WO2016021570A1

WO2016021570A1 - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: WO2016021570A1
Application number: PCT/JP2015/072015
Authority: WO
Inventors: アルム金; 隆之根木; 悟志南; 喜弘川月; 瑞穂近藤
Original assignee: 日産化学工業株式会社
Priority date: 2014-08-05
Filing date: 2015-08-04
Publication date: 2016-02-11
Also published as: TW201934589A; TWI684604B; JP6794257B2; TWI695847B; TW201620944A; JPWO2016021570A1

Abstract

The present invention pertains to a polymer composition containing: (A) a photosensitive side-chain polymer that exhibits liquid crystallinity within a prescribed temperature range; (B) a polymer having a side chain indicated by formula (b) [in the formula, A, B, S, T, X, P, Q, l1, l2, l3, b¹, and b² are as defined in the Description]; and (C) an organic solvent. In addition, the present invention pertains to a liquid crystal alignment film obtained from said composition and a production method for a substrate having said liquid crystal alignment film. As a result of the present invention, a novel polymer composition and a liquid crystal alignment film for in-plane switching liquid crystal display elements using same can be provided, said novel polymer composition providing a liquid crystal alignment film for in-plane switching liquid crystal display elements that is highly efficient, has alignment control properties, and has excellent electrical characteristics.

Description

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

The present invention relates to a novel liquid crystal aligning agent, a liquid crystal aligning film obtained therefrom, and a liquid crystal display element having the same. The liquid crystal display element obtained by the present invention is excellent in electrical 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.

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 film for a liquid crystal display element that is provided with high efficiency and orientation control ability and is excellent in electrical characteristics, and a liquid crystal display element. Another object of the present invention is to provide a liquid crystal aligning agent that provides a liquid crystal aligning film having an improved voltage holding ratio.

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 polymer having a side chain represented by the following formula (b);

[In the formula (b),
A and B are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, or — Represents 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;
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;
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;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
l3 is 0 or 1;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
The dashed line indicates that the bond may be a single bond or a double bond;
b ¹ and b ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and b ¹ and b ² together form a cyclic or chain structure having 2 to 5 carbon atoms. A saturated or unsaturated divalent hydrocarbon group may be formed, and the hydrocarbon group in which b ¹ and b ² are combined may be further substituted with a substituent b ³ , and b ³ Represents one or a plurality of substituents which are the same or different and are selected from a hydroxy group, a carboxyl group, a nitro group, a cyano group, a halogen group, an alkyl group and an alkoxy group. ]
And (C) a polymer composition containing an organic solvent.

<2> In the polymer composition according to <1>, the component (A) preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofleece transition.

<3> In the polymer composition of the above <1> or <2>, L in the formula (b) may be an oxygen atom.

<4> In the polymer composition according to any one of <1> to <3>, the component (A) and / or the component (B) further have a side chain represented by the following formula (0). It is good.

[Where:
A and B are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, or — Represents 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;
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;
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;
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;
G represents the following formulas (G-1), (G-2), (G-3) and (G-4)

(In the formula, a broken line represents a bond, R ⁵⁰ represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a phenyl group, and when there are a plurality of R ^50, they are the same or different from each other. T is an integer of 1 to 7, J represents O, S, NH or NR ⁵¹ , and R ⁵¹ represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group. Group.]

<5> In the polymer composition according to any one of <1> to <4>, the component (A) and / or the component (B) have a group selected from a pyridyl group, an amide group, and a urethane group. It may further have a side chain (b-2).

<6> In the polymer composition according to any one of <1> to <5>, the component (A) is any one photosensitive side selected from the group consisting of the following formulas (1) to (6) It is good to have a chain.

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.

<7> In the polymer composition according to any one of <1> to <5>, the component (A) is any one photosensitive side selected from the group consisting of the following formulas (7) to (10): It is good to have a chain.
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).

<8> In the polymer composition according to any one of <1> to <5>, the component (A) is any one photosensitive side selected from the group consisting of the following formulas (11) to (13) It is good to have a chain.
In the formula, A, X, l, m, m1 and R have the same definition as above.

<9> In the polymer composition according to any one of the above items <1> to <5>, the component (A) may have 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.

<10> In the polymer composition according to any one of <1> to <5>, 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.

<11> In the polymer composition according to any one of <1> to <5>, 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 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.

<12> In the polymer composition according to any one of <1> to <5>, 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.

<13> In the polymer composition according to any one of <1> to <12>, the component (A) is any one liquid crystal side selected from the group consisting of the following formulas (21) to (31) It is good to have a chain.
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 —.

<14> A step of applying the polymer composition according to any one of <1> to <13> 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.

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

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

<17> a step of preparing a substrate (first substrate) of <15>above;
[I ′] a step of forming a coating film by applying the polymer composition according to any one of the above <1> to <13> on a second substrate;
[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.

