CN105392866B

CN105392866B - Method for manufacturing substrate having liquid crystal alignment film for in-plane switching liquid crystal display element

Info

Publication number: CN105392866B
Application number: CN201480040016.3A
Authority: CN
Inventors: 川野勇太; 名木达哉; 根木隆之; 金尔润; 川月喜弘; 近藤瑞穂
Original assignee: Public University Corp Hyogo Prefecture University; Nissan Chemical Corp
Current assignee: Public University Corp Hyogo Prefecture University; Nissan Chemical Corp
Priority date: 2013-05-13
Filing date: 2014-05-13
Publication date: 2020-11-03
Anticipated expiration: 2034-05-13
Also published as: WO2014185411A1; CN105392866A; TWI628219B; KR102165624B1; KR20160007636A; JPWO2014185411A1; JP6510975B2; TW201510025A

Abstract

The invention provides a transverse electric field driven liquid crystal display element which is endowed with orientation control capability with high efficiency and has excellent afterimage characteristics. The present invention solves the above problems by a polymer composition comprising: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range; (B) an amine compound having 1 primary amino group and a nitrogen-containing aromatic heterocycle in the molecule, wherein the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; and (C) an organic solvent. In particular, the above problems are solved by a method for manufacturing a substrate having a liquid crystal alignment film, the method comprising the steps of: [I] a step of applying the composition to a substrate having a conductive film for driving a transverse electric field to form a coating film; [ II ] irradiating the coating film obtained in [ I ] with polarized ultraviolet light; and [ III ] heating the coating film obtained in [ II ].

Description

Method for manufacturing substrate having liquid crystal alignment film for in-plane switching liquid crystal display element

Technical Field

The present invention relates to a method for manufacturing a substrate having a liquid crystal alignment film for a transverse electric field driven liquid crystal display element. More specifically, the present invention relates to a novel method for manufacturing a liquid crystal display element having excellent afterimage characteristics.

Background

Liquid crystal display elements are known as display devices having light weight, thin cross-section, and low power consumption, and have been used for large-sized television applications and the like in recent years, and remarkable progress has been made. The liquid crystal display element is configured by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes, for example. Further, in the liquid crystal display element, an organic film containing an organic material is used as a liquid crystal alignment film to cause the liquid crystal to assume a desired alignment state between the substrates.

That is, the liquid crystal alignment film is a component of the liquid crystal display element, is formed on a surface of the substrate that is in contact with the liquid crystal and holds a role of aligning the liquid crystal in a specific direction between the substrates. Further, the liquid crystal alignment film is sometimes required to have a function of aligning the liquid crystal in a specific direction, for example, a direction parallel to the substrate, and a function of controlling the pretilt angle of the liquid crystal. The ability of such a liquid crystal alignment film to control the alignment of liquid crystals (hereinafter referred to as alignment control ability) is imparted by performing alignment treatment on an organic film constituting the liquid crystal alignment film.

As an alignment treatment method of a liquid crystal alignment film for imparting alignment controllability, a brushing method has been known. The brushing method refers to the following method: the surface of an organic film of polyvinyl alcohol, polyamide, polyimide, or the like on a substrate is rubbed (brushed) with a cloth of cotton, nylon, polyester, or the like in a certain direction, thereby aligning the liquid crystal in the rubbing direction (brushing direction). This brushing method is used in the production process of a conventional liquid crystal display element because it can easily realize a relatively stable liquid crystal alignment state. As the organic film used for the liquid crystal alignment film, a polyimide-based organic film having excellent reliability such as heat resistance and electrical characteristics is mainly selected.

However, the brush rubbing method of rubbing the surface of a liquid crystal alignment film made of polyimide or the like has a problem of generating dust and static electricity. Further, in recent years, the liquid crystal display element has become more highly clear, and the surface of the liquid crystal alignment film has not been uniformly rubbed with a cloth due to irregularities caused by the electrode on the substrate or the switching active element for driving the liquid crystal, and thus uniform liquid crystal alignment has not been achieved.

Therefore, as another alignment treatment method of a liquid crystal alignment film without brushing, a photo-alignment method has been actively studied.

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

As a main photo-alignment method, a decomposition type photo-alignment method is known. For example, a polyimide film is irradiated with polarized ultraviolet light, and anisotropic decomposition occurs due to the polarization direction dependency of ultraviolet absorption of the molecular structure. Then, the liquid crystal is aligned by the polyimide remaining without decomposition (see, for example, patent document 1).

Further, photo-alignment methods of photo-crosslinking type and photo-isomerization type are also known. For example, polyvinyl cinnamate is irradiated with polarized ultraviolet rays to cause dimerization reaction (crosslinking reaction) of double bond portions of 2 side chains parallel to polarized light. Then, the liquid crystal is aligned in a direction perpendicular to the polarization direction (see, for example, non-patent document 1). In addition, when a side chain type polymer having azobenzene in the side chain is used, polarized ultraviolet rays are irradiated to cause an isomerization reaction of the azobenzene portion of the side chain parallel to the polarized light, and the liquid crystal is aligned in the direction perpendicular to the polarization direction (see, for example, non-patent document 2).

As in the above example, in the method of aligning the liquid crystal alignment film by the photo-alignment method, it is not necessary to perform brushing, and there is no fear of generation of dust or static electricity. Further, the alignment treatment can be performed even on the substrate of the liquid crystal display element having the surface with irregularities, and thus the method for aligning the liquid crystal alignment film is suitable for an industrial production process.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 3893659

Non-patent document

Non-patent document 1: m.shadt et al, jpn.j.appl.phys.31,2155(1992).

Non-patent document 2: ichimura et al, chem.rev.100,1847(2000).

Disclosure of Invention

Problems to be solved by the invention

As described above, the photo-alignment method has a significant advantage in that it does not require a brushing process, as compared with a brushing method which has been industrially used as an alignment treatment method for a liquid crystal display element. In addition, the optical alignment method can control the alignment control ability by changing the irradiation amount of polarized light, compared to the rubbing method in which the alignment control ability by the rubbing is almost constant. However, when the photo-alignment method is intended to achieve an alignment controllability similar to that achieved by the rubbing method, a large amount of polarized light irradiation is required or stable liquid crystal alignment cannot be achieved.

For example, in the decomposition type photo-alignment method described in patent document 1, it is necessary to irradiate the polyimide film with ultraviolet light or the like emitted from a high-pressure mercury lamp with a power of 500W for 60 minutes, and it is necessary to irradiate a large amount of ultraviolet light for a long time. In addition, in the case of the dimerization type or photoisomerization type photoalignment method, a large amount of ultraviolet irradiation of about several J (joules) to several tens of J may be required. Further, in the photo-alignment method of photo-crosslinking type or photo-isomerization type, since thermal stability and photo stability of liquid crystal alignment are poor, there is a problem that alignment failure occurs and image sticking is shown when a liquid crystal display element is produced. In particular, in the liquid crystal display element of the transverse electric field driving type, since liquid crystal molecules are switched in a plane, liquid crystal alignment shift after liquid crystal driving is likely to occur, and display sticking caused by AC driving is regarded as a significant problem.

Therefore, in the photo-alignment method, highly efficient and stable liquid crystal alignment of alignment treatment is required, and a liquid crystal alignment film and a liquid crystal alignment agent capable of efficiently providing a liquid crystal alignment film with high alignment controllability are required.

The invention aims to provide a substrate with a liquid crystal alignment film for a transverse electric field driven liquid crystal display element, which is endowed with alignment control capability with high efficiency and has excellent afterimage characteristics, and the transverse electric field driven liquid crystal display element with the substrate.

In addition, an object of the present invention is to provide a liquid crystal cell of a transverse electric field drive type having improved voltage holding ratio by adsorbing ionic impurities in liquid crystal at an interface of a liquid crystal alignment film, and a liquid crystal alignment film used for the cell.

Means for solving the problems

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found the following invention.

<1> a polymer composition comprising:

(A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range;

(B) an amine compound having 1 primary amino group and a nitrogen-containing aromatic heterocycle in the molecule, wherein the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; and

(C) an organic solvent.

<2> in <1> above, the component (A) may have a photosensitive side chain which undergoes photocrosslinking, photoisomerization or photoFries rearrangement.

<3>As described above<1>Or<2>Wherein the component (B) may be represented by the following formula A- [1](in the formula, Y₁₁Is a 2-valent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, Y₁₂A nitrogen-containing aromatic heterocycle).

<4> in any one of the above <1> to <3>, the component (a) may have any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6).

Wherein A, B, D each independently represents a single bond, -O-, -CH₂-, -COO-, -OCO-, -CONH-, -NH-CO-, -CH-CO-O-or-O-CO-CH-;

s is C1-C12 alkylene, and hydrogen atoms bonded to the S are optionally substituted by halogen groups;

t is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto is optionally substituted with a halogen group;

Y₁represents a ring selected from a 1-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or a group in which 2 to 6 identical or different rings selected from these substituents are bonded via a bonding group B, and hydrogen atoms bonded to these are each independently optionally substituted by-COOR₀(in the formula, R₀Hydrogen atom or C1-5 alkyl group), -NO₂、-CN、-CH＝C(CN)₂-CH ═ CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

Y₂is selected from 2-valent benzene ring, naphthalene ring and biphenyl ringA furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms and a combination thereof, hydrogen atoms bonded to each of which is independently optionally substituted by-NO₂、-CN、-CH＝C(CN)₂-CH ═ CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

r represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or a group bonded to Y₁The same definition;

x represents a single bond, -COO-, -OCO-, -N-, -CH-, -C.ident.C-, -CH-CO-O-or-O-CO-CH-, and when the number of X reaches 2, X is optionally the same or different from each other;

cou represents coumarin-6-yl or coumarin-7-yl, the hydrogen atoms bonded to them each independently being optionally substituted by-NO₂、-CN、-CH＝C(CN)₂-CH ═ CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

one of q1 and q2 is 1 and the other is 0;

q3 is 0 or 1;

p and Q are each independently a group selected from the group consisting of a 2-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a C5-8 alicyclic hydrocarbon, and combinations thereof; wherein, when X is-CH-CO-O-, -O-CO-CH-and-CH-the side to which-CH-is bonded, P or Q is an aromatic ring, when the number of P is 2 or more, P is optionally the same as or different from each other, and when the number of Q is 2 or more, Q is optionally the same as or different from each other;

l1 is 0 or 1;

l2 is an integer of 0 to 2;

when l1 and l2 are both 0, A represents a single bond when T is a single bond;

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

h and I are each independently a group selected from the group consisting of a 2-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof.

<5> in any one of the above <1> to <3>, the component (a) may have any one photosensitive side chain selected from the group consisting of the following formulas (7) to (10).

In the formula, A, B, D, Y₁、X、Y₂And R has the same definition as above;

l represents an integer of 1 to 12;

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

n represents an integer of 0 to 12 (wherein, when n is 0, B is a single bond).

<6> in any one of the above <1> to <3>, the component (a) may have any one photosensitive side chain selected from the group consisting of the following formulas (11) to (13).

Wherein A, X, l, m1 and R have the same meanings as defined above.

<7> in any one of <1> to <3>, the component (A) may have a photosensitive side chain represented by the following formula (14) or (15).

In the formula, A, Y₁L, m1 and m2 have the same definitions as above.

<8> in any one of <1> to <3>, the component (A) may have a photosensitive side chain represented by the following formula (16) or (17).

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

<9> in any one of <1> to <3>, the component (A) may have a photosensitive side chain represented by the following formula (18) or (19).

In the formula, A, B, Y₁Q1, q2, m1 and m2 have the same definitions as above.

R₁Represents a hydrogen atom, -NO₂、-CN、-CH＝C(CN)₂-CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

<10> in any one of <1> to <3>, the component (A) may have a photosensitive side chain represented by the following formula (20).

In the formula, A, Y₁X, l and m have the same definitions as above.

<11> in any one of the above <1> to <10>, the component (a) may have any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).

