WO2015156314A1

WO2015156314A1 - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element

Info

Publication number: WO2015156314A1
Application number: PCT/JP2015/060964
Authority: WO
Inventors: 達哉名木; 勇太川野; 喜弘川月; 瑞穂近藤
Original assignee: 日産化学工業株式会社
Priority date: 2014-04-09
Filing date: 2015-04-08
Publication date: 2015-10-15
Also published as: TWI706028B; TW201606056A; JPWO2015156314A1; CN106232733A; KR20170002391A; KR102267878B1; JP6653648B2; CN106232733B

Abstract

The present invention provides: an in-plane switching liquid crystal display element which is provided with alignment control ability with high efficiency and has excellent image burn-in characteristics; and a novel composition for producing the liquid crystal display element. The present invention solves the above-described problem by a composition which contains (A) a photosensitive side-chain polymer which exhibits liquid crystallinity within a specific temperature range, (B) a compound that has 2-6 nitrogen atoms, to which at least one hydroxyalkyl group is bonded, in each molecule, and (C) an organic solvent.

Description

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

The present invention relates to a liquid crystal aligning agent used in the production of a horizontal electric field drive type liquid crystal display element, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element using the liquid crystal aligning film. More specifically, the present invention relates to a novel composition for producing a liquid crystal display device having excellent image sticking characteristics.

The liquid crystal display element is known as a light, thin, and low power consumption display device and has been remarkably developed in recent years. The liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes. In the liquid crystal display element, an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates.

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

As a method for aligning a liquid crystal alignment film for imparting alignment control ability, a rubbing method has been conventionally known. The rubbing method is a method of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide or polyimide on a substrate with a cloth such as cotton, nylon or polyester in the rubbing direction (rubbing direction). This is a method of aligning liquid crystals. Since this rubbing method can easily realize a relatively stable alignment state of liquid crystals, it has been used in the manufacturing process of conventional liquid crystal display elements. As an organic film used for the liquid crystal alignment film, a polyimide-based organic film excellent in reliability such as heat resistance and electrical characteristics has been mainly selected.

However, in the rubbing method of rubbing the surface of the liquid crystal alignment film made of polyimide or the like, generation of dust and static electricity may be a problem. In addition, due to the high definition of the liquid crystal surface element in recent years and the unevenness caused by the corresponding electrodes on the substrate and the switching active element for driving the liquid crystal, the surface of the liquid crystal alignment film cannot be uniformly rubbed with a cloth. In some cases, alignment of the liquid crystal could not be realized.

Therefore, a photo-alignment method has been actively studied as another method for aligning the liquid crystal alignment film without rubbing.

There are various photo alignment methods. Anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy.

A decomposition type photo-alignment method is known as a main photo-alignment method. In this method, for example, a polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition is caused by utilizing the polarization direction dependency of ultraviolet absorption of the molecular structure. Then, the liquid crystal is aligned by the polyimide remaining without being decomposed (see, for example, Patent Document 1).

As other photo-alignment methods, photo-crosslinking type and photoisomerization type photo-alignment methods are also known. In the photo-crosslinking type photo-alignment method, for example, polyvinyl cinnamate is used and irradiated with polarized ultraviolet rays to cause a dimerization reaction (cross-linking reaction) at double bond portions of two side chains parallel to the polarized light. Then, the liquid crystal is aligned in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1). In the photoisomerization type photo-alignment method, when a side chain type polymer having azobenzene in the side chain is used, polarized ultraviolet light is irradiated to cause an isomerization reaction in the azobenzene portion of the side chain parallel to the polarized light. The liquid crystal is aligned in a direction orthogonal to the direction (see, for example, Non-Patent Document 2).

As in the above example, the liquid crystal alignment film alignment treatment method by the photo alignment method does not require rubbing, and there is no fear of generation of dust or static electricity. An alignment process can be performed even on a substrate of a liquid crystal display element having an uneven surface, which is a method for aligning a liquid crystal alignment film suitable for an industrial production process.

Japanese Patent No. 3893659

As described above, the photo-alignment method has a great advantage because the rubbing process itself is not necessary as compared with the rubbing method that has been industrially used as an alignment treatment method for liquid crystal display elements. And compared with the rubbing method in which the alignment control ability becomes almost constant by rubbing, the photo alignment method can control the alignment control ability by changing the irradiation amount of polarized light. However, the photo-alignment method may require a large amount of polarized light irradiation to achieve the same degree of alignment control ability as the rubbing method, and stable liquid crystal alignment cannot be realized. There is.

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 from a high-pressure mercury lamp with an output of 500 W for 60 minutes. Become. Further, even in the case of dimerization type or photoisomerization type photo-alignment methods, a large amount of ultraviolet irradiation of about several J (joule) to several tens of J may be required. Furthermore, in the case of the photocrosslinking type or photoisomerization type photoalignment method, since the thermal stability and photostability of the liquid crystal alignment are poor, there is a concern that alignment defects and display burn-in may occur when a liquid crystal display element is used. was there. In particular, in a horizontal electric field drive type liquid crystal display element, since liquid crystal molecules are switched in a plane, alignment misalignment of liquid crystal after liquid crystal driving is likely to occur, and display burn-in caused by AC driving is a major issue.

Therefore, in the photo-alignment method, there is a demand for higher efficiency of alignment treatment and realization of stable liquid crystal alignment, and liquid crystal alignment films and liquid crystals that can impart high alignment control ability to the liquid crystal alignment film with high efficiency. There is a need for aligning agents.

An object of the present invention is to provide a liquid crystal alignment agent used in the production of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element using the liquid crystal alignment film.

As a result of intensive studies to achieve the above problems, the present inventors have found the following invention.
<1> (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range;
(B) a compound having 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule;
And (C) a polymer composition containing an organic solvent.

<2> In the above item <1>, the component (A) preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofleece transition.
<3> In the above <1> or <2>, a compound having 2 to 6 nitrogen atoms in one molecule to which at least one hydroxyalkyl group of the component (B) is bonded is represented by the following formula (b): It should be a thing.

(In the formula, R ¹ is an n-valent organic group,
L ¹ represents an alkylene or ^{N-X 1} of a single bond, 1 to 10 carbon atoms, ^{X 1} represents a hydrogen atom or an alkyl group and, ^{X 1} is form an alkylene and together with another ^{X 1} Or a ring structure may be formed by bonding to R ¹ ,
L ² represents a single bond or alkylene having 1 to 10 carbon atoms,
L ³ represents a single bond, NH or N-alkyl,
L ⁴ represents a single bond or alkylene having 1 to 10 carbon atoms,
L ⁵ represents a single bond or carbonyl, and when L ³ is NH or N-alkyl, L ⁴ and L ⁵ do not represent a single bond at the same time,
L ⁶ and L ⁷ each independently represent a linear or branched alkylene having 2 to 20 carbon atoms,
The alkylene in L ¹ , L ² , L ⁴ , L ⁶ and L ⁷ may be substituted with one or more substituents selected from the same or different from a halogen and a hydroxy group,
n is an integer of 2 to 6. )
<4> In the above item <3>, n is preferably 2 or 3.
<5> In the above item <3> or <4>, at least one of L ⁶ and L ⁷ may be represented by the following formula (b1).

In the formula, R ² to R ⁵ each independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group.
<6> In any one of the above items <3> to <5>, L ⁶ and L ⁷ in the formula (b) may both represent ethylene.
<7> In any one of the above items <3> to <6>, in R ¹ or L ¹ in formula (b), the atom directly bonded to the carbonyl group in formula (b) does not form an aromatic ring It should be a carbon atom.
<8> In any one of the above items <3> to <7>, R ¹ in the formula (b) is preferably represented by the following structure.

<9> In any one of the above items <1> to <8>, the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6). Good.

In the formula, A, B, and D are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—. Represents O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atom bonded to each independently represents —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.

<10> In any one of the above items <1> to <8>, the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (7) to (10): Good.
In which A, B, D, Y ₁ , X, Y ₂ and R have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (however, when n = 0, B is a single bond).

<11> In any one of the above items <1> to <8>, the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (11) to (13): Good.
In the formula, A, X, l, m, m1 and R have the same definition as above.

<12> In any one of the above items <1> to <8>, the component (A) preferably has a photosensitive side chain represented by the following formula (14) or (15).
In the formula, A, Y ₁ , l, m1 and m2 have the same definition as above.

<13> In any one of the above items <1> to <8>, the component (A) preferably has a photosensitive side chain represented by the following formula (16) or (17).
In the formula, A, X, l and m have the same definition as above.

<14> In any one of the above items <1> to <8>, the component (A) preferably has a photosensitive side chain represented by the following formula (18) or (19).
In the formula, A, B, Y ₁ , q1, q2, m1, and m2 have the same definition as above.
R ₁ is hydrogen _{_{atom, -NO 2, -CN, -CH =}} C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or alkyl of 1 to 5 carbon atoms Represents an oxy group.

<15> In any one of the above items <1> to <8>, the component (A) preferably has a photosensitive side chain represented by the following formula (20).
In the formula, A, Y ₁ , X, l and m have the same definition as above.

<16> In any one of the above items <1> to <15>, the component (A) has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31): Good.
In which A and B have the same definition as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO ₂ , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;
R ₂ is a hydrogen atom, —NO ₂ , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z ₁ and Z _{2 each} represents a single bond, —CO—, —CH ₂ O—, —CH═N—, —CF ₂ —.

<17> [I] A step of applying the composition according to any one of <1> to <16> above onto a substrate having a conductive film for driving a lateral electric field to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
The manufacturing method of the board | substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements by which orientation control ability was provided by having.
<18> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device manufactured by the manufacturing method according to <17>.
<19> A lateral electric field drive type liquid crystal display device having the substrate of <18> above.