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

According to the present invention, it is possible to provide a liquid crystal alignment film for a liquid crystal display element, which is imparted with a highly efficient alignment control ability and excellent in electrical characteristics, and a liquid crystal display element.
Further, in the present invention, by including the specific polymer as the component (B) in the polymer composition, a lateral electric field drive type liquid crystal element having an excellent voltage holding ratio even by low-temperature baking and a liquid crystal for the element An alignment film can be provided.

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 used in the production method of the present invention has a photosensitive side chain polymer that can exhibit liquid crystallinity (hereinafter, also simply referred to as a side chain polymer), and the polymer composition The coating film obtained by using the product 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), the monomer represented by the above formula (b) as the component (B) A polymer having repeating units derived from it is used. It was unexpected that the voltage holding ratio was greatly improved. 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.

<Polymer composition>
The polymer composition of the present invention comprises (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range,
(B) a polymer having a side chain represented by the following formula (b);

[In the formula (b),
A and B are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, or — Represents 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;
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;
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;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
l3 is 0 or 1;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
The dashed line indicates that the bond may be a single bond or a double bond;
b ¹ and b ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and b ¹ and b ² together form a cyclic or chain structure having 2 to 5 carbon atoms. , A saturated or unsaturated divalent hydrocarbon group may be formed, and the hydrocarbon group in which b ¹ and b ² are combined may be further substituted with a substituent b ³ , b ³ represents one or a plurality of substituents which are the same or different and are selected from a hydroxy group, a carboxyl group, a nitro group, a cyano group, a halogen group, an alkyl group and an alkoxy group. ]
And (C) contains 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 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 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 —.

[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.

The content of the photoreactive side chain in the side chain polymer as the component (A) of the present invention is preferably 10 mol% to 100 mol%, and preferably 15 mol% to 95 mol% from the viewpoint of liquid crystal alignment. More preferably, 20 mol% to 80 mol% is even more preferable.

The content of the liquid crystal side chain in the side chain polymer as the component (A) of the present invention is preferably 0 to 90 mol%, more preferably 5 mol% to 85 mol% or less from the viewpoint of liquid crystal orientation. 20 mol% to 80 mol% or less is more preferable.

<< (B) component >>
The polymer composition used in the present invention contains a polymer having a side chain represented by the following formula (b) as the component (B).

In Formula (b), A and B are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO. —O— or —O—CO—CH═CH— is represented.

In the formula (b), S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced with a halogen group.

In the formula (b), T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be replaced with a halogen group.

In the formula (b), X represents a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or — O—CO—CH═CH— is represented, and when the number of X is 2, X may be the same or different.

In formula (b), P and Q are each independently a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. A group selected from the group consisting of: wherein X is —CH═CH—CO—O—, —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded; Is an aromatic ring.

In the formula (b), l1 is 0 or 1.
l2 is an integer of 0-2.
l3 is 0 or 1.
When l1 and l2 are both 0, A represents a single bond when T is a single bond.
When l1 is 1, B represents a single bond when T is a single bond.
The broken line indicates that the bond may be a single bond or a double bond.

In formula (b), b ¹ and b ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and b ¹ and b ² together represent 2 to 5 carbon atoms. May form a cyclic or chain-like, saturated or unsaturated divalent hydrocarbon group, and the hydrocarbon group in which b ¹ and b ² are combined is further substituted with the substituent b ³ B ³ represents one or a plurality of substituents which are the same or different and are selected from a hydroxy group, a carboxyl group, a nitro group, a cyano group, a halogen group, an alkyl group and an alkoxy group.

[Monomer having side chain represented by formula (b)]

The component (B) does not use [photoreactive side chain monomer] among the exemplified monomers in the component (A), but has a polymerizable group and a group represented by the above formula (b) instead. A (co) polymer obtained by copolymerization using a monomer is preferred.
Therefore, the monomer that can be copolymerized with the monomer having a polymerizable group and the group represented by the above formula (b) includes the “liquid crystalline side chain monomer” and “other monomer” exemplified in the component (A). Can be mentioned.

The content of the side chain represented by the above formula (b) in the side chain type polymer as the component (B) of the present invention is preferably from 5 mol% to 100 mol% from the viewpoint of electrical characteristics, preferably 30 mol%. More preferred is from ˜100 mol%, and further more preferred is from 40 mol% to 100 mol%.

The content of the liquid crystalline side chain in the side chain polymer as the component (B) of the present invention is preferably 95 mol% or less, more preferably 70 mol% or less, and more preferably 60 mol% or less from the viewpoint of liquid crystal alignment. Is more preferable.

