition according to any one of claims 1 to 5, wherein the component (A) has a photosensitive side chain represented by the following formula (20), wherein A represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-; Y ₁ represents from 1 valence a ring selected from the group consisting of a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different selected from the substituents. The ring of 6 is bonded to the group formed by the bonding group B, and the hydrogen atoms bonded to the ring may be independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), - NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; X represents Single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, When the number of X becomes 2, X may be the same or different from each other; l represents an integer from 1 to 12, and m represents an integer from 0 to 2) The composition of any one of the items 1 to 12, wherein the component (A) has a liquid crystal side chain selected from any one of the group consisting of the following formulas (21) to (31), (wherein A and B have the same definitions as defined above; and Y ₃ is a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing hetero ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms; And a group selected from the group consisting of the combinations, and the hydrogen atoms bonded to the groups may be independently -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or a carbon number of 1~ Substituted by an alkyloxy group of 5; 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, Biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, alkyl group having 1 to 12 carbon atoms, or alkoxy group having 1 to 12 carbon atoms; q1 and q2 are 1 One is 0; l is an integer from 1 to 12, and m is an integer from 0 to 2. However, in equations (23) to (24), the total of all m is 2 or more, and equations (25) to (26) The total of all m is 1 or more, and m1, m2, and m3 each independently represent an integer of 1 to 3; and R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, and a combination. a benzene ring, a furan ring, a nitrogen-containing hetero ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and an alkyl group or an alkyloxy group; Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O -, -CH=N-, -CF ₂ -) A method for manufacturing a substrate having the liquid crystal alignment film, which is obtained by the steps of [I] to [III] The liquid crystal alignment film for an electric field drive type liquid crystal display element, [I] The step of applying the composition according to any one of claims 1 to 13 to a substrate having a conductive film for driving a transverse electric field to form a coating film [II] a step of irradiating the polarized ultraviolet ray to the coating film obtained in [I]; and [III] a step of heating the coating film obtained in [II]. A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element manufactured by the method of claim 14. A lateral electric field drive type liquid crystal display element having the substrate as claimed in claim 15. A method for producing a liquid crystal display device, comprising: a step of preparing a substrate (first substrate) as claimed in claim 15; a step of obtaining a second substrate having the liquid crystal alignment film; and [IV] Obtaining a lateral electric field drive type liquid crystal display device, wherein the step of obtaining the second substrate having the liquid crystal alignment film is performed by the step of [I'] to [III'], thereby obtaining a liquid crystal alignment film imparting an alignment control function; [I'] On the second substrate, a polymer composition having (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a specific temperature range, (B) a polyurea, and (C) an organic solvent is used. a step of coating to form a coating film; [II'] a step of irradiating the polarized ultraviolet ray to the coating film obtained by [I']; and [III'] heating the film obtained by [II']; [IV] the liquid crystal of the first and second substrates The alignment film has a step of arranging the first and second substrates facing each other to obtain a liquid crystal display element so that the liquid crystals are opposed to each other. A transverse electric field driven liquid crystal display element manufactured by the method of claim 17.