<20> a step of preparing a substrate (first substrate) of <18>above;
[I ′] on a second substrate (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range;
(B) A step of applying a polymer composition containing 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule and (C) an organic solvent to form a coating film ;
[II ′] a step of irradiating the coating film obtained in [I ′] with polarized ultraviolet rays; and [III ′] a step of heating the coating film obtained in [II ′];
Obtaining a liquid crystal alignment film imparted with alignment control ability by having a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment films of the first and second substrates via liquid crystal The liquid crystal display element is obtained by disposing the first and second substrates so as to face each other;
A method for producing a liquid crystal display element, comprising obtaining a lateral electric field drive type liquid crystal display element.

<21> A lateral electric field drive type liquid crystal display device manufactured according to the above <20>.

According to the present invention, there are provided a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate. Can do.
INDUSTRIAL APPLICABILITY The present invention can provide a liquid crystal alignment film that is less likely to be deteriorated by thermal stress over a long period of time, and a method for manufacturing a liquid crystal display element that exhibits stable and high display quality even in a high temperature environment. Suitable for display elements.
Since the lateral electric field drive type liquid crystal display device manufactured by the method of the present invention is provided with the alignment control ability with high efficiency, the display characteristics are not impaired even when continuously driven for a long time.
In the present invention, the polymer composition contains a compound having 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group as the component (B) in a molecule, so that it can be used for a long time in a high temperature environment. Thus, it is possible to form a liquid crystal alignment film in which the voltage holding ratio does not decrease. In addition, it is possible to form a liquid crystal alignment film with little change in voltage holding ratio depending on the firing temperature. That is, it is possible to provide a liquid crystal alignment film that is less susceptible to thermal degradation due to thermal stress over a long period of time and a liquid crystal display element that stably exhibits high display quality even in a high temperature environment.

It is a figure of one example which illustrates typically the introduction process of the anisotropy in the manufacturing method of the liquid crystal aligning film used for this invention, using the crosslinkable organic group for the photosensitive side chain, and introduced the anisotropic It is a figure when property is small. It is a figure of one example which illustrates typically the introduction process of the anisotropy in the manufacturing method of the liquid crystal aligning film used for this invention, using the crosslinkable organic group for the photosensitive side chain, and introduced the anisotropic It is a figure when the property is large. It is a figure of one example which illustrates typically the introduction processing of anisotropy in the manufacturing method of the liquid crystal aligning film used for the present invention, using the organic group which causes fleece transition or isomerization to the photosensitive side chain, and is introduced. It is a figure in case the anisotropy made is small. It is a figure of one example which illustrates typically the introduction processing of anisotropy in the manufacturing method of the liquid crystal aligning film used for the present invention, using the organic group which causes fleece transition or isomerization to the photosensitive side chain, and is introduced. It is a figure in case the anisotropy made is large.

As a result of intensive studies, the inventor has obtained the following knowledge and completed the present invention.
The polymer composition of the present invention has a photosensitive side chain polymer (hereinafter also simply referred to as a side chain polymer) that can exhibit liquid crystallinity, and is obtained using the polymer composition. The obtained coating film is a film having a photosensitive side chain polymer that can exhibit liquid crystallinity. This coating film is subjected to orientation treatment by irradiation with polarized light without being rubbed. And after polarized light irradiation, it will become the coating film (henceforth a liquid crystal aligning film) to which the orientation control ability was provided through the process of heating the side chain type polymer film. At this time, the slight anisotropy developed by the irradiation of polarized light becomes a driving force, and the liquid crystalline side chain polymer itself is efficiently reoriented by self-organization. As a result, a highly efficient alignment process can be realized as the liquid crystal alignment film, and a liquid crystal alignment film with high alignment control ability can be obtained.

In the polymer composition of the present invention, in addition to the side chain polymer as the component (A) and the organic solvent as the component (C), nitrogen having at least one hydroxyalkyl group bonded as the component (B) A compound having 2 to 6 atoms in one molecule is used. Thereby, even in a high temperature environment over a long period of time, there is little thermal deterioration and a high voltage holding ratio is exhibited. In addition, it is possible to form a liquid crystal alignment film with little change in voltage holding ratio depending on the firing temperature. In particular, the effect was increased by using a specific compound having 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule. In addition to the fact that these phenomena are caused by the addition of the component (B), the present inventors exerted the interaction between the component (A) and the component (B), and jumped to the desired effect. (Note that these include the inventor's view on the mechanism of the present invention and do not bind the present invention).

Hereinafter, embodiments of the present invention will be described in detail.
<Manufacturing method of substrate having liquid crystal alignment film> and <Manufacturing method of liquid crystal display element>
The method for producing a substrate having the liquid crystal alignment film of the present invention is
[I] (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range;
(B) a compound having 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule, and (C) a polymer composition containing an organic solvent, having a conductive film for driving a lateral electric field Applying on the substrate to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
Have
Through the above steps, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is imparted can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

Further, by preparing a second substrate in addition to the obtained substrate (first substrate), a lateral electric field drive type liquid crystal display element can be obtained.
For the second substrate, instead of using a substrate having no lateral electric field driving conductive film instead of a substrate having a lateral electric field driving conductive film, the above steps [I] to [III] (for lateral electric field driving) Since a substrate having no conductive film is used, for the sake of convenience, in this application, the steps [I ′] to [III ′] may be abbreviated as steps), thereby providing a first liquid crystal alignment film having alignment controllability. Two substrates can be obtained.

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

The steps [I] to [III] and [IV] of the production method of the present invention will be described below.
<Process [I]>
In step [I], a polymer composition comprising a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, a polyurea, and an organic solvent on a substrate having a conductive film for driving a lateral electric field. Is applied to form a coating film.

<Board>
Although it does not specifically limit about a board | substrate, When the liquid crystal display element manufactured is a transmission type, it is preferable that a highly transparent board | substrate is used. In that case, there is no particular limitation, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.
In consideration of application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can also be used.

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

<Polymer composition>
A polymer composition is applied on a substrate having a conductive film for driving a lateral electric field, particularly on the conductive film.
The polymer composition used in the production method of the present invention comprises: (A) a photosensitive side chain polymer that exhibits liquid crystallinity within a predetermined temperature range; and (B) at least one hydroxyalkyl group bonded thereto. A compound having 2 to 6 nitrogen atoms in one molecule; and (C) an organic solvent.

<< (A) Side chain polymer >>
The component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity within a predetermined temperature range.
The (A) side chain polymer preferably reacts with light in the wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in the temperature range of 100 ° C. to 300 ° C.
The (A) side chain polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm.
The (A) side chain polymer preferably has a mesogenic group in order to exhibit liquid crystallinity in the temperature range of 100 ° C to 300 ° C.

(A) The side chain type polymer has a photosensitive side chain bonded to the main chain, and can cause a crosslinking reaction, an isomerization reaction, or a light fleece rearrangement in response to light. The structure of the side chain having photosensitivity is not particularly limited, but a structure that undergoes a crosslinking reaction or photofleece rearrangement in response to light is desirable, and a structure that causes a crosslinking reaction is more desirable. In this case, even if exposed to external stress such as heat, the achieved orientation control ability can be stably maintained for a long period of time. The structure of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a rigid mesogenic component in the side chain structure. In this case, stable liquid crystal alignment can be obtained when the side chain polymer is used as a liquid crystal alignment film.

The polymer structure has, for example, a main chain and a side chain bonded to the main chain, and the side chain includes a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group, and a tip. A structure having a photosensitive group bonded to a moiety, which undergoes a crosslinking reaction or an isomerization reaction in response to light, or a main chain and a side chain bonded to the main chain, and the side chain also serves as a mesogenic component, and A structure having a phenylbenzoate group that undergoes a photo-Fries rearrangement reaction can be obtained.

More specific examples of the structure of the photosensitive side chain polymer that can exhibit liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl , A main chain composed of at least one selected from the group consisting of radical polymerizable groups such as maleimide and norbornene and siloxane, and a side chain consisting of at least one of the following formulas (1) to (6) It is preferable that

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

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

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

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

The side chain is preferably a photosensitive side chain represented by the following formula (18) or (19).
In the formula, A, B, Y1, q1, q2, m1, and m2 have the same definition as above.
R ₁ is hydrogen _{_{atom, -NO 2, -CN, -CH =}} C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or alkyl of 1 to 5 carbon atoms Represents an oxy group.

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

The (A) side chain polymer preferably has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).
In which A, B, q1 and q2 have the same definition as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO ₂ , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;
R ₂ is a hydrogen atom, —NO ₂ , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z ₁ and Z _{2 each} represents a single bond, —CO—, —CH ₂ O—, —CH═N—, —CF ₂ —.

<< Production Method of Photosensitive Side Chain Polymer >>
The photosensitive side chain polymer capable of exhibiting the above liquid crystallinity can be obtained by polymerizing the photoreactive side chain monomer having the above photosensitive side chain and the liquid crystalline side chain monomer.

[Photoreactive side chain monomer]
The photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at the side chain portion of the polymer when the polymer is formed.
As the photoreactive group possessed by the side chain, the following structures and derivatives thereof are preferred.

More specific examples of the photoreactive side chain monomer include radical polymerizable groups such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, etc. And a polymerizable side group composed of at least one selected from the group consisting of siloxane and a photosensitive side chain consisting of at least one of the above formulas (1) to (6), preferably, for example, the above formula (7 ) To (10), a photosensitive side chain comprising at least one of the above formulas (11) to (13), and a photosensitivity represented by the above formula (14) or (15). A photosensitive side chain, a photosensitive side chain represented by the above formula (16) or (17), a photosensitive side chain represented by the above formula (18) or (19), and a photosensitivity represented by the above formula (20). Sex side chain It is preferable that it has a structure.

[Liquid crystal side chain monomer]
The liquid crystalline side chain monomer is a monomer in which a polymer derived from the monomer exhibits liquid crystallinity and the polymer can form a mesogenic group at a side chain site.
As a mesogenic group having a side chain, even if it is a group having a mesogen structure alone such as biphenyl or phenylbenzoate, or a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid Good. As the mesogenic group possessed by the side chain, the following structure is preferable.