Wherein A, B, q1 and q2 have the same meanings as defined above;

Y₃is a group selected from the group consisting of 1-valent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, C5-C8 alicyclic hydrocarbon, and a combination thereof, and hydrogen atoms bonded thereto are each independently optionally substituted by-NO₂CN, -a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

R₃represents a hydrogen atom, -NO₂、-CN、-CH＝C(CN)₂-CH ═ CH — CN, a halogen group, a 1-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;

l represents an integer of 1 to 12, m represents an integer of 0 to 2, wherein in the formulae (23) to (24), the sum of all m is 2 or more, in the formulae (25) to (26), the sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;

R₂represents a hydrogen atom, -NO₂CN, -a halogen group, a 1-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and alicyclic hydrocarbon and alkyl or alkoxy with 5-8 carbon atoms;

Z₁、Z₂represents a single bond, -CO-, -CH₂O-、-CH＝N-、-CF₂-。

<12> a method for producing a substrate having a liquid crystal alignment film for a transverse electric field driven liquid crystal display element, which comprises the steps of:

[I] a step of applying the composition of any one of <1> to <11> on a substrate having a conductive film for driving a transverse electric field to form a coating film;

[ II ] irradiating the coating film obtained in [ I ] with polarized ultraviolet light; and

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

<13> a substrate having a liquid crystal alignment film for a transverse electric field driven type liquid crystal display element, which is produced by the method <12> above.

<14> a transverse electric field driving type liquid crystal display element having the substrate <13> above.

<15> a method for manufacturing a transverse electric field driven liquid crystal display element, which comprises the steps of:

preparing the substrate (1 st substrate) of the above <13 >;

a step of obtaining a2 nd substrate having the liquid crystal alignment film, the 2 nd substrate having the liquid crystal alignment film provided with an alignment control ability by including the following steps [ I ' ], [ II ' ] and [ III ' ]; and

[ IV ] a step of disposing the 1 st substrate and the 2 nd substrate in opposition to each other with the liquid crystal alignment films of the 1 st substrate and the 2 nd substrate facing each other with the liquid crystal interposed therebetween to obtain a liquid crystal display element,

the processes [ I ' ], [ II ' ] and [ III ' ] are:

[ I' ] a step of forming a coating film by applying a polymer composition on a2 nd substrate, the polymer composition comprising: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, (B)1 a crosslinkable compound having at least 1 substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, an alkoxy group, an alkoxyalkyl group, an oxetanyl group, an epoxy group, an isocyanate group, an oxetanyl group, a cyclocarbonate group, a trialkoxysilyl group, and a polymerizable unsaturated bond group in a molecule, and (C) an organic solvent;

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

[ III '] heating the coating film obtained in [ II' ].

<16> a transverse electric field driven type liquid crystal display element, which is manufactured by the method <15> above.

Further, the following invention is found as another aspect.

< P1> A method for producing a substrate having a liquid crystal alignment film for a transverse electric field driven liquid crystal display element, which comprises the steps of obtaining the liquid crystal alignment film to which an alignment control capability is imparted,

[I] a step of forming a coating film by applying a polymer composition onto a substrate having a conductive film for driving a transverse electric field, the polymer composition comprising: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, (B) an amine compound having 1 primary amino group and a nitrogen-containing aromatic heterocycle in the molecule, wherein the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, (C) an organic solvent;

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 undergoes photocrosslinking, photoisomerization or photofries rearrangement.

<P3>As described above<P1>Or<P2>Wherein the component (B) may be represented by the following formula A- [1](in the formula, Y₁₁Is a 2-valent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, Y₁₂A nitrogen-containing aromatic heterocycle).

< P4> in any one of the above < P1> to < P3>, the component (a) may have any one photosensitive side chain selected from the group consisting of the following formulae (1) to (6).

Y₂is a group selected from the group consisting of a 2-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a C5-C8 alicyclic hydrocarbon, and combinations thereof, and hydrogen atoms bonded thereto are each independently optionally substituted by-NO₂、-CN、-CH＝C(CN)₂-CH ═ CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

x represents a single bond, -COO-, -OCO-, -N-, -CH-, -C.ident.C-, -CH-CO-O-, or-O-CO-CH-;

one of q1 and q2 is 1 and the other is 0;

q3 is 0 or 1;

p and Q are each independently a group selected from the group consisting of a single bond, a 2-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a carbon number 5-8 alicyclic hydrocarbon, and a combination thereof. Wherein, X is-CH-CO-O-, -O-CO-CH-when, -CH-is bonded to the side of P or Q is an aromatic ring;

< P5> in any one of the above < P1> to < P3>, the component (a) may have any one photosensitive side chain selected from the group consisting of the following formulae (7) to (10).

In the formula, A, B, D, Y₁、X、Y₂And R has the same definition as above;

l represents an integer of 1 to 12;

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

n represents an integer of 0 to 12 (wherein, when n is 0, B is a single bond).

< P6> in any one of the above < P1> to < P3>, the component (a) may have any one photosensitive side chain selected from the group consisting of the following formulae (11) to (13).

Wherein A, X, l, m and R have the same meanings as defined above.

< P7> in any of the above < P1> to < P3>, the component (a) may have a photosensitive side chain represented by the following formula (14) or (15).

In the formula, A, Y₁X, l, m1 and m2 have the same definitions as above.

< P8> in any of the above < P1> to < P3>, the component (a) may have a photosensitive side chain represented by the following formula (16) or (17).

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

< P9> in any of the above < P1> to < P3>, the component (a) may have a photosensitive side chain represented by the following formula (18) or (19).

In the formula, A, B, Y₁Q1, q2, m1 and m2 have the same definitions as above.

R₁Represents a hydrogen atom, -NO₂、-CN、-CH＝C(CN)₂-CH-CN, halogen radical, carbon number1 to 5 alkyl groups or 1 to 5 alkoxy groups.

< P10> in any one of < P1> to < P3>, the component (a) may have a photosensitive side chain represented by the following formula (20).

In the formula, A, Y₁X, l and m have the same definitions as above.

< P11> in any one of the above < P1> to < P10>, the component (a) may have any one liquid crystalline side chain selected from the group consisting of the following formulae (21) to (31).

Wherein A, B, q1 and q2 have the same meanings as defined above;

l represents an integer of 1 to 12, m represents an integer of 0 to 2, wherein in the formulae (25) to (26), the sum of all m is 2 or more, in the formulae (27) to (28), the sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;

Z₁、Z₂represents a single bond, -CO-, -CH₂O-、-CH＝N-、-CF₂-。

< P12> A substrate having a liquid crystal alignment film for a transverse electric field driven liquid crystal display element, which is produced by any one of the above < P1> to < P11 >.

< P13> A transverse electric field driven liquid crystal display element having the substrate < P12 >.

< P14> a method for manufacturing a liquid crystal display element of a transverse electric field drive type, the method comprising the steps of:

preparing the substrate < P12> (the 1 st substrate);

a step of obtaining a2 nd substrate having a liquid crystal alignment film to which an alignment control capability is imparted by including the following steps [ I ' ], [ II ' ] and [ III ' ]; and

[ IV ] a step of disposing a1 st substrate and a2 nd substrate in opposition to each other with the liquid crystal alignment films of the 1 st substrate and the 2 nd substrate facing each other with the liquid crystal interposed therebetween to obtain a liquid crystal display element,

the processes [ I ' ], [ II ' ] and [ III ' ] are:

[ I' ] a step of forming a coating film by applying a polymer composition on a2 nd substrate, the polymer composition comprising: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, (B) an amine compound having 1 primary amino group and a nitrogen-containing aromatic heterocycle in the molecule, wherein the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, (C) an organic solvent;

[ III '] heating the coating film obtained in [ II' ].

< P15> a transverse electric field driven type liquid crystal display element, which is manufactured by the above < P14 >.

< P16> A composition for producing a liquid crystal alignment film for a transverse electric field driven liquid crystal display element, comprising: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range; (B) an amine compound having 1 primary amino group and a nitrogen-containing aromatic heterocycle in the molecule, wherein the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; and (C) an organic solvent.

<P17>As described above<P16>Wherein component (B) may be of the formula A- [ 1%](in the formula, Y₁₁Is a 2-valent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, Y₁₂A nitrogen-containing aromatic heterocycle).

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide a substrate having a liquid crystal alignment film for a transverse electric field driven liquid crystal display element, which has excellent afterimage characteristics and is provided with an alignment control capability at high efficiency, and a transverse electric field driven liquid crystal display element having the substrate.

The liquid crystal display element of the transverse electric field type manufactured by the method of the present invention is efficiently provided with an alignment control capability, and therefore, even if continuously driven for a long time, the display characteristics are not impaired.

In addition to the above-described effects, the present invention can provide a lateral electric field driven liquid crystal element having an improved voltage holding ratio by adsorbing ionic impurities in liquid crystal at the interface of a liquid crystal alignment film, and a liquid crystal alignment film used for the element.

Drawings

FIG. 1 is a view schematically illustrating an example of an anisotropy introduction treatment in 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 the introduced anisotropy is small.

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

Fig. 3 is a diagram schematically illustrating an example of the anisotropy introduction process in the method for producing a liquid crystal alignment film used in the present invention, in which an organic group that undergoes fries rearrangement or isomerization is used for a photosensitive side chain, and the introduced anisotropy is small.

Fig. 4 is a diagram schematically illustrating an example of the anisotropy introduction process in the method for producing a liquid crystal alignment film used in the present invention, and is a diagram when an organic group that undergoes fries rearrangement or isomerization is used for a photosensitive side chain and the introduced anisotropy is large.

Detailed Description

The present inventors have conducted extensive studies and, as a result, have obtained the following findings, thereby completing the present invention.

The polymer composition used in the production method of the present invention has a photosensitive side chain type polymer capable of exhibiting liquid crystallinity (hereinafter also simply referred to as a side chain type polymer), and a coating film obtained using the polymer composition is a film having a photosensitive side chain type polymer capable of exhibiting liquid crystallinity. The coating film is subjected to an alignment treatment by polarized light irradiation without being subjected to a brushing treatment. After the polarized light irradiation, the side chain polymer film is heated to form a coating film (hereinafter, also referred to as a liquid crystal alignment film) to which an alignment control ability is imparted. At this time, the minute anisotropy exhibited by the polarized light irradiation becomes a driving force, and the liquid crystalline side chain polymer itself is effectively reoriented by self-assembly. As a result, efficient alignment treatment can be achieved as a liquid crystal alignment film, and a liquid crystal alignment film to which high alignment controllability is imparted can be obtained.

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

< method for producing substrate having liquid crystal alignment film > and < method for producing liquid crystal display element >

The method for manufacturing a substrate having a liquid crystal alignment film according to the present invention includes the steps of:

[I] a step of forming a coating film by applying a polymer composition onto a substrate having a conductive film for driving a transverse electric field, the polymer composition comprising: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, (B) an amine compound having 1 primary amino group and a nitrogen-containing aromatic heterocycle in the molecule, wherein the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and (C) an organic solvent;

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

Through the above steps, a liquid crystal alignment film for a transverse electric field driven liquid crystal display element to which an alignment control capability is imparted can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

In addition to the substrate (1 st substrate) obtained above, the 2 nd substrate is prepared, whereby the in-plane electric field driven liquid crystal display element can be obtained.

The 2 nd substrate is obtained by using the above-mentioned steps [ I ] to [ III ] (since a substrate having no conductive film for driving a transverse electric field is used, it may be abbreviated as the steps [ I '] to [ III' ] in the present application for convenience sake) in place of the substrate having the conductive film for driving a transverse electric field, and the 2 nd substrate having the liquid crystal alignment film to which an alignment control capability is imparted can be obtained.

The method for manufacturing the transverse electric field driven liquid crystal display element comprises the following steps:

[ IV ] a step of disposing the 1 st substrate and the 2 nd substrate obtained as described above in such a manner that the liquid crystal alignment films of the 1 st substrate and the 2 nd substrate face each other with the liquid crystal interposed therebetween to obtain a liquid crystal display element. This makes it possible to obtain a transverse electric field driven liquid crystal display element.

The following describes the respective steps of [ I ] to [ III ] and [ IV ] included in the production method of the present invention.

< Process [ I ] >

In the step [ I ], a polymer composition is applied to a substrate having a conductive film for driving a transverse electric field to form a coating film, the polymer composition comprising: a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range; an amine compound having 1 primary amino group and a nitrogen-containing aromatic heterocycle in the molecule, wherein the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; and an organic solvent.

< substrate >

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

In addition, an opaque substrate such as a silicon wafer may be used in consideration of application to a reflective liquid crystal display element.

< conductive film for driving transverse electric field >

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

When the liquid crystal display element is a transmissive conductive film, examples of the conductive film include, but are not limited to, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and the like.