More specific examples of liquid crystalline side chain monomers include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other radical polymerizable groups A structure having a polymerizable group composed of at least one selected from the group consisting of siloxanes and a side chain composed of at least one of the above formulas (21) to (31) is preferable.

(A) The side chain polymer can be obtained by the polymerization reaction of the above-described photoreactive side chain monomer that exhibits liquid crystallinity. Further, it can be obtained by copolymerization of a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystalline side chain monomer, or by copolymerization of a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystalline side chain monomer. it can. Furthermore, it can be copolymerized with other monomers as long as the liquid crystallinity is not impaired.

Examples of other monomers include industrially available monomers capable of radical polymerization reaction.
Specific examples of the other monomer include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and , Etc. 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl. Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Propyl-2-adamantyl methacrylate, 8-me Le -8- tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate. (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 are also used. be able to.

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

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

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

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

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- N-di-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4′-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (2′-methoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (4′-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)]-2, 6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4 ′ -Methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylamino) Coumarin), 2- (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bi (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4, 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′ -Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2 -Dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (5-2,4-cyclopentadi -1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone 3,3 ′, 4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4 '-Di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2 -(3-methyl-3H-benzothiazol-2-ylidene) -1-naphthalen-2-yl-ethanone or 2- (3-methyl-1 3- benzothiazol -2 (3H) - ylidene) -1- (2-benzoyl) ethanone, and the like. These compounds may be used alone or in combination of two or more.

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

The organic solvent used for the polymerization reaction of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the generated polymer is soluble. Specific examples are given below.

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , Γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethyl Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene Glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropiate Lenglycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n- Hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropio Acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3- Examples thereof include ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like.

These organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer | macromolecule to produce | generate, you may mix and use the above-mentioned organic solvent in the range which the polymer | macromolecule produced | generated does not precipitate.
In radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction. Therefore, it is preferable to use an organic solvent that has been deaerated to the extent possible.

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

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

[Recovery of polymer]
When recovering the produced polymer from the reaction solution of the photosensitive side chain polymer capable of exhibiting liquid crystallinity obtained by the above reaction, the reaction solution is put into a poor solvent, The coalescence can be precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating. In addition, when the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.

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

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

In the polymer composition of the present embodiment, the resin component described above may be a photosensitive side chain polymer that can all exhibit the above-described liquid crystallinity, but does not impair the liquid crystal developing ability and the photosensitive performance. Other polymers may be mixed within the range. In that 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 are made of poly (meth) acrylate, polyamic acid, polyimide, and the like and are not a photosensitive side chain polymer that can exhibit liquid crystallinity.

<< (B) component >>
<Compounds having 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule>
The polymer composition used in the present invention contains a compound having 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule.

The compound may be any one, two, or all of the following effects i) to iii) when the polymer composition used in the present invention forms a liquid crystal alignment film. There is no particular limitation. i) Improving the film density of the liquid crystal alignment film, ii) Suppressing impurities oozing out from the lower part of the liquid crystal alignment film, or iii) Improving the liquid crystal alignment film by adsorbing impurities extracted into the liquid crystal The voltage holding ratio is achieved.

The compound is not particularly limited as long as it has 2 to 6 nitrogen atoms in a molecule to which at least one hydroxyalkyl group is bonded in the compound, but from the viewpoint of availability, A compound represented by the following formula (b) is one of preferred examples.

In formula (b), R ¹ is an n-valent organic group,
L ¹ represents an alkylene or ^{N-X 1} of a single bond, 1 to 10 carbon atoms, ^{X 1} represents a hydrogen atom or an alkyl group and, ^{X 1} is form an alkylene and together with another ^{X 1} Or a ring structure may be formed by bonding to R ¹ ,
L ² represents a single bond or alkylene having 1 to 10 carbon atoms,
L ³ represents a single bond, NH or N-alkyl,
L ⁴ represents a single bond or alkylene having 1 to 10 carbon atoms,
L ⁵ represents a single bond or carbonyl, and when L ³ is NH or N-alkyl, L ⁴ and L ⁵ do not represent a single bond at the same time,
L ⁶ and L ⁷ each independently represent a linear or branched alkylene having 2 to 20 carbon atoms, and the alkylene may be substituted with one or more substituents selected from a halogen and a hydroxy group. ,
n is an integer of 2 to 6.

The n-valent organic group of R ¹ in the formula (b) is an alkyl having 2 to 10 carbon atoms, a 5- or 6-membered carbocyclic or heterocyclic ring, or 2 to 4 of these rings directly or An n-valent group in which n hydrogen atoms have been removed from an aromatic ring or alicyclic hydrocarbon having a structure bonded or condensed via a linking group, wherein the linking group that bonds the ring structure is Alkylene having 1 to 6 carbon atoms, alkenylene or alkynylene, ═NR _b (wherein R _b represents a hydrogen atom or alkyl having 1 to 4 carbon atoms), —S—, —C (O) NH—, or —C (O) —O— represents an aromatic ring or alicyclic hydrocarbon represented by R ¹ , wherein carbon atoms other than those bonded to n L1 groups are substituted with oxygen atoms, nitrogen atoms or sulfur atoms. Carbon sources other than well and bonded to n L1 groups Hydrogen atoms of the above may be substituted with alkyl or halogen having 1 to 4 carbon atoms.

In the above (b), when L ¹ is NX ¹ , the number of carbon atoms of “alkyl” in X ¹ is typically 1 to 10, preferably 1 to 6, more preferably 1 to 4, Preferably it is 1-3.

The number of carbon atoms of the alkylene of L ¹ is preferably 1-6.
The number of carbon atoms of the alkylene of L ² is preferably 2-6.

In (b), the carbon number of the “alkyl” of the N-alkyl in L ³ is typically 1 to 10, preferably 1 to 6, more preferably 1 to 4, more preferably 1 to 3. It is.

The number of carbon atoms of the alkylene of L ⁴ is preferably 2-6.

The number of carbon atoms of the alkylene of L ⁶ and L ⁷ is preferably 2-6.

In the formula (b), “halogen” means fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine, more preferably fluorine.

Among them, it is preferable from the viewpoint of liquid crystal alignment that the atom directly bonded to the carbonyl group in R ¹ in the formula (b) is a carbon atom that does not form an aromatic ring. In addition, R ¹ in the formula (b) is preferably a group derived from an aliphatic hydrocarbon from the viewpoint of liquid crystal alignment and solubility as described above, and more preferably 1 to 10 carbon atoms.
In the formula (b), n represents an integer of 2 to 6, and n is preferably 2 to 4, more preferably 2 or 3, from the viewpoint of solubility.
In the formula (b), L ⁶ and L ⁷ are preferably structures represented by the following formula (b1) from the viewpoint of reactivity, and more preferably ethylene.

In the formula (b1), R ² to R ⁵ each independently represents any of a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group. Here, the “hydrocarbon group” typically represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group, preferably 1 to 10 carbon atoms. Represents an alkyl group.

In the structure represented by the formula (b), the structure of the R ¹ portion is preferably a structure selected from the following b2-1 to b2-47. More preferably, they are b2-1 to b2-29.

As the structure of the moiety bonded to R ¹ , a structure selected from b3-1 to b3-8 is preferable.

B3-1 to b3-8 are preferable as the structure bonded to the carbon atom, and b3-1 to b3-4 are preferable as the structure bonded to the nitrogen atom.

In the formula, n2 represents an integer of 1 to 20, preferably 2 to 10, and particularly preferably 2 to 7. n3 represents an integer of 1 to 10, preferably 2 to 10, and particularly preferably 2 to 7. n4 represents an integer of 2 to 20, preferably 2 to 10, and particularly preferably 2.

Specific examples of preferable component (B) include, for example, the following compounds T1 to T9, Primid XL-552, and Primid SF-4510.

More preferable examples of the component (B) include compounds of T1 to T7.

<Production of Compound of Formula (b-1)>
The synthesis method of the compound (B) is not particularly limited, but the compound represented by the following formula (b-1) is represented by the polycarboxylic acid represented by the following formula (X2) and the following formula (X1). It can be produced by reacting with a dialcoholamine compound.

Using the compound represented by the general formula X2 and the dialcoholamine compound represented by the formula X1 using a solvent inert to the reaction if necessary, and using a condensing agent in the presence of a base if necessary. By reacting, the compound represented by the formula b-1 can be obtained.

For the amount of the reaction substrate, 0.98 to 1.05 equivalents of the dialcoholamine compound represented by the formula X1 can be used with respect to one carboxyl group of the compound represented by the formula X2.

The condensing agent is not particularly limited as long as it is used for ordinary amide synthesis. For example, Mukaiyama reagent (2-chloro-N-methylpyridinium iodide), DCC (1,3-dicyclohexylcarbodiimide), WSC (1 -Ethyl-3- (3-dimethylaminopropyl) -carbodiimide hydrochloride), CDI (carbonyldiimidazole), dimethylpropynylsulfonium bromide, propargyltriphenylphosphonium bromide, DEPC (diethyl cyanophosphate) and the like are represented by the formula X2. 1 to 1.5 equivalents can be used per 1 carboxyl group of the compound.

In the case of using a solvent, the solvent to be used is not particularly limited as long as it does not inhibit the progress of the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatic hydrocarbons such as hexane and heptane. , Cycloaliphatic hydrocarbons, chlorobenzene, dichlorobenzene and other aromatic halogenated hydrocarbons, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene Aliphatic halogenated hydrocarbons such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, ethers such as 1,4-dioxane, esters such as ethyl acetate and ethyl propionate, N, N-dimethylformamide, N, N-dimethylacetamide, N- Amides chill-2-pyrrolidone, triethylamine, tributylamine, N, N-amines dimethylaniline, pyridine, pyridine picoline, etc., include acetonitrile and dimethyl sulfoxide. These solvents may be used alone or as a mixture of two or more thereof.

It is not always necessary to add a base, but when a base is used, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, sodium hydrogen carbonate, or potassium hydrogen carbonate. Alkali metal bicarbonates such as triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene, etc. An organic base or the like can be used in an amount of 1 to 4 equivalents relative to one carboxyl group of the compound represented by the formula X2.