In the case of a reflective liquid crystal display element, examples of the conductive film include, but are not limited to, materials that reflect light, such as aluminum.

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

< Polymer composition >

A polymer composition is applied to a substrate having a conductive film for driving a transverse electric field, and particularly, a polymer composition is applied to a conductive film.

The polymer composition used in the production method of the present invention contains: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range; (B) an amine compound having 1 primary amino group and a nitrogen-containing aromatic heterocycle in the molecule, wherein the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; and (C) an organic solvent.

[ side chain type Polymer (A) ]

(A) 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 reacted with light having a wavelength of 250 to 400nm and exhibit liquid crystallinity at a temperature of 100 to 300 ℃.

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

(A) The side chain type polymer preferably has a mesogen group because it exhibits liquid crystallinity at a temperature of 100 to 300 ℃.

(A) The side chain type polymer has a main chain to which a photosensitive side chain is bonded, and is capable of undergoing a crosslinking reaction, an isomerization reaction, or a photo-fries rearrangement in response to light. The side chain structure having photosensitivity is not particularly limited, and is preferably a structure in which a crosslinking reaction or a photo-fries rearrangement occurs in response to light, and more preferably a structure in which a crosslinking reaction occurs. At this time, the achieved orientation controllability can be stably maintained for a long period of time even if exposed to external stress such as heat. The structure of the photosensitive side chain type polymer film capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, and a mesogen component having a rigid side chain structure is preferable. In this case, when the side chain polymer is formed into a liquid crystal alignment film, stable liquid crystal alignment can be obtained.

The structure of the polymer can be, for example, as follows: a main chain and a side chain bonded to the main chain, wherein the side chain has a liquid crystal component such as biphenyl, terphenyl, phenylcyclohexyl, phenylbenzoate, azophenyl and the like, and a photosensitive group which is bonded to the tip portion and which is subjected to a crosslinking reaction or an isomerization reaction by induced light; has a main chain and a side chain bonded thereto, the side chain having a benzoate group which is both a mesogen component and is subjected to a photo-Fries rearrangement reaction.

More specific examples of the structure of the photosensitive side chain type polymer film capable of exhibiting liquid crystallinity preferably include a structure having a main chain composed of at least 1 selected from the group consisting of a radical polymerizable group such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α -methylene- γ -butyrolactone, styrene, vinyl, maleimide, norbornene and the like, and a siloxane, and a side chain containing at least 1 selected from the group consisting of the following formulas (1) to (6).

Y₂is a group selected from the group consisting of a 2-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a C5-C8 alicyclic hydrocarbon, and combinations thereof, and hydrogen atoms bonded thereto are each independently optionally substituted by-NO₂、-CN、-CH＝C(CN)₂-CH ═ CH-CN, halogen radicals,Alkyl group having 1 to 5 carbon atoms or alkoxy group having 1 to 5 carbon atoms;

one of q1 and q2 is 1 and the other is 0;

q3 is 0 or 1;

l1 is 0 or 1;

l2 is an integer of 0 to 2;

when l1 and l2 are both 0, A represents a single bond when T is a single bond;

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

The side chain may be any one of photosensitive side chains selected from the group consisting of the following formulae (7) to (10).

In the formula, A, B, D, Y₁、X、Y₂And R has the same definition as above;

l represents an integer of 1 to 12;

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

n represents an integer of 0 to 12 (wherein, when n is 0, B is a single bond).

The side chain may be any one of photosensitive side chains selected from the group consisting of the following formulae (11) to (13).

Wherein A, X, l, m1 and R have the same meanings as defined above.

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

In the formula, A, Y₁L, m1 and m2 have the same definitions as above.

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

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

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

In the formula, A, B, Y₁Q1, q2, m1 and m2 have the same definitions as above.

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

In the formula, A, Y₁X, l and m have the same definitions as above.

The side chain polymer (a) may have any liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).

Wherein A, B, q1 and q2 have the same meanings as defined above;

Z₁、Z₂represents a single bond, -CO-, -CH₂O-、-CH＝N-、-CF₂-。

[ production method of photosensitive side-chain type Polymer ]

The photosensitive side chain polymer capable of exhibiting liquid crystallinity can be obtained by polymerizing a photoreactive side chain monomer having the photosensitive side chain and a liquid crystalline side chain monomer.

[ photoreactive side chain monomer ]

Photoreactive side chain monomers refer to: in the case of forming a polymer, a monomer of the polymer having a photosensitive side chain at a side chain site of the polymer can be formed.

The photoreactive group in the side chain is preferably represented by the following structure or a derivative thereof.

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

In the present application, as photoreactive and/or liquid crystalline side chain monomers, novel compounds (1) to (11) represented by the following formulae (1) to (11) are provided; and compounds (12) to (17) represented by the following formulae (12) to (17).

Wherein R represents a hydrogen atom or a methyl group; s represents an alkylene group having 2 to 10 carbon atoms; r¹⁰Represents Br or CN; s represents an alkylene group having 2 to 10 carbon atoms; u represents 0 or 1; and Py represents 2-pyridyl, 3-pyridyl or 4-pyridyl. In addition, v represents 1 or 2.

[ liquid Crystal side chain monomer ]

The liquid crystalline side chain monomer means: a polymer derived from the monomer exhibits liquid crystallinity, and the polymer is a monomer capable of forming a mesogen group at a side chain position.

The mesogen group of the side chain may be a group having a mesogen structure alone, such as biphenyl or phenyl benzoate, or a group having a mesogen structure in which side chains are hydrogen-bonded to each other, such as benzoic acid. The mesogen group of the side chain is preferably of the following structure.

More specific examples of the liquid crystalline side chain monomer are preferably those having a structure having a polymerizable group composed of at least 1 selected from the group consisting of a hydrocarbon, a (meth) acrylate, an itaconate, a fumarate, a maleate, α -methylene- γ -butyrolactone, styrene, a vinyl group, a maleimide, norbornene and other radical polymerizable groups, and a siloxane, and a side chain containing at least 1 of the above formulas (21) to (31).

(A) The side chain type polymer can be obtained by polymerization of the photoreactive side chain monomer exhibiting liquid crystallinity. The side chain monomer is obtained by copolymerization of a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystalline side chain monomer, or copolymerization of a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystalline side chain monomer. Further, the monomer may be copolymerized with another monomer within a range not impairing the liquid crystal property expressing ability.

Examples of the other monomers include industrially available monomers capable of radical polymerization.

Specific examples of the other monomer include unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, and the like.

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, anthryl methyl acrylate, phenyl acrylate, 2,2, 2-trifluoroethyl acrylate, t-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecanyl acrylate, and 8-ethyl-8-tricyclodecanyl acrylate.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2, 2-trifluoroethyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecanyl methacrylate, and mixtures thereof, And 8-ethyl-8-tricyclodecyl methacrylate and the like. (meth) acrylate compounds having a cyclic ether group such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate and (3-ethyl-3-oxetanyl) methyl (meth) acrylate can also be used.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The method for producing the side chain polymer of the present embodiment is not particularly limited, and an industrially applicable general method can be used. Specifically, the polymer can be produced by cationic polymerization, radical polymerization, or anionic polymerization of a vinyl group using a liquid crystalline side chain monomer or a photoreactive side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control and the like.

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

The radical thermal polymerization initiator is a compound that generates radicals by heating to a temperature above the decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydrogen peroxides (hydrogen peroxide, t-butyl peroxide, cumene peroxide, etc.), dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (e.g., dibutylperoxycyclohexane), alkyl peroxyesters (e.g., t-butyl peroxyneodecanoate, t-butyl peroxypivalate, and t-amyl 2-ethylcyclohexanoate), persulfates (e.g., potassium persulfate, sodium persulfate, and ammonium persulfate), and azo compounds (e.g., azobisisobutyronitrile and 2, 2' -bis (2-hydroxyethyl) azobisisobutyronitrile). Such radical thermal polymerization initiators may be used in 1 kind alone, or 2 or more kinds may be used in combination.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that starts radical polymerization by light irradiation. Examples of such a radical photopolymerization initiator include benzophenone, Michler's ketone, 4 ' -bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2, 4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4 ' -isopropylphenylacetone, 1-hydroxycyclohexylphenylketone, isopropylbenzoin ether, isobutylbenzoin ether, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, and, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4 ' -bis (tert-butylperoxycarbonyl) benzophenone, 3,4,4 ' -tris (tert-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2- (4 ' -methoxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2- (3 ', 4 ' -dimethoxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2- (2 ', 4 ' -dimethoxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 4-dimethylaminobenzoate, 4-dimethylaminob, 2- (2 ' -methoxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4 ' -pentyloxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 4- [ p-N, N-bis (ethoxycarbonylmethyl) ] -2, 6-bis (trichloromethyl) s-triazine, 1, 3-bis (trichloromethyl) -5- (2 ' -chlorophenyl) s-triazine, 1, 3-bis (trichloromethyl) -5- (4 ' -methoxyphenyl) s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3 ' -carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetrakis (4-ethoxycarbonylphenyl) -1,2 ' -biimidazole, 2 ' -bis (2, 4-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2, 4-dibromophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2,4, 6-trichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3, 6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, bis (5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3 ', 4,4 ' -tetrakis (tert-butylperoxycarbonyl) benzophenone, 3 ', 4,4 ' -tetrakis (tert-hexylperoxycarbonyl) benzophenone, 3 ' -bis (methoxycarbonyl) -4,4 ' -bis (tert-butylperoxycarbonyl) benzophenone, 3,4 ' -bis (methoxycarbonyl) -4,3 ' -bis (t-butylperoxycarbonyl) benzophenone, 4 ' -bis (methoxycarbonyl) -3,3 ' -bis (t-butylperoxycarbonyl) benzophenone, 2- (3-methyl-3H-benzothiazol-2-ylidene) -1-naphthalen-2-yl-ethanone, or 2- (3-methyl-1, 3-benzothiazol-2 (3H) -ylidene) -1- (2-benzoyl) ethanone, and the like. These compounds may be used alone or in combination of two or more.

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

The organic solvent used for the polymerization reaction of the photosensitive side chain type polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the polymer to be produced is soluble in the organic solvent. Specific examples thereof are listed below.

Examples thereof include: n, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylsulfoxide, gamma-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentyl ketone, methylnonyl ketone, methylethyl ketone, methylisoamyl ketone, methylisopropyl ketone, methylcellosolve, ethylcellosolve, methylcellosolve acetate, ethylcellosolve acetate, butylcarbitol, ethylcarbitol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol, Diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl propionate, ethyl propionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, and the like.

These organic solvents may be used alone or in combination. Further, the solvent that does not dissolve the produced polymer may be mixed with the organic solvent and used as long as the produced polymer is not precipitated.

In addition, in radical polymerization, oxygen in an organic solvent may cause inhibition of the polymerization reaction, and therefore, it is preferable to use the organic solvent after degassing as much as possible.

The polymerization temperature in the radical polymerization can be selected from any temperature of 30 to 150 ℃, and preferably from 50 to 100 ℃. The reaction may be carried out at any concentration, and when the concentration is too low, it is difficult to obtain a polymer having a high molecular weight, and when the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult, and therefore the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction is carried out at a high concentration in the initial stage, and an organic solvent may be added thereafter.

In the radical polymerization reaction, when the ratio of the radical polymerization initiator to the monomer is large, the molecular weight of the obtained polymer becomes small, and when the ratio of the radical polymerization initiator to the monomer is small, the molecular weight of the obtained polymer becomes large, and therefore the ratio of the radical polymerization initiator to the polymerized monomer is preferably 0.1 to 10 mol%. In addition, various monomer components, solvents, initiators, and the like may be added during the polymerization.

[ recovery of Polymer ]

When the polymer produced is recovered from the reaction solution of the photosensitive side chain type polymer capable of exhibiting liquid crystallinity obtained by the above reaction, the reaction solution may be charged into a poor solvent to precipitate the polymer. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer precipitated by being put into the poor solvent may be recovered by filtration and then dried at normal temperature or under reduced pressure or dried by heating. Further, when the operation of re-dissolving the polymer recovered by precipitation in the organic solvent and re-precipitating and recovering is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent in this case include alcohols, ketones, hydrocarbons and the like, and when 3 or more kinds of poor solvents selected from these are used, the purification efficiency is further improved, which is preferable.

The molecular weight of the side chain polymer (a) of the present invention is preferably 2000 to 1000000, more preferably 5000 to 100000, in terms of the strength of the obtained coating film, the workability in forming the coating film, and the uniformity of the coating film, as measured by Gel Permeation Chromatography (GPC).

[ preparation of Polymer composition ]

The polymer composition used in the present invention is preferably prepared in the form of a coating liquid so as to be suitable for forming a liquid crystal alignment film. That is, the polymer composition used in the present invention is preferably prepared in the form of a solution in which a resin component for forming a resin coating is dissolved in an organic solvent. Here, the resin component is a resin component containing the photosensitive side chain type polymer capable of exhibiting liquid crystallinity described above. In this case, the content of the resin component is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 3 to 10% by mass.

In the polymer composition of the present embodiment, the resin component may be all of the above-mentioned photosensitive side chain type polymers capable of expressing liquid crystallinity, and other polymers may be mixed in the range not impairing the liquid crystal expression ability and the photosensitive property. In this case, the content of the other polymer in the resin component is 0.5 to 80% by mass, preferably 1 to 50% by mass.

Examples of such other polymers include polymers that include poly (meth) acrylates, polyamic acids, polyimides, and the like and are not photosensitive side chain type polymers capable of exhibiting liquid crystallinity.

< amine Compound >

The polymer composition used in the present invention has a specific amine compound, specifically an amine compound having 1 primary amino group and a nitrogen-containing aromatic heterocycle in the molecule, and having the primary amino group bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

The specific amine compound is not particularly limited as long as it exerts the following effects i) and/or ii) when the polymer composition used in the present invention is formed into a liquid crystal alignment film. i) Adsorbing ionic impurities in the liquid crystal at the interface of the liquid crystal alignment film, and/or ii) improving the voltage holding ratio.

The amount of the specific amine compound is not particularly limited as long as the above-mentioned effects are exhibited, and may be 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the polymer composition used in the present invention.

Specific examples of the aliphatic hydrocarbon group include a linear alkylene group, an alkylene group having a branched structure, and a 2-valent hydrocarbon group having an unsaturated bond. The aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and further preferably 1 to 10 carbon atoms.

Specific examples of the 2-valent nonaromatic cyclic hydrocarbon group include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloeicosane ring, tricyclicosane ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, and adamantane ring. Preferably a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon rings, more preferably 3 to 15 carbon rings, and further preferably 3 to 10 carbon rings.

The nitrogen-containing aromatic heterocycle contained in the amine compound may contain at least 1, preferably 1 to 4 nitrogen-containing aromatic heterocycle selected from the group consisting of the following compounds represented by the formula [20a ]]And formula [20b]And formula [20c](in the formula, Z₂A linear or branched alkyl group having 1 to 5 carbon atoms) is used.

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

More preferred aminationThe compound may be of the formula A- [ 1%](in the formula, Y₁₁Is a 2-valent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, Y₁₂A nitrogen-containing aromatic heterocycle). Formula A- [1]In, Y₁₂The organic group is not particularly limited as long as it is a 2-valent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

Formula A- [1]Preferred of (1) Y₁₁The organic group may be a 2-valent organic group having 1 selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. The non-aromatic cyclic hydrocarbon group may have the above structure. Y is₁₁More preferably, the aliphatic hydrocarbon group has 1 to 15 carbon atoms, and includes a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring, and an adamantane ring. Y is₁₁Particularly preferably a linear or branched alkylene group having 1 to 10 carbon atoms.

In addition, Y₁₁-CH in any aliphatic or non-aromatic cyclic hydrocarbyl radical not adjacent to an amino group₂-optionally interrupted by-O-, -NH-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -S- (O)₂-、-CF₂-、-C(CF₃)₂-、-C(CH₃)₂-、-Si(CH₃)₂-、-O-Si(CH₃)₂-、-Si(CH₃)₂-O-、-O-Si(CH₃)₂-O-, a 2-valent cyclic hydrocarbyl or heterocyclic ring substitution. The hydrogen atom bonded to any carbon atom is optionally substituted with a C1-20 linear or branched alkylene group, a cyclic hydrocarbon group, a C1-10 fluoroalkyl group, a heterocycle, a fluorine atom, or a hydroxyl group.

Specific examples of the 2-valent cyclic hydrocarbon group include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a phenalene ring, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, a cyclooctadecane ring, a cyclononadecane ring, a cycloeicosane ring, a tricyclicosane ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, and an adamantane ring.

Specific examples of the 2-valent heterocyclic ring include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, a purine ring, a thiadiazole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a quinoline ring, a phenanthroline ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, and an acridine ring.

Formula A- [1]Y in (1)₁₂Is a nitrogen-containing aromatic heterocycle, and may contain a compound selected from the group consisting of the following compounds [20a ]]And formula [20b]And formula [20c]Aromatic cyclic hydrocarbons having at least 1 structure in the group. Specific examples thereof include the above-described structure. Among these, preferred are a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, and a phthalazine ring.

In addition, from the viewpoint of ease of electrostatic interaction called hydrogen bond, in which a salt is formed between a nitrogen-containing aromatic heterocycle and a carboxyl group in a specific polyimide, Y is₁₁Preferably bound to a group other than Y₁₂Formula [20a ] contained in]And formula [20b]And formula [20c]Adjacent substituents.

Further, formula A- [1]As Y₁₂The nitrogen-containing aromatic heterocyclic ring of (2) may have a substituent of a halogen atom and/or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, or the like.

Formula A- [1]Y in (1)₁₁And Y₁₂The preferred combination of (a) and (b) is: y is₁₁Is selected from1 of 2-valent organic groups selected from the group consisting of C1-20 aliphatic hydrocarbon groups and C3-20 non-aromatic cyclic hydrocarbon groups, Y₁₂Is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring or a phthalazine ring. In addition, Y is₁₂The nitrogen-containing aromatic heterocyclic ring of (2) may have a substituent of a halogen atom and/or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, or the like.

As a further preferred amine compound, the following formula A- [2](in the formula, Y₁₃Is a 2-valent aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms, Y₁₄Is a single bond or-O-, -NH-, -S-, -SO₂-or a C1-19 organic radical having a valence of 2. In addition, Y₁₃And Y₁₄The total carbon atoms are 1 to 20. Y is₁₅Is a nitrogen-containing aromatic heterocycle. ) Amine compounds are shown.

Formula A- [2]Y in (1)₁₃Is a C1-10 2-valent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Specific examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a tridecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, a cyclooctadecane ring, a cyclononadecane ring, a cycloeicosane ring, a tricyclicosane ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring and the like. More preferably, a C1-10 linear or branched alkylene group, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a cyclic alkyl group, a cyclicTridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring. Particularly preferably a C1-10 linear or branched alkylene group.

Y₁₃In any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group, which is contained in (A)₂-optionally interrupted by-O-, -NH-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -S- (O)₂-、-CF₂-、-C(CF₃)₂-、-C(CH₃)₂-、-Si(CH₃)₂-、-O-Si(CH₃)₂-、-Si(CH₃)₂-O-、-O-Si(CH₃)₂-O-, a 2-valent cyclic hydrocarbyl or heterocyclic ring substitution. The hydrogen atom bonded to any carbon atom is optionally substituted with a C1-20 linear or branched alkyl group, a cyclic hydrocarbon group, a C1-10 fluoroalkyl group, a heterocycle, a fluorine atom, or a hydroxyl group. Cyclic hydrocarbon radicals and heterocycles mentioned herein and compounds of formula A- [1]Y in (1)₁₁The definitions are synonymous.

Formula A- [2]Y in (1)₁₄Is a single bond or-O-, -NH-, -S-, -SO₂-or a C1-19 organic radical having a valence of 2. The C1-19 2-valent organic group is a C1-19 2-valent organic group, optionally containing an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, etc. Such Y is listed below₁₄Specific examples of (3) are as follows.

Examples thereof include single bonds, -O-, -NH-, -S-, -SO₂-, C1-19 alkyl, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CF₂-、-C(CF₃)₂-、-CH(OH)-、-C(CH₃)₂-、-Si(CH₃)₂-、-O-Si(CH₃)₂-、-Si(CH₃)₂-O-、-O-Si(CH₃)₂-O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloeicosane ring, tricycloeicosane ring, bicycloheptane ring, decadecane ringA hydronaphthalene ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a phenalene ring, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, a purine ring, a thiadiazole ring, a pyridazine ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a quinoline ring, a phenanthroline ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an acridine ring, an oxazole ring, a piperazine ring, a piperidine ring, a dioxane ring, a morpholine ring, or the like. As Y₁₄Optionally, they comprise more than 2.

Specific examples of the group containing 2 or more include-NH-CH₂-、-NH-C₂H₄-、-NH-C₃H₆-、-NH-C₄H₈-、-S-CH₂-、-S-C₂H₄-、-S-C₃H₆-、-S-C₄H₈-、-O-CH₂-、-O-C₂H₄-、-O-C₃H₆-、-O-C₄H₈-、-NH-CO-CH₂-、-NH-CO-C₂H₄-、-NH-CO-C₃H₆-、-NH-CO-C₄H₈-、-CO-CH₂-、-CO-C₂H₄-、-CO-C₃H₆-、-CO-C₄H₈-、-CO-NH-CH₂-、-CO-NH-C₂H₄-、-CO-NH-C₃H₆-、-CO-NH-C₄H₈-、-NH-CH₂-CH(CH₃)-、-NH-C₂H₄-CH(CH₃)-、-NH-C₃H₆-CH(CH₃)-、-NH-C₄H₈-CH(CH₃)-、-S-CH₂-CH(CH₃)-、-S-C₂H₄-CH(CH₃)-、-S-C₃H₆-CH(CH₃)-、-S-C₄H₈-CH(CH₃)-、-O-CH₃-CH(CH₃)-、-O-C₂H₄-CH(CH₃)-、-O-C₃H₆-CH(CH₃)-、-O-C₄H₈-CH(CH₃)-、-NH-CO-CH₂-CH(CH₃)-、-NH-CO-C₂H₄-CH(CH₃)-、-NH-CO-C₃H₆-CH(CH₃)-、-NH-CO-C₄H₈-CH(CH₃)-、-CH(OH)-CH₂-、-CH(OH)-C₂H₄-、-CH(OH)-C₃H₆-、-CH(OH)-C₄H₈-、-CH(CH₂OH)-CH₂-、-CH(CH₂OH)-C₂H₄-、-CH(CH₂OH)-C₃H₆-、-CH(CH₂OH)-C₄H₈-、-NH-CH(CH₂OH)-CH₂-、-CO-NH-CH(CH₂OH)-CH₂-、-NH-CO-CH(CH₂OH)-CH₂-、-CO-CH(CH₂OH)-CH₂-、-S-CH(CH₂OH)-CH₂-、-O-CH(CH₂OH)-CH₂-、-CH(N(CH₃)₂)-、-C₆H₄-O-、-C₆H₄-NH-、-C₆H₄-CO-NH-、-C₆H₄-NH-CO-、-C₆H₄-CO-、-C₆H₄-CH₂-、-C₆H₄-S-, etc.

Formula A- [2]Y in (1)₁₅Is a nitrogen-containing aromatic heterocycle with the formula A1]Y in (1)₁₂The same definition is applied. Specific examples thereof include the above Y₁₂The same structure. Among these, preferred is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring.

In addition, from the viewpoint of ease of electrostatic interaction called hydrogen bond, in which a salt is formed between a nitrogen-containing aromatic heterocycle and a carboxyl group in a specific polyimide, Y is₁₄Preferably bound to a group other than Y₁₅Formula [20a ] contained in]And formula [20b]Or formula [20c]Adjacent carbon atoms.

Further, formula A- [2]As Y₁₅The nitrogen-containing aromatic heterocyclic ring of (A) optionally has a halogen atom and/or an organic groupThe organic group may optionally contain a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, or the like.