The reaction temperature can be set to an arbitrary temperature from −60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrarily within a range of 5 minutes to 100 hours. Can be set.

In general, for example, 1 to 20 equivalents of the compound represented by the formula X1 and 1 to 4 equivalents of WSC (1-ethyl-3- (3- Using a condensing agent such as dimethylaminopropyl) -carbodiimide hydrochloride) or CDI (carbonyldiimidazole), and if necessary, in the presence of a base such as 1 to 4 equivalents of potassium carbonate, triethylamine, pyridine, 4- (dimethylamino) pyridine, etc. The reaction is preferably carried out at 0 ° C. to the reflux temperature of these solvents for 10 minutes to 24 hours using no solvent or a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane. .

Further, known methods described in the literature from the compound represented by the formula X2, for example, a method of reacting with a chlorinating agent such as thionyl chloride, phosphorus pentachloride or oxalyl chloride, an organic acid halogen such as pivaloyl chloride or isobutyl chloroformate The compound represented by the formula b-1 can also be synthesized by reacting the compound with a compound X1 after reacting with a compound in the presence of the above-described base if necessary.

In this case, 0.98 to 1.05 equivalent of the dialcoholamine compound represented by the formula X1 can be used with respect to one carboxyl group of the compound represented by the formula X2, and if necessary, in the presence of a base. By reacting, the compound represented by the formula b-1 can be obtained.

In the case of using a solvent, the solvent to be used is not particularly limited as long as it does not inhibit the progress of the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatic hydrocarbons such as hexane and heptane. , Cycloaliphatic hydrocarbons, chlorobenzene, dichlorobenzene and other aromatic halogenated hydrocarbons, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene Aliphatic halogenated hydrocarbons such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, ethers such as 1,4-dioxane, esters such as ethyl acetate and ethyl propionate, dimethylformamide, dimethylacetamide, N -Methyl-2-pyro Amides such as Don, amines such as triethylamine, tributylamine and N, N-dimethylaniline, pyridines such as pyridine and picoline, alcohols such as methanol, ethanol and ethylene glycol, acetonitrile, dimethyl sulfoxide, sulfolane, 1, Examples include 3-dimethyl-2-imidazolidinone and water. These solvents may be used alone or as a mixture of two or more thereof.

When using a base, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal alkoxides such as sodium ethoxide and potassium tertiary butoxide, lithium diisopropylamide, lithium hexamethyldisilazane, sodium amide and the like Alkali metal amides, organic metal compounds such as tertiary butyl lithium, alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 4- (dimethylamino) ) An organic base such as pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene or the like is used in an amount of 1 to 4 equivalents relative to one ester group of the compound represented by the formula X2. it can.

Generally, 0.98 to 1.05 equivalent of compound X2 is used with respect to 1 equivalent of amino group of compound X1, and polar such as tetrahydrofuran, 1,4-dioxane, acetonitrile, N, N-dimethylformamide, etc. 0 to 90 ° C. using 1 to 3 equivalents of sodium hydride, potassium tertiary butoxide, potassium hydroxide, potassium carbonate, triethylamine or pyridine as a base, if necessary, with respect to 1 equivalent of the amino group of compound X2. The reaction is preferably carried out in the temperature range of 10 minutes to 24 hours.

<Production of compound of formula (b-2)>
The compound represented by the following formula b-2 can be produced by reacting the polyisocyanate compound represented by the following formula X3 with the compound X1.

In the reaction of isocyanate X3 and dialcohol amine X1, the amount of dialcohol amine X1 used may be 0.98 to 1.2 equivalent times the amount of one isocyanate group contained in isocyanate X3. More preferably, it is 1.0 to 1.02 equivalent times.

The reaction solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogens such as carbon tetrachloride, chloroform and 1,2-dichloroethane Hydrocarbons; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; ethyl acetate and ethyl propionate N-containing aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone; Dimethyl sulfoxide, sulfolane, etc. Sulfur aprotic polar solvent; pyridine, pyridines picoline and the like. These solvents may be used alone or as a mixture of two or more thereof. Preferred are toluene, acetonitrile and ethyl acetate, and more preferred are toluene and ethyl acetate.

The amount of the solvent used (reaction concentration) is not particularly limited, but the reaction may be carried out without using a solvent. When a solvent is used, it is 0.1 to 100 times by mass with respect to the isocyanate compound (C). These solvents may be used. The amount is preferably 0.5 to 30 times by mass, more preferably 1 to 10 times by mass.

The reaction temperature is not particularly limited, but is, for example, −90 to 150 ° C., preferably −30 to 100 ° C., and more preferably 0 to 80 ° C.

The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.

A catalyst may be added to shorten the reaction time. Examples thereof include dibutyltin dilaurate, dioctyltin bis (isooctyl thioglycolate), dibutyltin bis (isooctyl thioglycolate), dibutyltin diacetate, etc. Organotin compounds of: triethylamine, trimethylamine, tripropylamine, tributylamine, diisopropylethylamine, N, N-dimethylcyclohexylamine, pyridine, tetramethylbutanediamine, N-methylmorpholine, 1,4-diazabicyclo-2.2.2 -Amines such as octane, 1,8-diazabicyclo [5.4.0] undecene, 1,5-diazabicyclo [4.3.0] nonene-5; p-toluenesulfonic acid, methanesulfonic acid, fluorosulfuric acid, etc. of Inorganic acids such as sulfuric acid, phosphoric acid and perchloric acid; titanium compounds such as tetrabutyl titanate, tetraethyl titanate and tetraisopropyl titanate; bismuth compounds such as bismuth tris (2-ethylhexanoate); quaternary An ammonium salt etc. are mentioned. These catalysts may be used alone or in combination of two or more. These catalysts are preferably liquid or soluble in the reaction solvent.

When a catalyst is added, the catalyst may be used in an amount of 0.005 to 100 wt%, preferably 0.05 to 10 wt%, more preferably based on the total amount (mass) of the compound having an isocyanate group. 0.1 to 5 wt%. If an organotin compound, a titanium compound, or a bismuth compound is used as the catalyst, the amount is preferably 0.005 to 0.1 wt%.

The reaction can be carried out at normal pressure or under pressure, and may be batch or continuous.

<Production of compound of formula (b-3)>
For the compound represented by the following formula b-3, a polyamine compound represented by the following formula X4 and a carboxylic acid represented by the following formula X5 are reacted to form a polycarboxylic acid represented by the following formula X6. After the conversion, it can be produced by reacting the dialcoholamine compound represented by the formula X1.

In the reaction between Compound X4 and Compound X5, the amount of the reaction substrate can be 0.98 to 1.05 equivalent of Compound X5 with respect to 1 equivalent of the amino group of Compound X4.

When using a base, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal alkoxides such as sodium ethoxide and potassium tertiary butoxide, lithium diisopropylamide, lithium hexamethyldisilazane, sodium amide and the like Alkali metal amides, organic metal compounds such as tertiary butyl lithium, alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 4- (dimethylamino) ) An organic base such as pyridine and imidazole 1,8-diazabicyclo [5.4.0] undecene can be used in an amount of 1 to 4 equivalents based on one amino group of the compound represented by the formula X4.

In general, for example, using Compound X4 and 0.98 to 1.05 equivalent of Compound X5 with respect to 1 equivalent of the amino group of Compound X4, tetrahydrofuran, 1,4-dioxane, acetonitrile, N, N— In a polar solvent such as dimethylformamide, if necessary, 1 to 3 equivalents of sodium hydride, potassium tertiary butoxide, potassium hydroxide, potassium carbonate, triethylamine, pyridine and the like are used as a base with respect to 1 equivalent of the amino group of compound X4. The reaction is preferably carried out in the temperature range of 0 to 90 ° C. for 10 minutes to 24 hours.

The reaction conditions between compound X6 and compound X1, the equivalent amount of the substrate, and the like conform to the reaction conditions between compound X2 and compound X1.

<Production of compound of formula (b-4)>
For the compound represented by the following formula b-4, a polyamine compound represented by the following formula X4 and an acid halide represented by the following formula X7 were reacted to obtain a polyamide represented by the following formula X8. Then, it can manufacture by making the dialcoholamine compound represented by the said formula X1 react.

Compound X7 requires the above-mentioned compound X5 in a known manner, for example, a method of reacting with a chlorinating agent such as thionyl chloride, phosphorus pentachloride or oxalyl chloride, an organic acid halide such as pivaloyl chloride or isobutyl chloroformate, and the like. Then, it can be obtained by reacting in the presence of the base described above. The reaction conditions in the reaction between X7 and X4, the equivalent amount of the substrate, and the like are in accordance with the reaction conditions between the compound X2 and the compound X1.

<Production of compound of formula (b-5)>
The compound represented by the following formula b-5 is converted into a compound represented by the following formula X10 by reacting an acrylic acid derivative represented by the following formula X9 with the above compound X1, and then converted to the above formula X4. It can manufacture by making the polyamine compound represented by these react.

<Production of compound of formula (b-6)>
With respect to the compound represented by the following formula b-6, the acrylic acid derivative represented by the above formula X9 and the above compound X4 are reacted to convert to the compound represented by the following formula X11, and then the above compound X1 It can manufacture by making it react.

<Production of other compounds of formula (b)>
After that, various kinds of compounds (B) can be synthesized by applying the above reaction conditions.

In the above formulas X1 to X9 and b-1 to b-6, R ¹ , n2, L ⁶ , L ⁷ and n represent the same meaning as described above, J represents a chlorine atom, bromine atom, iodine atom, C ₁ -C ₄ alkylcarbonyloxy group (eg pivaloyloxy group), C ₁ -C ₄ alkyl sulfonate group (eg methanesulfonyloxy group), C ₁ -C ₄ haloalkyl sulfonate group (eg trifluoromethanesulfonyloxy group), aryl Represents a good leaving group such as a sulfonate group (for example, benzenesulfonyloxy group, p-toluenesulfonyloxy group) or an azolyl group (for example, imidazol-1-yl group), J ² represents Cl and the like; ³ represents an alkoxy group such as a methoxy group or an ethoxy group.