Formula A- [2]Y in (1)₁₃、Y₁₄And Y₁₅The preferred combination of (a) and (b) is: y is₁₃A C1-10 linear or branched alkylene group, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring or an adamantane ring, and Y₁₄A single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, -O-, -NH-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -S-, -SO₂-、-CF₂-、-C(CF₃)₂-、-Si(CH₃)₂-、-O-Si(CH₃)₂-、-Si(CH₃)₂-O-、-O-Si(CH₃)₂-O-、-CH(OH)-、-NH-CH₂-、-NH-C₂H₄-、-NH-C₃H₆-、-NH-C₄H₈-、-S-CH₂-、-S-C₂H₄-、-S-C₃H₆-、-S-C₄H₈-、-O-CH₂-、-O-C₂H₄-、-O-C₃H₆-、-O-C₄H₈-、-NH-CO-CH₂-、-NH-CO-C₂H₄-、-NH-CO-C₃H₆-、-NH-CO-C₄H₈-、-CO-CH₂-、-CO-C₂H₄-、-CO-C₃H₆-、-CO-C₄H₈-、-CO-NH-CH₂-、-CO-NH-C₂H₄-、-CO-NH-C₃H₆-、-CO-NH-C₄H₈-、-NH-CH₂-CH(CH₃)-、-NH-C₂H₄-CH(CH₃)-、-NH-C₃H₆-CH(CH₃)-、-NH-C₄H₈-CH(CH₃)-、-S-CH₂-CH(CH₃)-、-S-C₂H₄-CH(CH₃)-、-S-C₃H₆-CH(CH₃)-、-S-C₄H₈-CH(CH₃)-、-O-CH₃-CH(CH₃)-、-O-C₂H₄-CH(CH₃)-、-O-C₃H₆-CH(CH₃)-、-O-C₄H₈-CH(CH₃)-、-NH-CO-CH₂-CH(CH₃)-、-NH-CO-C₂H₄-CH(CH₃)-、-NH-CO-C₃H₆-CH(CH₃)-、-NH-CO-C₄H₈-CH(CH₃)-、-CH(OH)-CH₂-、-CH(OH)-C₂H₄-、-CH(OH)-C₃H₆-、-CH(OH)-C₄H₈-、-CH(CH₂OH)-CH₂-、-CH(CH₂OH)-C₂H₄-、-CH(CH₂OH)-C₃H₆-、-CH(CH₂OH)-C₄H₈-、-NH-CH(CH₂OH)-CH₂-、-CO-NH-CH(CH₂OH)-CH₂-、-NH-CO-CH(CH₂OH)-CH₂-、-CO-CH(CH₂OH)-CH₂-、-S-CH(CH₂OH)-CH₂-、-O-CH(CH₂OH)-CH₂-、-CH(N(CH₃)₂)-、-C₆H₄-O-、-C₆H₄-NH-、-C₆H₄-CO-NH-、-C₆H₄-NH-CO-、-C₆H₄-CO-、-C₆H₄-CH₂-、-C₆H₄-S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, Y₁₅Is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring or a phthalazine ring. In addition, Y is₁₅The nitrogen-containing aromatic heterocyclic ring of (2) may have a substituent of a halogen atom and/or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, or the like.

Formula A- [2]Y in (1)₁₃、Y₁₄And Y₁₅Is: y is₁₃A C1-5 linear or branched alkylene group, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, or an adamantane ring, Y₁₄A single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, -O-, -NH-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -S (O)₂-、-CH(OH)-、-NH-CH₂-、-S-CH₂-、-O-CH₂-、-O-C₂H₄-、-NH-CO-CH₂-、-CO-CH₂-、-CO-NH-CH₂-、-NH-CH₂-CH(CH₃)-、-S-CH₂-CH(CH₃)-、-O-CH₃-CH(CH₃)-、-NH-CO-CH₂-CH(CH₃)-、-CH(OH)-CH₂-、-CH(OH)-C₂H₄-、-CH(CH₂OH)-CH₂-、-NH-CH(CH₂OH)-CH₂-、-CO-NH-CH(CH₂OH)-CH₂-、-NH-CO-CH(CH₂OH)-CH₂-、-CO-CH(CH₂OH)-CH₂-、-S-CH(CH₂OH)-CH₂-、-O-CH(CH₂OH)-CH₂-、-CH(N(CH₃)₂)-、-C₆H₄-O-、-C₆H₄-NH-、-C₆H₄-CO-NH-、-C₆H₄-NH-CO-、-C₆H₄-CO-、-C₆H₄-CH₂-、-C₆H₄-S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, or phenalene ring, Y₁₅Is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring or a phthalazine ring. In addition, Y is₁₅The nitrogen-containing aromatic heterocyclic ring of (2) may have a substituent containing a halogen atom and/or an organic group optionally containing a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom or the likeAnd (4) adding the active ingredients.

Formula A- [2]Y in (1)₁₃、Y₁₄And Y₁₅Are: y is₁₃A C1-5 linear or branched alkylene group, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, or a cyclohexane ring, Y₁₄A single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, -O-, -NH-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CH (OH) -, -NH-CH₂-、-S-CH₂-、-O-CH₂-、-NH-CO-CH₂-、-CO-CH₂-、-CO-NH-CH₂-、-NH-CH₂-CH(CH₃)-、-S-CH₂-CH(CH₃)-、-O-CH₃-CH(CH₃)-、-NH-CO-CH₂-CH(CH₃)-、-CH(OH)-CH₂-、-CH(OH)-C₂H₄-、-CH(CH₂OH)-CH₂-、-NH-CH(CH₂OH)-CH₂-、-CO-NH-CH(CH₂OH)-CH₂-、-NH-CO-CH(CH₂OH)-CH₂-、-CO-CH(CH₂OH)-CH₂-、-S-CH(CH₂OH)-CH₂-、-O-CH(CH₂OH)-CH₂-、-CH(N(CH₃)₂)-、-C₆H₄-O-、-C₆H₄-NH-、-C₆H₄-CO-NH-、-C₆H₄-NH-CO-、-C₆H₄-CO-、-C₆H₄-CH₂-、-C₆H₄-S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring or anthracene ring, Y₁₅Is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, or benzimidazole ring. In addition, Y is₁₅The nitrogen-containing aromatic heterocyclic ring of (2) may have a substituent of a halogen atom and/or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, or the like.

Formula A- [2]Y in (1)₁₃、Y₁₄And Y₁₅Particularly preferred combinations of (a) are: y is₁₃Is a C1-5 linear chain orBranched alkylene, cyclobutane or cyclohexane ring, Y₁₄Is a single bond, -O-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CH (OH) -, a benzene ring, a naphthalene ring, a fluorene ring or an anthracene ring, Y₁₅Is pyrrole ring, imidazole ring, pyrazole ring, pyridine ring or pyrimidine ring. In addition, Y is₁₅The nitrogen-containing aromatic heterocyclic ring of (2) may have a substituent of a halogen atom and/or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, or the like.

Specific examples of the specific amine compound as the component (B) in the present invention include compounds M1 to M156.

More preferable examples of the compound include M6 to M8, M10, M16 to M21, M31 to M36, M40 to M45, M47 to M57, M59 to M63, M68, M69, M72 to M82, M95 to M98, M100 to M103, M108 to M125, M128 to M137, M139 to M143, and M149 to M156. More preferably, M6 to M8, M16 to M20, M32 to M36, M40, M41, M44, M49 to M54, M59 to M62, M68, M69, M75 to M82, M100 to M103, M108 to M112, M114 to M116, M118 to M121, M125, M134 to M136, M139, M140, M143, M150, and M152 to M156.

< organic solvent >

The organic solvent used in the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent capable of dissolving the resin component. Specific examples thereof are listed below.

Examples thereof include: n, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylsulfoxide, γ -butyrolactone, 3-methoxy-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 1, 3-dimethylimidazolidinone, ethylpentyl ketone, methylnonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl carbonate, methyl glycol dimethyl ether, methyl 4-hydroxy-4-methyl-2-pentanone, methyl ethyl ketone, methyl ethyl, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, and the like. They may be used alone or in combination.

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

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

Examples thereof include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol acetate, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, methyl cellosolve acetate, ethylene glycol monobutyl ether, propylene glycol monobutyl, Diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol ether, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl 3-methoxypropion, And solvents having low surface tension such as 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, n-butyl lactate, and isoamyl lactate.

These poor solvents may be used in 1 kind, or may be used in combination of two or more kinds. When the solvent as described above is used, the solvent is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the whole solvent, in order not to significantly reduce the solubility of the whole solvent contained in the polymer composition.

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

More specifically, for example, Eftop (registered trademark) 301, EF303, EF352 (manufactured by Tohkem products corporation); megafac (registered trademark) F171, F173, R-30 (manufactured by DIC CORPORATION); FluoradFC430, FC431 (manufactured by Sumitomo 3M Limited); asahiguard (registered trademark) AG710 (manufactured by Asahi glass Co., Ltd.); surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106(AGC SEIMICHEMICAL CO., LTD., manufactured by Ltd.), and the like. The proportion of the surfactant to be used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the resin component contained in the polymer composition.

Specific examples of the compound for improving the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds described below.

Examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriamine, N-trimethoxysilylpropyltriamine, 10-trimethoxysilyl-1, 4, 7-triazacyclodecane, 10-triethoxysilyl-1, 4, 7-triazacyclodecane, 9-trimethoxysilyl-3, 6-diaza-nonyl acetate, 9-triethoxysilyl-3, 6-diaza-nonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, n-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc.

Further, in order to improve the adhesion between the substrate and the liquid crystal alignment film and to prevent the deterioration of electrical characteristics due to a backlight when constituting the liquid crystal display element, an additive such as a phenolplast-based or epoxy-containing compound may be contained in the polymer composition. Specific examples of the phenolic plastic additive are shown below, but the additive is not limited to this structure.

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

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

As additives, photosensitizers may also be used. Preference is given to colourless sensitizers and triplet sensitizers.

As the photosensitizer, there are aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), coumarins, carbonyldicoumarin, aromatic 2-hydroxyketones, and amino-substituted aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono-or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3-methyl-. beta. -naphthothiazoline, 2- (. beta. -naphthoylmethylene) -3-methylbenzothiazoline, 2- (. alpha. -naphthoylmethylene) -3-methylbenzothiazoline, and the like, 2- (4-benzimidomethylene) -3-methylbenzothiazoline, 2- (beta-naphthoylmethylene) -3-methyl-beta-naphthothiazoline, 2- (4-benzimidomethylene) -3-methyl-beta-naphthothiazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-beta-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-beta-naphthooxazoline, 2- (beta-naphthoylmethylene) -3-methylbenzoxazolin, 2- (alpha-naphthoylmethylene) -3-methylbenzoxazolin, 2- (4-benzimidomethylene) -3-methylbenzoxazolin, oxazoline, 2- (beta-naphthoylmethylene) -3-methyl-beta-naphthooxazoline, 2- (4-benziylmethylene) -3-methyl-beta-naphthooxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-beta-naphthooxazoline), benzothiazole, nitroaniline (m-or p-nitroaniline, 2,4, 6-trinitroaniline) or nitroacenaphthylene (5-nitroacenaphthylene), (2- [ (m-hydroxy-p-methoxy) styryl ] benzothiazole, benzoin alkyl ether, N-alkylated phthalein, acetophenone ketal (2, 2-dimethoxyacetophenone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol and 9-anthracenecarboxylic acid), Benzopyran, azoindolizine, melolonoumarin, and the like.

Aromatic 2-hydroxyketones (benzophenone), coumarins, carbonyldicumarol, acetophenone, anthraquinone, xanthone, thioxanthone and acetophenone ketals are preferred.

In addition to the above-mentioned substances, a dielectric or conductive substance may be added to the polymer composition for the purpose of changing electrical characteristics such as dielectric constant and conductivity of the liquid crystal alignment film, and a crosslinkable compound may be added for the purpose of improving hardness and density of the film when the liquid crystal alignment film is produced, within a range not to impair the effects of the present invention.

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

As for the coating method, a method using screen printing, offset printing, flexographic printing, inkjet method, or the like is generally industrially used. As other coating methods, there are a dipping method, a roll coating method, a slit coating method, a spin coating method (spin coating method), a spray coating method, and the like, and they can be used according to the purpose.

The polymer composition is applied to a substrate having a conductive film for driving a transverse electric field, and then the solvent is evaporated at 50 to 200 ℃, preferably 50 to 150 ℃ by a heating means such as a hot plate, a thermal cycle oven or an IR (infrared) oven, thereby obtaining a coating film. The drying temperature in this case is preferably lower than the liquid crystal phase appearance temperature of the side chain type polymer.