A compound having 2 to 6 nitrogen atoms to which at least one hydroxyalkyl group is bonded in one molecule will not exert sufficient liquid crystal alignment regulating ability or will have an adverse effect from the viewpoint of solubility or too little if too much. The effects of the present invention cannot be obtained. Therefore, the addition amount of the compound having 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in the molecule is preferably 0.1 to 20% by mass with respect to the polymer of component (A). 1 to 10% by mass is more preferable.

<< (C) Organic solvent >>
The organic solvent used for the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below.
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4 Methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, etc. Is mentioned. These may be used alone or in combination.

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

The following are mentioned as a specific example of the solvent (poor solvent) which improves the uniformity of film thickness and surface smoothness.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipro Lenglycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, 1-hexanol, n-hexane, n-pentane, n-octane Diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1 -Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- 1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactyl isoamyl ester, etc. Examples include solvents having surface tension.

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

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

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Examples thereof include propyltrimethoxysilane and N-bis (oxyethylene) -3-aminopropyltriethoxysilane.

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

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

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

A photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.
As photosensitizers, aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, 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-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene)- 3-methylbenzothia Phosphorus, 2- (β-naphthoylmethylene) -3-methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene)- 3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α-naphthoylmethylene) ) -3-methylbenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthoxazoline, 2- (4-biphenoyl) Methylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β- Ftoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p -Methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol And 9-anthracenecarboxylic acid), benzopyran, azoindolizine, melocoumarin and the like.
Aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferred.

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

The method for applying the polymer composition described above onto a substrate having a conductive film for driving a lateral electric field is not particularly limited.
In general, the application method is generally performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), or a spray method, and these may be used depending on the purpose.

After the polymer composition is applied on a substrate having a conductive film for driving a horizontal electric field, it is 50 to 200 ° C., preferably 50 to 200 ° C. by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven. The solvent can be evaporated at 150 ° C. to obtain a coating film. The drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain polymer.
If the thickness of the coating film is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is.
In addition, it is also possible to provide the process of cooling the board | substrate with which the coating film was formed to room temperature after the [I] process and before the following [II] process.

<Process [II]>
In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When irradiating the surface of the coating film with polarized ultraviolet rays, the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction. As the ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used. For example, ultraviolet light having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.

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

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

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

By having the above steps, the production method of the present invention can realize highly efficient introduction of anisotropy into the coating film. And a board | substrate with a liquid crystal aligning film can be manufactured highly efficiently.

<Process [IV]>
The step [IV] is performed in the same manner as in the above [I ′] to [III ′], similarly to the substrate (first substrate) obtained in [III] and having the liquid crystal alignment film on the conductive film for lateral electric field driving. The obtained liquid crystal alignment film-attached substrate (second substrate) having no conductive film is placed oppositely so that both liquid crystal alignment films face each other through liquid crystal, and a liquid crystal cell is formed by a known method. This is a step of manufacturing a lateral electric field drive type liquid crystal display element. In the steps [I ′] to [III ′], a substrate having no lateral electric field driving conductive film was used in place of the substrate having the lateral electric field driving conductive film in the step [I]. It can be carried out in the same manner as in steps [I] to [III]. Since the difference between the steps [I] to [III] and the steps [I ′] to [III ′] is only the presence or absence of the conductive film, the description of the steps [I ′] to [III ′] is omitted. To do.

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

The manufacturing method of the board | substrate with a coating film of this invention irradiates the polarized ultraviolet-ray, after apply | coating a polymer composition on a board | substrate and forming a coating film. Next, by heating, high-efficiency anisotropy is introduced into the side chain polymer film, and a substrate with a liquid crystal alignment film having a liquid crystal alignment control ability is manufactured.
The coating film used in the present invention realizes the introduction of highly efficient anisotropy into the coating film by utilizing the principle of molecular reorientation induced by the side chain photoreaction and liquid crystallinity. . In the production method of the present invention, in the case of a structure having a photocrosslinkable group as a photoreactive group in the side chain polymer, after forming a coating film on the substrate using the side chain polymer, polarized ultraviolet rays are formed. After irradiation and then heating, a liquid crystal display element is formed.

Hereinafter, an embodiment using a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group is the first embodiment, a structure having a photofleece rearrangement group or a group causing isomerization as a photoreactive group An embodiment using the side chain type polymer will be referred to as a second embodiment.

FIG. 1 schematically shows an anisotropic introduction process in a method for producing a liquid crystal alignment film using a side chain polymer having a structure having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. It is a figure of one example demonstrated to. FIG. 1 (a) is a diagram schematically showing the state of the side chain polymer film before irradiation with polarized light, and FIG. 1 (b) is a schematic diagram showing the state of the side chain polymer film after irradiation with polarized light. FIG. 1 (c) is a diagram schematically showing the state of the side-chain polymer film after heating, and particularly when the introduced anisotropy is small, that is, the first aspect of the present invention. 1 is a schematic diagram when the ultraviolet ray irradiation amount in the step [II] is within a range of 1% to 15% of the ultraviolet ray irradiation amount that maximizes ΔA.

FIG. 2 is a schematic illustration of anisotropy introduction treatment in a method for producing a liquid crystal alignment film using a side chain polymer having a structure having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. It is a figure of one example demonstrated to. FIG. 2A is a diagram schematically showing the state of the side chain polymer film before irradiation with polarized light, and FIG. 2B is a schematic diagram showing the state of the side chain polymer film after irradiation with polarized light. FIG. 2 (c) is a diagram schematically showing the state of the side-chain polymer film after heating, and particularly when the introduced anisotropy is large, that is, the first aspect of the present invention. 1 is a schematic diagram when the ultraviolet ray irradiation amount in the step [II] is within a range of 15% to 70% of the ultraviolet ray irradiation amount that maximizes ΔA.

FIG. 3 shows a side chain polymer having a structure having a photo-isomerizable group as a photoreactive group or a photo-Fleece rearrangement group represented by the above formula (18) in the second embodiment of the present invention. It is a figure of one example which illustrates typically the introduction process of anisotropy in the manufacturing method of the used liquid crystal aligning film. FIG. 3A is a diagram schematically showing the state of the side chain polymer film before polarized light irradiation, and FIG. 3B is a schematic diagram of the state of the side chain polymer film after polarized light irradiation. FIG. 3 (c) is a diagram schematically showing the state of the side-chain polymer film after heating, and particularly when the introduced anisotropy is small, that is, the first aspect of the present invention. 2 is a schematic diagram when the ultraviolet irradiation amount in the step [II] is within a range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA.

FIG. 4 shows the production of a liquid crystal alignment film using a side chain polymer having a structure having a photo-Fleece rearrangement group represented by the above formula (19) as a photoreactive group in the second embodiment of the present invention. It is a figure of one example which illustrates typically the introduction processing of anisotropy in a method. FIG. 4A is a diagram schematically showing the state of the side chain polymer film before irradiation with polarized light, and FIG. 4B is a schematic diagram of the state of the side chain polymer film after irradiation with polarized light. FIG. 4 (c) is a diagram schematically showing the state of the side-chain polymer film after heating. In particular, when the introduced anisotropy is large, that is, 2 is a schematic diagram when the ultraviolet irradiation amount in the step [II] is within a range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA.

In the first embodiment of the present invention, in the process of introducing anisotropy into the coating film, the ultraviolet irradiation amount in the step [II] is in the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA. In the case, first, the coating film 1 is formed on the substrate. As shown to Fig.1 (a), in the coating film 1 formed on the board | substrate, it has a structure where the side chain 2 arranges at random. According to the random arrangement of the side chain 2 of the coating film 1, the mesogenic component and the photosensitive group of the side chain 2 are also randomly oriented, and the coating film 1 is isotropic.

In the first embodiment of the present invention, in the treatment for introducing anisotropy into the coating film, the ultraviolet irradiation amount in the step [II] is in the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ΔA. In the case, first, the coating film 3 is formed on the substrate. As shown in FIG. 2A, the coating film 3 formed on the substrate has a structure in which the side chains 4 are randomly arranged. According to the random arrangement of the side chains 4 of the coating film 3, the mesogenic components and the photosensitive groups of the side chains 4 are also randomly oriented, and the coating film 2 is isotropic.

In the second embodiment of the present invention, a side chain type having a structure having a photo-isomerizable group or a photo-Fleece rearrangement group represented by the above formula (18) in the treatment for introducing anisotropy into the coating film. In the case of using a liquid crystal alignment film using a polymer, when the ultraviolet irradiation amount in the step [II] is in the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, first, The coating film 5 is formed. As shown in FIG. 3A, the coating film 5 formed on the substrate has a structure in which the side chains 6 are randomly arranged. According to the random arrangement of the side chain 6 of the coating film 5, the mesogenic component and the photosensitive group of the side chain 6 are also randomly oriented, and the side chain type polymer film 5 is isotropic.

In the second embodiment of the present invention, liquid crystal alignment using a side chain type polymer having a structure having a light Fleece rearrangement group represented by the above formula (19) in the treatment for introducing anisotropy into the coating film In the case of using a film, when the ultraviolet irradiation amount in the step [II] is within the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, first, the coating film 7 is formed on the substrate. . As shown in FIG. 4A, the coating film 7 formed on the substrate has a structure in which the side chains 8 are arranged at random. According to the random arrangement of the side chains 8 of the coating film 7, the mesogenic components and the photosensitive groups of the side chains 8 are also randomly oriented, and the coating film 7 is isotropic.

In the first embodiment, when the ultraviolet irradiation amount in the step [II] is within the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA, On the other hand, polarized ultraviolet rays are irradiated. Then, as shown in FIG. 1B, the photosensitive group of the side chain 2a having the photosensitive group among the side chains 2 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to dimerization reaction or the like. Causes a photoreaction. As a result, the density of the side chain 2a that has undergone photoreaction becomes slightly higher in the polarization direction of the irradiated ultraviolet light, and as a result, very small anisotropy is imparted to the coating film 1.

In the first embodiment, when the ultraviolet irradiation amount in the step [II] is within the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ΔA, On the other hand, polarized ultraviolet rays are irradiated. Then, as shown in FIG. 2B, the photosensitive group of the side chain 4a having the photosensitive group among the side chains 4 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to dimerization reaction or the like. Causes a photoreaction. As a result, the density of the side chain 4a that has undergone photoreaction increases in the polarization direction of the irradiated ultraviolet light, and as a result, a small anisotropy is imparted to the coating film 3.

In the second embodiment of the present invention, using a liquid crystal alignment film using a photoisomerizable group or a side chain polymer having a structure having a photo-Fleece rearrangement group represented by the above formula (18), [II] When the ultraviolet ray irradiation amount in the step is in the range of 1% to 70% of the ultraviolet ray irradiation amount that maximizes ΔA, the isotropic coating film 5 is irradiated with polarized ultraviolet rays. Then, as shown in FIG. 3 (b), the photosensitive group of the side chain 6a having the photosensitive group among the side chains 6 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to light fleece rearrangement or the like. Causes a photoreaction. As a result, the density of the side chain 6a subjected to photoreaction becomes slightly higher in the polarization direction of the irradiated ultraviolet rays, and as a result, very small anisotropy is imparted to the coating film 5.

In the second embodiment of the present invention, the amount of ultraviolet irradiation in the step [II] is obtained using a coating film using a side chain polymer having a structure having a photo-Fleece rearrangement group represented by the above formula (19). Is within the range of 1% to 70% of the amount of UV irradiation that maximizes ΔA, the isotropic coating film 7 is irradiated with polarized UV light. Then, as shown in FIG. 4 (b), the photosensitive group of the side chain 8a having the photosensitive group among the side chains 8 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to light fleece rearrangement or the like. Causes a photoreaction. As a result, the density of the side chain 8a that has undergone photoreaction 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 the first embodiment, when the ultraviolet irradiation amount in the step [II] is within the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA, the coating film 1 after the polarized light irradiation 1 Is heated to a liquid crystal state. Then, as shown in FIG.1 (c), in the coating film 1, the amount of the generated crosslinking reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular thereto. In this case, since the amount of the crosslinking reaction generated in the direction parallel to the polarization direction of the irradiated ultraviolet ray is very small, this crosslinking reaction site functions as a plasticizer. Therefore, the liquid crystallinity in the direction perpendicular to the polarization direction of the irradiated ultraviolet light is higher than the liquid crystallinity in the parallel direction, and the side chain 2 containing the mesogenic component is reoriented by self-organizing in the direction parallel to the polarization direction of the irradiated ultraviolet light. 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 first embodiment, when the ultraviolet irradiation amount in the step [II] is in the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the coating film after polarized light irradiation 3 is heated to a liquid crystal state. Then, as shown in FIG. 2C, in the side chain type polymer film 3, the amount of the generated crosslinking reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular thereto. Therefore, the side chain 4 containing the mesogenic component is reoriented by self-organizing in a direction parallel to the polarization direction of the irradiated ultraviolet light. 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 the second embodiment, a coating film using a side-chain polymer having a structure having a photo-isomerizable group or a photo-Fleece rearrangement group represented by the above formula (18) is used. Thus, when the ultraviolet irradiation amount in the step [II] is within the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the coating film 5 after polarized irradiation is heated to be in a liquid crystal state. Then, as shown in FIG.3 (c), in the coating film 5, the quantity of the produced | generated light fleece rearrangement reaction differs between the direction parallel to the polarization direction of irradiation ultraviolet rays, and a perpendicular | vertical direction. In this case, since the liquid crystal alignment force of the light fleece rearrangement generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet light is stronger than the liquid crystal alignment force of the side chain before the reaction, it is self-organized in the direction perpendicular to the polarization direction of the irradiated ultraviolet light. The side chain 6 containing the mesogenic component is reoriented. As a result, the very small anisotropy of the coating film 5 induced by the photofleece rearrangement reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 5.

Similarly, in the second embodiment, a coating film using a side chain type polymer having a structure having a photofleece rearrangement group represented by the above formula (19) is used. When the ultraviolet irradiation amount is in the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the coated film 7 after polarized irradiation is heated to a liquid crystal state. Then, as shown in FIG. 4 (c), in the side chain polymer film 7, the amount of the generated light fleece rearrangement reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet light and the direction perpendicular thereto. . Since the anchoring force of the optical fleece rearrangement 8 (a) is stronger than that of the side chain 8 before the rearrangement, when a certain amount or more of the optical fleece rearrangement occurs, it is self-assembled in a direction parallel to the polarization direction of the irradiated ultraviolet light. The side chain 8 containing the mesogenic component is reoriented. As a result, the small anisotropy of the coating film 7 induced by the photofleece 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 is a liquid crystal alignment film having anisotropy introduced with high efficiency and excellent alignment control ability by sequentially performing irradiation of polarized ultraviolet rays on the coating film and heat treatment. can do.

And in the coating film used for the method of the present invention, the irradiation amount of polarized ultraviolet rays to the coating film and the heating temperature in the heat treatment are optimized. Thereby, introduction of anisotropy into the coating film with high efficiency can be realized.

The optimum irradiation amount of polarized ultraviolet rays for introducing highly efficient anisotropy into the coating film used in the present invention is such that the photosensitive group undergoes photocrosslinking reaction, photoisomerization reaction, or photofries rearrangement reaction in the coating film. Corresponds to the irradiation amount of polarized ultraviolet rays to optimize the amount. As a result of irradiating the coating film used in the present invention with polarized ultraviolet rays, if the photo-crosslinking reaction, photoisomerization reaction, or photo-fleece rearrangement reaction has few photosensitive groups in the side chain, the amount of photoreaction will not be sufficient. . In that case, sufficient self-organization does not proceed even after heating. On the other hand, as a result of irradiating polarized ultraviolet rays to the structure having a photocrosslinkable group in the coating film used in the present invention, the crosslinking reaction between the side chains is caused when the photosensitive group of the side chain undergoing the crosslinking reaction becomes excessive. Too much progress. In that case, the resulting film may become rigid and hinder the progress of self-assembly by subsequent heating. In addition, when the coating film used in the present invention is irradiated with polarized ultraviolet rays to the structure having the light Fleece rearrangement group, if the photosensitive group of the side chain that undergoes the light Fleece rearrangement reaction becomes excessive, the liquid crystallinity of the coating film Will drop too much. In that case, the liquid crystallinity of the obtained film is also lowered, which may hinder the progress of self-assembly by subsequent heating. Furthermore, when irradiating polarized ultraviolet light to a structure having a photo-fleece rearrangement group, if the amount of ultraviolet light irradiation is too large, the side-chain polymer is photodegraded, preventing the subsequent self-organization by heating. It may become.

Therefore, in the coating film used in the present invention, the optimum amount of the photopolymerization reaction, photoisomerization reaction, or photofleece rearrangement reaction of the side chain photosensitive group by irradiation with polarized ultraviolet rays is the side chain polymer film. It is preferably 0.1 to 40 mol%, more preferably 0.1 to 20 mol% of the photosensitive group possessed by. By making the amount of the photo-reactive side chain photosensitive group within such a range, the self-organization in the subsequent heat treatment proceeds efficiently, and the formation of highly efficient anisotropy in the film is possible. Become.

In the coating film used in the method of the present invention, by optimizing the irradiation amount of polarized ultraviolet rays, photocrosslinking reaction or photoisomerization reaction of photosensitive groups or photofleece rearrangement reaction in the side chain of the side chain polymer film Optimize the amount of. Then, in combination with the subsequent heat treatment, highly efficient introduction of anisotropy into the coating film used in the present invention is realized. In that case, a suitable amount of polarized ultraviolet rays can be determined based on the evaluation of ultraviolet absorption of the coating film used in the present invention.

That is, with respect to the coating film used in the present invention, the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorption in the vertical direction after the irradiation with the polarized ultraviolet ray are measured. From the measurement result of ultraviolet absorption, ΔA, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays, is evaluated. Then, the maximum value of ΔA (ΔAmax) realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet light that realizes it are obtained. In the production method of the present invention, a preferable amount of polarized ultraviolet rays to be irradiated in the production of the liquid crystal alignment film can be determined on the basis of the amount of polarized ultraviolet rays to realize this ΔAmax.

In the production method of the present invention, the amount of irradiation of polarized ultraviolet rays onto the coating film used in the present invention is preferably in the range of 1% to 70% of the amount of polarized ultraviolet rays that realizes ΔAmax. More preferably, it is within the range of 50%. In the coating film used in the present invention, the irradiation amount of polarized ultraviolet light within the range of 1% to 50% of the amount of polarized ultraviolet light that realizes ΔAmax is 0. 0% of the entire photosensitive group of the side chain polymer film. 1 mol% to 20 mol% corresponds to the amount of polarized ultraviolet light that undergoes a photocrosslinking reaction.

From the above, in the production method of the present invention, in order to achieve highly efficient anisotropy introduction into the coating film, a suitable heating temperature as described above is set based on the liquid crystal temperature range of the side chain polymer. It is good to decide. Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 100 ° C. to 200 ° C., the heating temperature after irradiation with polarized ultraviolet light is desirably 90 ° C. to 190 ° C. By doing so, greater anisotropy is imparted to the coating film used in the present invention.

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

As described above, the lateral electric field drive type liquid crystal display element substrate produced by the composition of the present invention and the method using the composition or the lateral electric field drive type liquid crystal display element having the substrate has excellent reliability. It can be suitably used for a large-screen high-definition liquid crystal television.