When the thickness of the coating film is too large, it is disadvantageous in terms of power consumption of the liquid crystal display element, and when the thickness of the coating film is too small, reliability of the liquid crystal display element may be lowered, and therefore, it is preferably 5nm to 300nm, more preferably 10nm to 150 nm.

Further, after the step [ I ] and before the next step [ II ], a step of cooling the substrate having the coating film formed thereon to room temperature may be provided.

< Process [ II ] >

In the step [ II ], the coating film obtained in the step [ I ] is irradiated with polarized ultraviolet rays. When polarized ultraviolet light is irradiated to the film surface of the coating film, the substrate is irradiated with the polarized ultraviolet light from a specific direction through a polarizing plate. As the ultraviolet ray to be used, ultraviolet rays having a wavelength in the range of 100nm to 400nm can be used. Preferably, the optimum wavelength is selected by means of a filter or the like according to the kind of the coating film to be used. Further, for example, ultraviolet rays having a wavelength in the range of 290 to 400nm can be selectively used so that the photocrosslinking reaction can be selectively induced. As the ultraviolet rays, light emitted from a high-pressure mercury lamp, for example, can be used.

The irradiation amount with respect to the polarized ultraviolet ray depends on the coating film to be used. The irradiation amount is preferably in the range of 1% to 70%, more preferably in the range of 1% to 50%, of the amount of polarized ultraviolet light that achieves the maximum value of Δ a (hereinafter also referred to as Δ Amax), which is the difference between the ultraviolet absorbance of the coating film in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance of the coating film in the direction perpendicular to the polarization direction of the polarized ultraviolet light.

< Process [ III ] >

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

Heating means such as a hot plate, a thermal cycle type oven, or an IR (infrared ray) type oven can be used for heating. The heating temperature may be determined in consideration of the temperature at which the coating film used exhibits liquid crystallinity.

The heating temperature is preferably within a temperature range at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as a liquid crystal display temperature). It can be predicted that: in the case of a film surface such as a coating film, the liquid crystal display temperature on the coating film surface is lower than that when a photosensitive side chain polymer exhibiting liquid crystallinity is observed as a whole. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal display temperature on the surface of the coating film. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is preferably a temperature in a range having a lower limit of 10 ℃ lower than the lower limit of the temperature range of the liquid crystal display temperature of the side chain polymer used and an upper limit of 10 ℃ lower than the upper limit of the liquid crystal temperature range. When the heating temperature is lower than the above temperature range, the effect of increasing anisotropy by heat tends to be insufficient in the coating film, and when the heating temperature is too high as compared with the above temperature range, the state of the coating film tends to be close to an isotropic liquid state (isotropic phase), and in this case, it may be difficult to reorient the coating film in one direction by self-assembly.

The liquid crystal display temperature is: the surface of the side chain polymer or the coating film has a temperature not lower than the glass transition temperature (Tg) at which the phase transition from the solid phase to the liquid crystal phase occurs, and not higher than the homogeneous phase transition temperature (Tiso) at which the phase transition from the liquid crystal phase to the homogeneous phase (isotropic phase) occurs.

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

By having the above steps, the production method of the present invention can efficiently introduce anisotropy into a coating film. Further, a substrate with a liquid crystal alignment film can be efficiently produced.

< Process [ IV ] >

The step IV is a step of preparing a transverse electric field driven liquid crystal display element by disposing a substrate (1 st substrate) having a liquid crystal alignment film on the transverse electric field driving conductive film obtained in the step III and a substrate (2 nd substrate) having a liquid crystal alignment film without a conductive film obtained in the same manner as in the steps I 'to III' so as to face each other with the liquid crystal alignment films of both substrates facing each other through a liquid crystal, and preparing a liquid crystal cell by a known method. In the steps [ I '] to [ III' ], the steps can be performed in the same manner as the steps [ I ] to [ III ], except that a substrate having no conductive film for driving a lateral electric field is used in the step [ I ] instead of the substrate having the conductive film for driving a lateral electric field. The steps [ I ] to [ III ] are different from the steps [ I '] to [ III' ] only in the presence or absence of the conductive film, and therefore, the steps [ I '] to [ III' ] are omitted from description.

When an example of manufacturing a liquid crystal cell or a liquid crystal display element is described, the following method can be exemplified: a method of preparing the 1 st substrate and the 2 nd substrate, spreading spacers on the liquid crystal alignment film of one substrate, attaching the substrates to each other with the liquid crystal alignment film surface facing inward, injecting liquid crystal under reduced pressure, and sealing the substrates; or a method of dropping liquid crystal onto the liquid crystal alignment film surface on which the spacers are dispersed, and then attaching and sealing the substrate. In this case, it is preferable to use a substrate having an electrode with a comb-tooth structure for driving a transverse electric field as one substrate. The spacer diameter in this case is preferably 1 to 30 μm, more preferably 2 to 10 μm. The spacer diameter determines the distance between the pair of substrates for sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.

In the method for producing a substrate with a coating film of the present invention, after a coating film is formed by applying the polymer composition onto a substrate, polarized ultraviolet rays are irradiated. Then, by heating, the anisotropy is efficiently introduced into the side chain type polymer film, and a substrate with a liquid crystal alignment film having a liquid crystal alignment controllability is manufactured.

The coating film used in the present invention realizes efficient introduction of anisotropy into the coating film by utilizing the principle of molecular reorientation induced by photoreaction of side chains and self-assembly based on liquid crystallinity. In the production method of the present invention, when the side chain type polymer has a structure in which a photocrosslinkable group is a photoreactive group, a liquid crystal display element is produced by forming a coating film on a substrate using the side chain type polymer, irradiating the coating film with polarized ultraviolet rays, and then heating the coating film.

Hereinafter, an embodiment of a side chain type polymer using a structure having a photocrosslinkable group as a photoreactive group will be referred to as an embodiment 1, and an embodiment of a side chain type polymer using a structure having a photofries rearrangement group or a group which undergoes isomerization as a photoreactive group will be referred to as an embodiment 2, and will be described.

Fig. 1 is a diagram schematically illustrating an example of an anisotropy introduction process in a method for producing a liquid crystal alignment film, in which a side chain polymer having a structure in which a photocrosslinkable group is a photoreactive group is used in embodiment 1 of the present invention. Fig. 1 (a) is a diagram schematically illustrating a state of the side chain type polymer film before the polarized light irradiation, fig. 1 (b) is a diagram schematically illustrating a state of the side chain type polymer film after the polarized light irradiation, fig. 1 (c) is a diagram schematically illustrating a state of the side chain type polymer film after the heating, and particularly, a diagram schematically illustrating a case where the introduced anisotropy is small, that is, in the 1 st aspect of the present invention, the ultraviolet irradiation amount in the [ II ] step is in a range of 1% to 15% of the maximum ultraviolet irradiation amount.

Fig. 2 is a view schematically illustrating an example of an anisotropy introduction process in a method for producing a liquid crystal alignment film, in which a side chain polymer having a structure in which a photocrosslinkable group is a photoreactive group is used in embodiment 1 of the present invention. Fig. 2 (a) is a diagram schematically illustrating a state of the side chain type polymer film before the polarized light irradiation, fig. 2 (b) is a diagram schematically illustrating a state of the side chain type polymer film after the polarized light irradiation, fig. 2 (c) is a diagram schematically illustrating a state of the side chain type polymer film after the heating, and particularly, a diagram when the introduced anisotropy is large, that is, in the 1 st aspect of the present invention, the ultraviolet irradiation amount in the [ II ] step is within a range of 15% to 70% of the ultraviolet irradiation amount at which Δ a is maximized.

Fig. 3 is a view schematically illustrating an example of the anisotropy introduction process in the method for producing a liquid crystal alignment film, in which a side chain polymer having a structure in which a photoisomerization group or a photo-fries rearrangement group represented by the above formula (18) is used as a photoreactive group in embodiment 2 of the present invention. Fig. 3 (a) is a diagram schematically illustrating a state of the side chain type polymer film before the polarized light irradiation, fig. 3 (b) is a diagram schematically illustrating a state of the side chain type polymer film after the polarized light irradiation, fig. 3 (c) is a diagram schematically illustrating a state of the side chain type polymer film after the heating, and particularly, a diagram when the introduced anisotropy is small, that is, in the 2 nd aspect of the present invention, the ultraviolet irradiation amount in the [ II ] step is in a range of 1% to 70% of the ultraviolet irradiation amount at which Δ a is maximized.

Fig. 4 is a view schematically illustrating an example of the anisotropy introduction process in the method for producing a liquid crystal alignment film, in which a side chain polymer having a structure in which a photo-fries rearrangement group represented by the above formula (19) is used as a photoreactive group in embodiment 2 of the present invention. Fig. 4 (a) is a diagram schematically illustrating a state of the side chain type polymer film before the polarized light irradiation, fig. 4 (b) is a diagram schematically illustrating a state of the side chain type polymer film after the polarized light irradiation, fig. 4 (c) is a diagram schematically illustrating a state of the side chain type polymer film after the heating, and particularly, a diagram when the introduced anisotropy is large, that is, in the 2 nd aspect of the present invention, the ultraviolet irradiation amount in the [ II ] step is in a range of 1% to 70% of the ultraviolet irradiation amount at which Δ a is maximized.

In the 1 st aspect of the present invention, when the ultraviolet irradiation amount in the [ II ] step is in the range of 1% to 15% of the ultraviolet irradiation amount at which Δ a is maximized by introducing the anisotropic treatment to the coating film, first, the 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 chains 2 are randomly arranged. The mesogen component and the photosensitive group of the side chain 2 are also randomly oriented according to the random arrangement of the side chain 2 of the coating film 1, and the coating film 1 is isotropic.

In the 1 st aspect of the present invention, when the ultraviolet irradiation amount in the [ II ] step is in the range of 15% to 70% of the ultraviolet irradiation amount at which Δ a is maximized by introducing the anisotropic treatment to the coating film, first, the 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 are randomly arranged. The mesogen component and the photosensitive group of the side chain 4 are also randomly oriented by the random arrangement of the side chain 4 of the coating film 3, and the coating film 2 is isotropic.

In the 2 nd aspect of the present invention, when a liquid crystal alignment film using a side chain polymer having a structure with a photoisomerization group or a photo-fries rearrangement group represented by the above formula (18) is applied by introducing anisotropy into a coating film, when the amount of ultraviolet irradiation in the [ II ] step is in the range of 1% to 70% of the amount of ultraviolet irradiation with Δ a maximized, first, a coating film 5 is formed on a substrate. As shown in fig. 3 (a), the coating film 5 formed on the substrate has a structure in which the side chains 6 are arranged randomly. The mesogen component and the photosensitive group of the side chain 6 are also randomly oriented by the random arrangement of the side chain 6 of the coating film 5, and the side chain type polymer film 5 is isotropic.

In the 2 nd aspect of the present invention, when a liquid crystal alignment film using a side chain polymer having a structure of a photo-fries rearrangement group represented by the above formula (19) is applied by introducing anisotropy into a coating film, when the amount of ultraviolet irradiation in the [ II ] step is in the range of 1% to 70% of the amount of ultraviolet irradiation with Δ a maximized, first, a coating film 7 is formed on a substrate. As shown in fig. 4 (a), the coating film 7 formed on the substrate has a structure in which the side chains 8 are arranged randomly. The mesogen component and the photosensitive group of the side chain 8 are also randomly oriented by the random arrangement of the side chain 8 of the coating film 7, and the coating film 7 is isotropic.

In the 1 st aspect of the present embodiment, when the ultraviolet irradiation amount in the [ II ] step is in the range of 1% to 15% of the maximum ultraviolet irradiation amount Δ a, the isotropic coating film 1 is irradiated with polarized ultraviolet rays. As a result, as shown in fig. 1 (b), the photosensitive group of the side chain 2a having a photosensitive group among the side chains 2 arranged in the direction parallel to the polarization direction of ultraviolet rays preferentially undergoes a photoreaction such as dimerization. As a result, the density of the photoreactive side chain 2a is slightly increased in the polarization direction of the ultraviolet light, and as a result, very small anisotropy is imparted to the coating film 1.