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

The analyzer and analysis conditions employed in the synthesis of the specific glycidyl compound of the present invention are as follows.
(Measurement of ¹ H-NMR)
Apparatus: Varian NMR System 400NB (400 MHz) (manufactured by Varian)
Measuring solvent: CDCl ₃ (deuterated chloroform), DMSO-d ₆ (deuterated dimethyl sulfoxide)
Reference substance: TMS (tetramethylsilane) (δ: 0.0 ppm, ¹ H), CDCl ₃ (δ: 77.0 ppm, ¹³ C)

Abbreviations used in the examples are as follows.
<Methacrylic monomer>

MA1 was synthesized by a synthesis method described in a patent document (WO2011-084546).
MA2 was synthesized by the synthesis method described in the patent document (Japanese Patent Laid-Open No. 9-118717).

<Hydroxyalkyl compound>
T1: Primid XL-552: (N, N, N ′, N′-tetrakis- (2-hydroxyethyl) -adipamide)
T2: Primid SF-4510
T1 and T2 used were purchased commercially.

<Comparative example>
X1: Tetraglycidyldiaminodiphenylmethane (YH-434L)
X1 was a commercially purchased product.
<Organic solvent>
THF: Tetrahydrofuran NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve

<Polymerization initiator>
AIBN: 2,2′-azobisisobutyronitrile

<Polymerization Example 1: Polymethacrylic acid>
MA1 (13.3 g, 40.0 mmol) and MA2 (18.4 g, 60.0 mmol) were dissolved in THF (182.3 g), and after deaeration with a diaphragm pump, AIBN (0.82 g, 5.0 mmol) was added and deaeration was performed again. Thereafter, the mixture was reacted at 50 ° C. for 30 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (1500 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain a methacrylate polymer powder.
56.0 g of NMP was added to 6.0 g of the obtained powder, and the mixture was stirred at room temperature for 3 hours. A methacrylate polymer solution (M1) having a solid content concentration of 10.0 wt% was obtained. The polymer was completely dissolved at the end of stirring.

<Polymerization Example 2: Polymethacrylic acid>
After MA1 (6.64 g, 20.0 mmol) and MA2 (24.5 g, 80.0 mmol) were dissolved in THF (181.2 g) and deaerated with a diaphragm pump, AIBN (0.82 g, 5.0 mmol) was added and deaeration was performed again. Thereafter, the mixture was reacted at 50 ° C. for 30 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (1500 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain a methacrylate polymer powder.

54.0 g of NMP was added to 6.0 g of the obtained powder, and the mixture was stirred at room temperature for 3 hours. A methacrylate polymer solution (M2) having a solid content concentration of 10.0 wt% was obtained. The polymer was completely dissolved at the end of stirring.

<Synthesis Example 1>
Synthesis of specific hydroxyl alkyl compound (T3)

To a acetonitrile solution (125 g) of piperazine (25.0 g, 300 mmol), methyl acrylate (56.8 g, 660 mmol) was added dropwise over 1 hour, followed by stirring at room temperature for 2 hours. The resulting solution was concentrated to give T3-1 as a colorless oil. (Yield: 77.8 g, Yield: 100%)
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 3.58 (6H, s), 2.54-2.50 (4H, m), 2.46-2.33 (4H, m), 32.33 (8H, br).

A DMF solution (129 g) to which T3-1 (12.9 g, 50 mmol), diethanolamine (11.0 g, 105 mmol) and sodium ethoxide (0.34 g, 5 mmol) were added was stirred at room temperature for 18 hours. Thereafter, the precipitated white solid was collected by filtration and recrystallized from methanol (130 g) to obtain T3. (Yield: 11.6 g, Yield: 57.3%)
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 4.84-4.82 (2H, t), 4.66-4.64 (2H, t), 3.53-3.30 (16H, m), 2.49 (8H, br), 2.36 (8H, br).

<Synthesis Example 2>
Synthesis of specific hydroxyl alkyl compound (T4)

Methyl acrylate (5.68 g, 66 mmol) was added dropwise to an acetonitrile solution (31.5 g) of 1,3-di-4-piperidylpropane (6.31 g, 30 mmol) over 1 hour, followed by stirring at room temperature for 2 hours. did. The resulting solution was concentrated to give T4-1 as a colorless oil. (Yield: 11.5 g, Yield: 100%)
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 3.68 (6H, s), 2.86 (4H, d), 2.67 (4H, t), 2.52 (4H, t), 1.96-1.92 (4H, m ), 1.66-1.64 (4H, m), 1.27 (2H, br), 1.12 (10H, br).

An ethanol solution (57.3 g) containing T4-1 (11.5 g, 30 mmol), diethanolamine (9.46 g, 90 mmol) and sodium ethoxide (0.20 g, 3 mmol) was stirred at room temperature for 18 hours. After concentration, the resulting solid was recrystallized with IPA (76.4 g) to obtain T4. (Yield: 5.60 g, Yield: 35.5%)
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 4.86 (2H, br), 4.67 (2H, br), 3.50-3.30 (16H, m), 2.82-2.78 (4H, m), 2.55-2.47 (8H, m), 1.87-1.81 (4H, m), 1.60-1.57 (4H, m), 1.25-1.03 (12H, m).

<Synthesis Example 3>
Synthesis of specific hydroxyl alkyl compound (T5)

To a DMF solution (39.3 g) of diethanolamine (15.8 g, 150 mmol),

dicyclohexylmethane

4,4′-diisocyanate (11.5 g, 30 mmol) was added dropwise at room temperature over 1 hour, and at room temperature for 18 hours. Stir. After adding THF (120g) to the obtained solution and stirring at room temperature for 2 hours, the depositing white solid was collect | recovered by filtration and T5 was obtained. (Yield: 10.8 g, Yield: 45.7%)
¹ H-NMR (400 MHz, DMSO-d, δ ppm): 6.43 (2H, d), 6.05 (2H, d), 5.04 (2H, br), 4.88-4.86 (2H, t), 3.63 (1H, br) , 3.51-3.44 (8H, m), 3.34-3.24 (9H, m), 1.78-1.65 (4H, m), 1.51-1.41 (6H, m), 1.19-1.03 (8H, m). 0.92-0.83 ( 2H, m).

<Synthesis Example 4>
Synthesis of specific hydroxyl alkyl compound (T6)

Methyl acrylate (5.68 g, 66 mmol) was added dropwise to an acetonitrile solution (25.2 g) of 4,4′-bipiperidine (5.05 g, 30 mmol) over 1 hour, and the mixture was stirred at room temperature for 2 hours. The resulting solution was concentrated to obtain T6-1 as a colorless oil. (Yield: 10.3 g, Yield: 99.9%)
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 3.68 (6H, s), 2.93-2.89 (4H, m), 2.69-265 (4H, m), 2.55-2.50 (4H, t), 1.96 -1.89 (4H, m), 1.69-1.66 (4H, m), 1.30-1.23 (4H, m), 1.09-0.99 (2H, m).

An ethanol solution (51.0 g) containing T6-1 (10.2 g, 30 mmol), diethanolamine (9.46 g, 90 mmol) and sodium ethoxide (0.20 g, 3 mmol) was stirred at room temperature for 18 hours. After concentration, the obtained solid was recrystallized with IPA (60.5 g) to obtain T6. (Yield: 4.92 g, Yield: 33.7%)
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 4.83 (2H, br), 4.66-4.33 (2H, t), 3.50-3.29 (16H, m), 2.86-2.83 (4H, m), 2.51 -2.41 (8H, m), 1.83-1.78 (4H, m), 1.61-1.58 (4H, m), 1.18-0.94 (6H, m).

<Synthesis Example 5>
Synthesis of specific hydroxyl alkyl compound (T7)

Methyl acrylate (56.0 g, 650 mmol) was added dropwise to a methanol solution (263 g) of diethanolamine (52.6 g, 500 mmol) over 1 hour, and the mixture was stirred at room temperature for 2 hours. The resulting solution was concentrated to obtain T7-1 as a colorless oil. (Yield: 99.7 g, Yield: 95.9%)
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 4.26 (2H, t), 3.54 (3H, s), 3.37-3.33 (4H, m), 2.73-2.70 (2H, m), 2.46 (4H , t), 2.38 (2H, t).

An ethanol solution (43.1 g) to which T7-1 (22.9 g, 120 mmol), piperazine (4.31 g, 50 mmol) and sodium ethoxide (0.34 g, 5 mmol) were added was stirred under reflux conditions for 18 hours. Then, it was concentrated, and T7 was obtained by repulping the obtained solid with IPA (86.2 g). (Yield: 6.46 g, Yield: 31.9%)
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 4.70 (4H, br), 3.52-3.29 (16H, m), 2.56-2.25 (4H, m), 2.50 (8H, br), 2.27 (8H , br).

<Example 1>
BCS 33.33 g and T1 0.15 g were added to 50.0 g of the methacrylic polymer solution M1 obtained in Polymerization Example 1, and the mixture was stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent AL1.

<Examples 2 to 19>
Liquid crystal aligning agents AL2 to AL19 of Examples 2 to 19 were obtained in the same manner as in Example 1 except that the compositions shown in Table 1 were used, and liquid crystal cells were produced using these. Further, the voltage holding ratio (VHR) and the afterimage characteristics were measured by the same method as in Example 1. The results are also shown in Table 1.

<Comparative Examples 1 to 3 (Controls 1 to 3)>
Using the polymer solutions (M1, M2) obtained in Polymerization Examples 1 and 2, a liquid crystal cell was prepared in the same manner as in the case of using the liquid crystal aligning agent (AL1), and VHR and afterimage characteristics were obtained in the same manner. Evaluated.

[Production of liquid crystal cell]
Using the liquid crystal aligning agent (AL1) obtained above, a liquid crystal cell was prepared according to the procedure shown below.
The substrate used was a glass substrate having a size of 30 mm × 40 mm and a thickness of 0.7 mm, on which comb-like pixel electrodes formed by patterning an ITO film were arranged.
The pixel electrode has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements whose central portion is bent. The width in the short direction of each electrode element is 10 μm, and the distance between the electrode elements is 20 μm. Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements. It has a shape that bends and resembles a bold-faced koji.

Each pixel is divided into upper and lower portions with a central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel. The electrode elements of the pixel electrode are formed so as to form an angle of −15 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It is comprised so that it may become a reverse direction.
The liquid crystal aligning agent (AL1) obtained above was spin-coated on the prepared substrate with electrodes. Subsequently, it dried for 90 second with a 70 degreeC hotplate, and formed the liquid crystal aligning film with a film thickness of 100 nm. Next, the coating film surface was irradiated with 313 nm ultraviolet rays through a polarizing plate at 15 mJ / cm ² and then heated on a hot plate at 150 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film.

Further, a coating film was similarly formed on a glass substrate having a columnar spacer with a height of 4 μm on which no electrode was formed as a counter substrate, and an orientation treatment was performed. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one substrate. Next, the other substrate was bonded so that the liquid crystal alignment film faces each other and the alignment direction was 0 °, and then the sealing agent was thermally cured to produce an empty cell. A liquid crystal cell having a configuration of an IPS (In-Plane Switching) mode liquid crystal display element is injected into this empty cell by a vacuum injection method by injecting liquid crystal MLC-2041 (manufactured by Merck), sealing the injection port. Obtained.

Regarding the liquid crystal aligning agents (AL2 to AL9) obtained in Examples 2 to 19, liquid crystal cells were prepared using the same method as AL1.

(Orientation observation)
A liquid crystal cell was produced by the above method. Thereafter, reorientation treatment was performed in an oven at 120 ° C. for 60 minutes. Thereafter, the polarizing plate was observed through a polarizing microscope in a crossed Nicol state.
When the liquid crystal cell was rotated to be in a black display state, a state in which there was no bright spot or poor alignment was considered good. As a result of observing the orientation, all the examples and comparative examples (

controls

1, 2, 3) showed good liquid crystal orientation.

(Voltage holding ratio (VHR) evaluation)
Using the liquid crystal cell produced above, an AC voltage of 16 Vpp was applied for 168 hours at a frequency of 30 Hz in a constant temperature environment of 70 ° C. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited and left as it was at room temperature for 1 hour. A voltage of 1 V was applied to the obtained cell at a temperature of 70 ° C. for 60 μs, a voltage after 16.67 ms was measured, and how much the voltage could be held was calculated as a voltage holding ratio (VHR). Further, VHR after a constant temperature environment of 70 ° C. was calculated, and VHR (initial) −VHR (after aging) was shown as ΔVHR in Table 1 below. The voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technica.

The results were as shown in Table 1 below.

As shown in Table 1, the examples according to the present invention are more detailed in Examples 1, 3, 10 than the comparative example in which the component (A) is common and the component (B) is not included. , 12, 14, 16 and Control 1, and Examples 4 to 9 and Control 2 have a smaller ΔVHR value, and the voltage holding ratio (VHR) does not decrease due to thermal aging. I understand.

A liquid crystal cell was produced in the same manner as the above liquid crystal cell production method except that the firing temperature was 100 ° C. and 150 ° C.

As shown in Table 2, in the example according to the present invention, the initial value of the voltage holding ratio (VHR) is improved compared to the comparative examples (controls 1 and 3) by including the component (B). It can be seen that there is little change in the voltage holding ratio (VHR) due to the baking temperature, and a good voltage holding ratio can be obtained at a low baking temperature.

<Afterimage evaluation>
The liquid crystal cell for IPS mode prepared in Example 1 is installed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and the backlight is turned on with no voltage applied, and the brightness of the transmitted light The arrangement angle of the liquid crystal cell was adjusted so as to be the smallest. Then, the rotation angle when the liquid crystal cell was rotated from the angle at which the second region of the pixel was darkest to the angle at which the first region was darkest was calculated as the initial orientation azimuth. Next, an alternating voltage of 16 V _PP was applied in a 70 ° C. oven at a frequency of 30 Hz for 168 hours. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited and left as it was at room temperature for 1 hour. After standing, the orientation azimuth was measured in the same manner, and the difference in orientation azimuth before and after AC driving was calculated as an angle Δ (deg.). The same measurement was performed in other examples. As a result, in all the examples, the angle Δ was 0.1 or less.

FIG.
1 Side

chain polymer membrane

2, 2a Side chain Fig. 2
3 Side

chain polymer membrane

4, 4a Side chain Fig. 3
5 Side

chain polymer membrane

6, 6a Side chain Fig. 4
7 Side

chain polymer membrane

8, 8a Side chain

Claims

(A) a photosensitive side chain polymer that exhibits liquid crystallinity within a predetermined temperature range;
(B) A compound having 2 to 6 nitrogen atoms in one molecule to which at least one hydroxyalkyl group is bonded, and (C) a composition containing an organic solvent.
The composition according to claim 1, wherein the component (A) has a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofleece transition.
The composition according to claim 1 or 2, wherein the compound (B) is a compound represented by the following formula (b) having 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule. .

(In the formula, R 1 is an n-valent organic group,
L 1 represents an alkylene or N-X 1 of a single bond, 1 to 10 carbon atoms, X 1 represents a hydrogen atom or an alkyl group and, X 1 is form an alkylene and together with another X 1 Or a ring structure may be formed by bonding to R 1 ,
L 2 represents a single bond or alkylene having 1 to 10 carbon atoms,
L 3 represents a single bond, NH or N-alkyl,
L 4 represents a single bond or alkylene having 1 to 10 carbon atoms,
L 5 represents a single bond or carbonyl, and when L 3 is NH or N-alkyl, L 4 and L 5 do not represent a single bond at the same time,
L 6 and L 7 each independently represent a linear or branched alkylene having 2 to 20 carbon atoms,
The alkylene in L 1 , L 2 , L 4 , L 6 and L 7 may be substituted with one or more substituents selected from the same or different from halogen and hydroxy groups, and n is an integer of 2 to 6 . )
The composition according to claim 3, wherein n is 2 or 3.
The composition according to claim 3 or 4, wherein at least one of L 6 and L 7 is represented by the following formula (b1).

(In the formula, R 2 to R 5 each independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group.)
The composition according to any one of claims 3 to 5, wherein L 6 and L 7 in the formula (b) both represent ethylene.
7. In R 1 or L 1 in formula (b), the atom directly bonded to the carbonyl group in formula (b) is a carbon atom that does not form an aromatic ring. The composition as described.
The composition according to any one of claims 3 to 7, wherein R 1 in the formula (b) has a structure selected from the following b2-1 to b2-29.
The component (A) is represented by the following formulas (1) to (6)
(Wherein A, B and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO Represents —O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH— May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof. )
The composition according to any one of claims 1 to 8, which has any one photosensitive side chain selected from the group consisting of:
The component (A) is represented by the following formulas (7) to (10)
(Wherein A, B and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO Represents —O— or —O—CO—CH═CH—;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (provided that when n = 0, B is a single bond);
Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atom bonded to each independently represents —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 )
The composition according to any one of claims 1 to 8, which has any one photosensitive side chain selected from the group consisting of:
The component (A) is represented by the following formulas (11) to (13)
(Wherein A is independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—) Or represents —O—CO—CH═CH—;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, and m2 represents an integer of 1 to 3;
R represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or a phase selected from those substituents. Each of the hydrogen atoms bonded to them is independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5). -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms (It may be substituted with an oxy group or represents a hydroxy group or an alkoxy group having 1 to 6 carbon atoms)
The composition according to any one of claims 1 to 8, which has any one photosensitive side chain selected from the group consisting of:
(A) component is the following formula (14) or (15)
(Wherein each A is independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, Or represents —O—CO—CH═CH—;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
l represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3)
The composition according to any one of claims 1 to 8, which has a photosensitive side chain represented by the formula:
(A) component is following formula (16) or (17)
Wherein A is a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, or —O—. Represents CO—CH═CH—;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
l represents an integer of 1 to 12, and m represents an integer of 0 to 2)
The composition according to any one of claims 1 to 8, which has a photosensitive side chain represented by the formula:
(A) component is a following formula (18) or (19)
(Wherein A and B are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O) Represents — or —O—CO—CH═CH—;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
one of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3;
R 1 represents a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group)
The composition according to any one of claims 1 to 8, which has any one photosensitive side chain selected from the group consisting of:
(A) component is following formula (20)
Wherein A is a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, or —O Represents —CO—CH═CH—;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms May be substituted with an alkyloxy group;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
l represents an integer of 1 to 12, and m represents an integer of 0 to 2)
The composition according to any one of claims 1 to 8, which has a photosensitive side chain represented by the formula:
The component (A) is represented by the following formulas (21) to (31)
Wherein A and B have the same definition as above;
Y 3 is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO 2 , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R 3 is a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing Represents a heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (23) to (24), the sum of all m is 2 or more, and formulas (25) to (26 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;
R 2 is a hydrogen atom, —NO 2 , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z 1 and Z 2 represent a single bond, —CO—, —CH 2 O—, —CH═N—, —CF 2 —)
The composition according to any one of claims 1 to 15, which has any one liquid crystalline side chain selected from the group consisting of:
[I] A step of applying the composition according to any one of claims 1 to 16 onto a substrate having a conductive film for driving a lateral electric field to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
The manufacturing method of the board | substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements by which orientation control ability was provided by having.
A substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element manufactured by the method according to claim 17.
A lateral electric field drive type liquid crystal display element comprising the substrate according to claim 18.
A step of preparing a substrate (first substrate) according to claim 18;
[I ′] on a second substrate (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range;
(B) A step of applying a polymer composition containing 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule and (C) an organic solvent to form a coating film ;
[II ′] a step of irradiating the coating film obtained in [I ′] with polarized ultraviolet rays; and [III ′] a step of heating the coating film obtained in [II ′];
Obtaining a liquid crystal alignment film imparted with alignment control capability by having a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment of the first and second substrates via liquid crystal A step of obtaining a liquid crystal display element by arranging the first and second substrates to face each other so that the films face each other;
A method for producing a liquid crystal display element, comprising obtaining a lateral electric field drive type liquid crystal display element.
A lateral electric field drive type liquid crystal display device manufactured by the method according to claim 20.