In the 1 st aspect of the present embodiment, when the ultraviolet irradiation amount in the [ II ] step is in the range of 15% to 70% of the maximum ultraviolet irradiation amount Δ a, the isotropic coating film 3 is irradiated with polarized ultraviolet rays. As a result, as shown in fig. 2 (b), the photosensitive group of the side chain 4a having a photosensitive group among the side chains 4 arranged in the direction parallel to the polarization direction of ultraviolet rays preferentially undergoes a photoreaction such as dimerization. As a result, the density of the photoreactive side chain 4a increases in the polarization direction of the irradiated ultraviolet light, and as a result, small anisotropy is imparted to the coating film 3.

In embodiment 2 of the present invention, a liquid crystal alignment film using a side chain polymer having a structure with a photoisomerization group or a photo-fries rearrangement group represented by formula (18) is used, and when the amount of ultraviolet irradiation in the step [ II ] is within a range of 1% to 15% of the amount of ultraviolet irradiation at which Δ a is maximized, polarized ultraviolet rays are irradiated to the isotropic coating film 5. As a result, as shown in fig. 3 (b), the photoreaction such as photo-fries rearrangement occurs preferentially in the photosensitive group of the side chain 6a having a photosensitive group among the side chains 6 arranged in the direction parallel to the polarization direction of the ultraviolet light. As a result, the density of the photoreactive side chain 6a is slightly increased in the polarization direction of the ultraviolet light, and as a result, very small anisotropy is imparted to the coating film 5.

In embodiment 2 of the present embodiment, a coating film using a side chain polymer having a structure with a photo-fries rearrangement group represented by the above formula (19) is applied, and when the amount of ultraviolet irradiation in the [ II ] step is in the range of 1% to 70% of the amount of ultraviolet irradiation with Δ a at maximum, polarized ultraviolet rays are irradiated to the isotropic coating film 7. As a result, as shown in fig. 4 (b), the photoreaction such as photo-fries rearrangement occurs preferentially in the photosensitive group of the side chain 8a having a photosensitive group among the side chains 8 arranged in the direction parallel to the polarization direction of the ultraviolet light. As a result, the density of the photoreactive side chain 8a increases in the polarization direction of the irradiated ultraviolet light, and as a result, small anisotropy is imparted to the coating film 7.

Next, in embodiment 1 of the present embodiment, when the ultraviolet irradiation amount in the [ II ] step is in the range of 1% to 15% of the maximum ultraviolet irradiation amount Δ a, the coating film 1 irradiated with polarized light is heated to be in a liquid crystal state. As a result, as shown in fig. 1 (c), the amount of crosslinking reaction that occurs in the coating film 1 differs between the direction parallel to the polarization direction of the irradiated ultraviolet light and the direction perpendicular to the polarization direction of the irradiated ultraviolet light. In this case, since the amount of the crosslinking reaction occurring in the direction parallel to the polarization direction of the irradiated ultraviolet ray is very small, the crosslinking reaction site functions as a plasticizer. Therefore, the liquid crystallinity in the direction perpendicular to the polarization direction of the irradiated ultraviolet ray is higher than the liquid crystallinity in the direction parallel to the polarization direction of the irradiated ultraviolet ray, and the self-assembly occurs in the direction parallel to the polarization direction of the irradiated ultraviolet ray, and the side chain 2 including the mesogen component is reoriented. As a result, the very small anisotropy of the coating film 1 induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 1.

Similarly, in the embodiment 1 of the present embodiment, when the ultraviolet irradiation amount in the [ II ] step is in the range of 15% to 70% of the ultraviolet irradiation amount at which Δ a is maximized, the coating film 3 after the polarized light irradiation is heated to be in a liquid crystal state. As a result, as shown in fig. 2 (c), the side chain polymer film 3 has a difference in the amount of crosslinking reaction occurring between the direction parallel to the polarization direction of the irradiated ultraviolet ray and the direction perpendicular to the polarization direction of the irradiated ultraviolet ray. Therefore, the self-assembly occurs in the direction parallel to the polarization direction of the irradiated ultraviolet ray, and the side chain 4 including the mesogen component is reoriented. As a result, the small anisotropy of the coating film 3 induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 3.

Similarly, in embodiment 2 of the present embodiment, a coating film using a side chain polymer having a structure with a photoisomerizable group or a photo-fries rearrangement group represented by the above formula (18) is applied, and when the ultraviolet irradiation amount in the [ II ] step is in 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), the amount of the photo fries rearrangement reaction that occurs in the coating film 5 differs between the direction parallel to the polarization direction of the irradiated ultraviolet light and the direction perpendicular to the polarization direction of the irradiated ultraviolet light. At this time, since the liquid crystal alignment force of the photo-fries rearrangement occurring in the direction perpendicular to the polarization direction of the irradiated ultraviolet ray is stronger than the liquid crystal alignment force of the side chain before the reaction, the direction perpendicular to the polarization direction of the irradiated ultraviolet ray is self-assembled, and the side chain 6 including the liquid crystal original component is re-aligned. As a result, the very small anisotropy of the coating film 5 induced by the photo-fries rearrangement reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 5.

Similarly, in embodiment 2 of the present embodiment, a coating film using a side chain polymer having a structure with a photo-fries rearrangement group represented by formula (19) is applied, and when the amount of ultraviolet irradiation in the [ II ] step is in the range of 1% to 70% of the amount of ultraviolet irradiation with Δ a at the maximum, the coating film 7 after polarized light irradiation is heated to be in a liquid crystal state. As a result, as shown in fig. 4 (c), the amount of photo fries rearrangement reaction that occurs in the side chain polymer film 7 differs between the direction parallel to the polarization direction of the irradiated ultraviolet light and the direction perpendicular to the polarization direction of the irradiated ultraviolet light. Since the anchoring strength of the photo-fries rearrangement 8(a) is stronger than that of the side chain 8 before the rearrangement, when a certain amount or more of the photo-fries rearrangement occurs, self-assembly occurs in a direction parallel to the polarization direction of the irradiated ultraviolet rays, and the side chain 8 including the mesogen component is reoriented. As a result, the small anisotropy of the coating film 7 induced by the photo-fries rearrangement reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 7.

Therefore, the coating film used in the method of the present invention can be made into a liquid crystal alignment film having excellent alignment controllability by efficiently introducing anisotropy into the coating film by sequentially performing irradiation of polarized ultraviolet rays and heat treatment on the coating film.

The coating film used in the method of the present invention is optimized in the irradiation amount of polarized ultraviolet rays to be irradiated to the coating film and the heating temperature for the heating treatment. This enables efficient introduction of anisotropy into the coating film.

The irradiation amount of polarized ultraviolet ray optimal for efficiently introducing anisotropy into the coating film used in the present invention corresponds to the irradiation amount of polarized ultraviolet ray that optimizes the amount of photocrosslinking reaction, photoisomerization reaction, or photofries rearrangement reaction of the photosensitive group in the coating film. When the photosensitive group of the side chain which undergoes a photocrosslinking reaction, a photoisomerization reaction or a photoFries rearrangement reaction is small as a result of irradiating polarized ultraviolet rays to the coating film used in the present invention, a sufficient photoreactive amount cannot be obtained. In this case, sufficient self-assembly does not proceed even after the subsequent heating. On the other hand, in the coating film used in the present invention, when the photosensitive group of the side chain which undergoes the crosslinking reaction is excessive as a result of irradiating the structure having the photocrosslinkable group with polarized ultraviolet rays, the crosslinking reaction between the side chains proceeds excessively. At this time, the obtained film becomes rigid, and the progress of self-assembly by heating thereafter may be hindered. In addition, when the structure having a photo-fries rearrangement group is irradiated with polarized ultraviolet light, and the photosensitive group of the side chain having a photo-fries rearrangement reaction is excessively increased, the liquid crystallinity of the coating film is excessively decreased. In this case, the liquid crystallinity of the obtained film is also reduced, and the progress of self-assembly by heating may be hindered. Further, when polarized ultraviolet light is irradiated to a structure having a photo-fries rearrangement group, if the irradiation amount of ultraviolet light is too large, the side chain polymer is photolyzed, and the progress of self-assembly by heating thereafter may be hindered.

Therefore, in the coating film used in the present invention, the optimum amount of the side-chain photosensitive group to undergo the photocrosslinking reaction, photoisomerization reaction, or photo fries rearrangement reaction by irradiation with polarized ultraviolet light is preferably 0.1 to 40 mol%, more preferably 0.1 to 20 mol%, of the photosensitive group of the side-chain polymer film. When the amount of the photosensitive group in the side chain to be photoreactive is in such a range, self-assembly in the subsequent heat treatment advances efficiently, and high-efficiency anisotropy in the film can be formed.

In the coating film used in the method of the present invention, the amount of photocrosslinking reaction, photoisomerization reaction, or photofries rearrangement reaction of the photosensitive group in the side chain of the side chain-type polymer film is optimized by optimizing the irradiation amount of the polarized ultraviolet ray. Further, the anisotropy can be efficiently introduced into the coating film used in the present invention together with the subsequent heat treatment. In this case, the appropriate amount of polarized ultraviolet light can be evaluated based on the ultraviolet absorption of the coating film used in the present invention.

That is, with respect to the coating film used in the present invention, ultraviolet absorption in a direction parallel to the polarization direction of the polarized ultraviolet ray and ultraviolet absorption in a direction perpendicular to the polarization direction of the polarized ultraviolet ray after irradiation with the polarized ultraviolet ray were measured. From the measurement result of the ultraviolet absorption, Δ a, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet ray in the coating film, was evaluated. Then, the maximum value of Δ a (Δ Amax) realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet rays realizing this were obtained. In the production method of the present invention, the amount of polarized ultraviolet light irradiated with a preferred amount in the production of the liquid crystal alignment film can be determined with reference to the amount of polarized ultraviolet light irradiation that achieves Δ Amax.

In the production method of the present invention, the irradiation amount of the polarized ultraviolet ray with which the coating film used in the present invention is irradiated is preferably in the range of 1% to 70%, more preferably in the range of 1% to 50%, of the amount of the polarized ultraviolet ray that realizes Δ Amax. In the coating film used in the present invention, the irradiation amount of polarized ultraviolet light in the range of 1% to 50% of the amount of polarized ultraviolet light that can achieve Δ Amax corresponds to the amount of polarized ultraviolet light that causes a photocrosslinking reaction of 0.1% to 20% by mole of the entire photosensitive groups of the side chain polymer film.

As described above, in the production method of the present invention, in order to efficiently introduce anisotropy into a coating film, the above-described appropriate heating temperature may be determined based on the liquid crystal temperature range of the side chain polymer. Therefore, for example, when the liquid crystal temperature of the side chain polymer used in the present invention is in the range of 100 to 200 ℃, the heating temperature after irradiation with polarized ultraviolet rays is desirably 90 to 190 ℃. By setting in this way, a coating film used in the present invention is provided with greater anisotropy.

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

As described above, the substrate for a transverse electric field driven liquid crystal display element manufactured by the method of the present invention or the transverse electric field driven liquid crystal display element having the substrate is excellent in reliability and can be suitably used for a large-screen and high-definition liquid crystal television or the like.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Examples

The methacrylic monomers MA1 and MA2 and the additives T1 and T2 used in the examples are shown below.

MA1 and M2 were synthesized as follows. That is, MA1 was synthesized by the synthesis method described in patent document (WO 2011-084546). MA2 was synthesized by a synthesis method described in patent literature (Japanese patent laid-open No. 9-118717).

Commercially available additives T1 (3-aminomethylpyridine) and T2(1- (3-aminopropyl) imidazole) were used as additives.

Note that, the following description will be given of the reagent used in the present example.

(organic solvent)

THF: tetrahydrofuran.

NMP: n-methyl-2-pyrrolidone.

BC: butyl cellosolve.

(polymerization initiator)

AIBN: 2, 2' -azobisisobutyronitrile.

< Synthesis example 1>

MA1(4.99g, 15.0mmol) and MA2(4.60g, 15.0mmol) were dissolved in THF (88.5g), degassed with a diaphragm pump, and then AIBN (0.246g, 1.5mmol) was added and degassed again. Thereafter, the reaction was carried out at 50 ℃ for 30 hours to obtain a polymer solution of methacrylate ester. The polymer solution was added dropwise to diethyl ether (1000ml), and the resulting precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ℃ to obtain a methacrylate polymer powder.

NMP (54.0g) was added to the resulting methacrylate polymer powder (6.0g), and the mixture was stirred at room temperature for 5 hours to dissolve the polymer powder. BC (40.0g) was added to the solution and stirred to obtain a methacrylic polymer solution B1.

< example 1>

T10.015g was added to 15.0 g of the methacrylic polymer solution B15 obtained in Synthesis example 1, and the mixture was stirred at room temperature for 3 hours to obtain a polymer solution A1. The polymer solution is directly used as a liquid crystal aligning agent for forming a liquid crystal alignment film.

Using this liquid crystal aligning agent a1, a liquid crystal cell was produced according to the following procedure. The substrate was a glass substrate having a size of 30mm × 40mm and a thickness of 0.7mm, and a substrate on which a comb-shaped pixel electrode formed by patterning an ITO film was arranged was used.

The pixel electrode has a comb-tooth shape in which a plurality of "<" -shaped electrode elements are arranged with the central portion thereof bent. The width of each electrode element in the width direction was 10 μm, and the interval between the electrode elements was 20 μm. Since the pixel electrode forming each pixel is formed by arranging a plurality of "<" -shaped electrode elements each having a bent central portion, each pixel has a shape similar to a bold "<" -shaped electrode element, which is bent at the central portion in the same manner as the electrode elements, instead of a rectangular shape.

Each pixel is divided vertically with a curved portion at the center thereof as a boundary, and has a1 st region on the upper side and a2 nd region on the lower side of the curved portion. When comparing the 1 st region and the 2 nd region of each pixel, the forming directions of the electrode elements constituting the pixel electrodes are different. That is, when the alignment treatment direction of the liquid crystal alignment film described later is set as a reference, the electrode elements of the pixel electrode are formed so as to make an angle of +15 ° (clockwise) in the 1 st region of the pixel, and the electrode elements of the pixel electrode are formed so as to make an angle of-15 ° (clockwise) in the 2 nd region of the pixel. That is, the 1 st region and the 2 nd region of each pixel are configured as follows: the directions of the rotation (planar switching) of the liquid crystal in the substrate plane induced by applying a voltage between the pixel electrode and the counter electrode are opposite to each other.

< preparation of liquid Crystal cell >

The liquid crystal aligning agent a1 obtained in example 1 was spin-coated on the above-mentioned electrode-carrying substrate prepared. Then, the resultant was dried on a hot plate at 70 ℃ for 90 seconds to form a liquid crystal alignment film having a film thickness of 100 nm. Then, the thickness of the film was adjusted to 20mJ/cm through a polarizing plate²The coated surface was irradiated with ultraviolet rays of 313nm and then heated on a hot plate at 150 ℃ for 10 minutes to obtain a substrate with a liquid crystal alignment film. Further, as the counter substrate, a coating film was formed in the same manner as the glass substrate having no electrode and a columnar spacer with a height of 4 μm, and subjected to an alignment treatment. A sealant (XN-1500T, manufactured by Katachi chemical Co., Ltd.) was printed on the liquid crystal alignment film of one substrate. Next, another substrate was attached so that the liquid crystal alignment film faces each other and the alignment direction was 0 °, and then the sealant was thermally cured to prepare an empty cell. Liquid crystal MLC-2041 (manufactured by merckcorroporation) was injected into the empty cell by a reduced pressure injection method, and the injection port was sealed, thereby obtaining a liquid crystal cell including a liquid crystal display element of IPS (In-plane Switching) mode.

< evaluation of Voltage Holding Ratio (VHR) >

Using the liquid crystal cell fabricated as described above, an ac voltage of 16Vpp was applied at a frequency of 30Hz for 168 hours in a constant temperature environment of 70 ℃. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left as they were at room temperature for 1 hour. The voltage of 5V was applied to the obtained cell at a temperature of 70 ℃ for 60. mu.s, the voltage after 16.67ms was measured, and the degree to which the voltage could be held was calculated as the Voltage Holding Ratio (VHR). The voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by TOYO Corporation.

The composition of the liquid crystal aligning agent of example 1 and the results of VHR are shown in table 1.

< example 2>

A polymer solution a2 of example 2 was obtained in the same manner as in example 1 except that T2 was used in place of T1 in example 1, and a liquid crystal cell was prepared in the same manner as in example 1 to measure the voltage holding ratio. The results are shown in Table 1.

< control 1>

In comparative example 1, a liquid crystal cell was prepared in the same manner as in example 1 except that the polymer solution B1 obtained in synthesis example 1 was used as a liquid crystal aligning agent, and the voltage holding ratio was measured. The results are shown in Table 1.

[ Table 1]

TABLE 1 compositions and Voltage holding ratios VHR of examples 1 and 2 and comparative examples

As can be seen from Table 1: by using the additive in examples 1 and 2, the Voltage Holding Ratio (VHR) was improved as compared with control 1 in which no additive was used.

< evaluation of afterimage >

The IPS mode liquid crystal cell prepared in example 1 was placed between 2 polarizing plates arranged so that the polarization axes were perpendicular, the backlight was turned on in a state where no voltage was applied, and the arrangement angle of the liquid crystal cell was adjusted so that the brightness of transmitted light was minimized. Then, the rotation angle at which the liquid crystal cell is rotated from the darkest angle in the 2 nd region to the darkest angle in the 1 st region of the pixel is calculated as the initial orientation azimuth angle. Next, 16V was applied in an oven at 60 ℃ for 168 hours at a frequency of 30Hz_PPThe alternating voltage of (1). Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left as they were at room temperature for 1 hour. After the placement, the orientation azimuth is likewise determined, andthe difference in orientation angle between before and after ac driving is calculated as an angle Δ (degrees, deg.). The same applies to other examples. As a result, in all examples, the angle Δ was 0.1 or less. By irradiating a side chain type polymer film exhibiting liquid crystallinity with ultraviolet rays and then heating the film within a liquid crystal exhibiting temperature range, the liquid crystal aligning ability is efficiently imparted to the entire polymer by self-assembly, or almost no misalignment of the alignment orientation is observed even after long-term AC driving.

Description of the reference numerals

FIG. 1 shows a schematic view of a

1-side chain type polymeric membrane

2. 2a side chain

FIG. 2

3-side chain type polymeric membrane

4. 4a side chain

FIG. 3

5-side chain type polymer film

6.6 a side chain

FIG. 4

7 side chain type polymeric membrane

8. 8a side chain

Claims

1. A polymer composition comprising:

(A) a photosensitive side chain polymer exhibiting liquid crystallinity in a temperature range of 100 to 300 ℃;

(C) an organic solvent, and a solvent mixture comprising an organic solvent,

the component (A) has a photosensitive side chain which can generate photocrosslinking, photoisomerization or photoFries rearrangement,

the component (A) has any one of photosensitive side chains selected from the group consisting of the following formulas (1) to (6),

Y₁represents a ring selected from a 1-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or a group in which 2 to 6 identical or different rings selected from these substituents are bonded via a bonding group B, and hydrogen atoms bonded to these are each independently optionally substituted by-COOR₀、-NO₂、-CN、-CH＝C(CN)₂a-CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, wherein R is₀Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;

one of q1 and q2 is 1 and the other is 0;

q3 is 0 or 1;

l1 is 0 or 1;

l2 is an integer of 0 to 2;

when l1 and l2 are both 0, A represents a single bond when T is a single bond;

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

h and I are each independently a group selected from the group consisting of a 2-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof,

the component (A) has a main chain composed of at least 1 selected from the group consisting of hydrocarbons, (meth) acrylates, itaconates, fumarates, maleates, α -methylene- γ -butyrolactones, styrene, vinyls, maleimides, norbornenes and siloxanes,

the component (A) has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31),

wherein A and B have the same meanings as defined above;

one of q1 and q2 is 1 and the other is 0;

Z₁、Z₂represents a single bond, -CO-, -CH₂O-、-CH＝N-、-CF₂-，

The component (B) is an amine compound represented by the following formula A1,

Y₁₁y is a 2-valent organic group having 1 selected from the group consisting of C1-20 aliphatic hydrocarbon groups and C3-20 non-aromatic cyclic hydrocarbon groups₁₂Is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring or phthalazine ring, and Y is₁₂The carbon atom of the nitrogen-containing aromatic heterocycle of (a) optionally has a halogen atom,

the component (B) is 0.01 to 10 parts by mass based on 100 parts by mass of the polymer composition.

2. The composition according to claim 1, wherein component (A) has any one of photosensitive side chains selected from the group consisting of the following formulas (7) to (10),

l represents an integer of 1 to 12;

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

n represents an integer of 0 to 12, wherein when n is 0, B is a single bond;

r represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or a group bonded to Y₁The same definition.

3. The composition according to claim 1, wherein component (A) has any one of photosensitive side chains selected from the group consisting of the following formulas (11) to (13),

wherein A each independently represents a single bond, -O-, -CH₂-, -COO-, -OCO-, -CONH-, -NH-CO-, -CH-CO-O-or-O-CO-CH-;

l represents an integer of 1 to 12, m represents an integer of 0 to 2, and m1 represents an integer of 1 to 3;

r represents a ring selected from among 1-valent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings and C5-8 alicyclic hydrocarbons, or a group in which 2 to 6 identical or different rings selected from among these substituents are bonded via a bonding group B, and hydrogen atoms bonded thereto are each independently optionally substituted by-COOR₀、-NO₂、-CN、-CH＝C(CN)₂a-CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, wherein R is₀Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or R represents a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms.

4. The composition according to claim 1 or 2, wherein the component (A) has a photosensitive side chain represented by the following formula (14) or (15),

Y₁represents a ring selected from a 1-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or a group in which 2 to 6 rings, which are the same or different, selected from these substituents are bonded via a bonding group B, and the bonding is performedIn each case independently of their hydrogen atoms optionally substituted by-COOR₀、-NO₂、-CN、-CH＝C(CN)₂a-CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, wherein R is₀Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;

l represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3.

5. The composition according to claim 1 or 2, wherein the component (A) has a photosensitive side chain represented by the following formula (16) or (17),

wherein A represents a single bond, -O-, -CH₂-, -COO-, -OCO-, -CONH-, -NH-CO-, -CH-CO-O-or-O-CO-CH-;

l represents an integer of 1 to 12, and m represents an integer of 0 to 2.

6. The composition according to claim 1 or 2, wherein the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (18) or (19),

wherein A, B each independently represents a single bond, -O-, -CH₂-, -COO-, -OCO-, -CONH-, -NH-CO-, -CH-CO-O-or-O-CO-CH-;

Y₁represents a ring selected from a 1-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or a group in which 2 to 6 identical or different rings selected from these substituents are bonded via a bonding group B, and hydrogen atoms bonded to these are independently bonded to each otherIs selected from-COOR₀、-NO₂、-CN、-CH＝C(CN)₂a-CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, wherein R is₀Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;

one of q1 and q2 is 1 and the other is 0;

l represents an integer of 1 to 12, m1 and m2 represent an integer of 1 to 3;

7. The composition according to claim 1 or 2, wherein the component (A) has a photosensitive side chain represented by the following formula (20),

l represents an integer of 1 to 12, and m represents an integer of 0 to 2.

8. A method for manufacturing a substrate having a liquid crystal alignment film for a transverse electric field driven liquid crystal display element, the method comprising the steps of:

[I] a step of forming a coating film by applying the composition according to any one of claims 1 to 7 on a substrate having a conductive film for driving a transverse electric field;

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

9. A substrate having a liquid crystal alignment film for a transverse electric field driven type liquid crystal display element, which is produced by the method according to claim 8.

10. A transverse electric field driving type liquid crystal display element having the substrate according to claim 9.

11. A method for manufacturing a transverse electric field driven liquid crystal display element, comprising the steps of:

preparing a1 st substrate as the substrate according to claim 9;

[ IV ] a step of disposing the 1 st substrate and the 2 nd substrate in opposition to each other with the liquid crystal alignment films of the 1 st substrate and the 2 nd substrate facing each other with the liquid crystal interposed therebetween to obtain a liquid crystal display element;

the processes [ I ' ], [ II ' ] and [ III ' ] are:

[ I' ] a step of forming a coating film by applying a polymer composition on a2 nd substrate, the polymer composition comprising: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a temperature range of 100 to 300 ℃, (B) an amine compound having 1 primary amino group and a nitrogen-containing aromatic heterocycle in the molecule, wherein the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; and (C) an organic solvent;

[ III '] heating the coating film obtained in [ II' ].

12. A transverse electric field driven type liquid crystal display element produced by the method according to claim 11.