<Specific copolymer unit>
In the present invention, either one or both of the polymer as the component (A) and the polymer as the component (B) can contain a specific copolymer for the purpose of further improving the properties. Examples of the specific copolymer unit include a side chain represented by the following formula (0) and the following side chain (b-2).

[Side Chain Represented by Formula (0)]
The side chain represented by Formula (0) is as follows.

In the formula, A and B are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—. Or represents —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;
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;
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;
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;
G represents the following formulas (G-1), (G-2), (G-3) and (G-4)

(In the formula, a broken line represents a bond, R ⁵⁰ represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a phenyl group, and when there are a plurality of R ^50, they are the same or different from each other. T is an integer of 1 to 7, J represents O, S, NH or NR ⁵¹ , and R ⁵¹ represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group. Group.

More specific examples of the monomer having a side chain represented by the formula (0) include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide. It is preferably a structure having a polymerizable group composed of at least one selected from the group consisting of radical polymerizable groups such as norbornene and siloxane, and a side chain represented by the above formula (0).

Among such monomers, specific examples of monomers having an epoxy group include compounds such as glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and allyl glycidyl ether. Among them, glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5 Hexene, 1,7-octadiene monoepoxide, and the like.

Specific examples of the monomer having thiirane include those in which the epoxy structure of the monomer having the epoxy group is replaced with thiirane.

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

Examples of the monomer having an oxetane group include (meth) acrylic acid ester having an oxetane group. Among such monomers, 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3- Ethyl-oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetane, 3- (Acryloyloxymethyl) -2-phenyl-oxetane, 2- (methacryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyl) Oxymethyl) -4-trifluoromethyl oxetane are preferable, 3- (methacryloyloxy) -3-ethyl - oxetane, 3- (acryloyloxy-methyl) -3-ethyl - oxetane, and the like.

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

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

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

[Side chain (b-2)]
The side chain (b-2) is a side chain having a group selected from a pyridyl group, an amide group and a urethane group. By containing such a side chain (b-2), in order to reduce the elution of ionic impurities and promote the crosslinking reaction of the group represented by the above formula (0) when a liquid crystal alignment film is formed. Or a more durable liquid crystal aligning film can be obtained. In order to produce a polymer having a side chain (b-2), a monomer having a side chain (b-2) may be copolymerized.

Examples of the monomer having such a side chain (b-2) 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 siloxane and a side chain having a pyridyl group, an amide group and a urethane group is preferable. NH in the amide group and urethane group may or may not be substituted. Examples of the substituent in the case where it may be substituted include an alkyl group, an amino-protecting group, and a benzyl group.

Among such monomers, specific examples of monomers having a pyridyl group include 2- (2-pyridylcarbonyloxy) ethyl (meth) acrylate and 2- (3-pyridylcarbonyloxy) ethyl (meth) acrylate. 2- (4-pyridylcarbonyloxy) ethyl (meth) acrylate, and the like.

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

<< Polymer manufacturing process >>
The photosensitive side chain polymer capable of expressing the liquid crystallinity of the component (A) or the component (B) is obtained by polymerizing the photoreactive side chain monomer having the photosensitive side chain and the liquid crystalline side chain monomer. Can be obtained.

(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. Further, it can be copolymerized with the monomer that gives the side chain (0) or the monomer that gives the side chain (b-2).

The polymer which is the component (B) is not used in the above component (A), but instead of using the [liquid crystalline side chain monomer], instead of using the monomer represented by the above formula (b). It can be obtained by polymerization. Further, it can be copolymerized with a monomer that gives the side chain (b-2).

In addition, the component (A) and / or the component (B) can be copolymerized with other monomers as long as the characteristics are 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.

Hereinafter, the production method of the component (A) and the production method of the component (B) are collectively referred to as a production method of the side chain polymer of the present embodiment. The method for producing 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.

The molecular weight of the (B) 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 coating film uniformity. The weight average molecular weight is preferably 2,000 to 1,000,000, more preferably 1,000 to 150,000.

In the case where the side chain polymer as the component (A) and / or the component (B) of the present invention further contains a side chain represented by the formula (0), the content is improved in reliability and liquid crystal alignment. From the viewpoint of the influence on the property, it is preferably 20 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less.

In the case where the side chain polymer as the component (A) and / or the component (B) of the present invention further contains a side chain (b-2), the content is improved in reliability and liquid crystal orientation. From the point of influence, 80 mol% or less is preferable, 60 mol% or less is more preferable, and 40 mol% or less is still more preferable.

The side chain type polymer as the component (A) and / or the component (B) of the present invention includes a photoreactive side chain, a side chain represented by the above formula (b), a liquid crystalline side chain, and the above formula (0). And other side chains other than the above side chain (b-2). If the content is (A), the total content of the photoreactive side chain, the liquid crystalline side chain, the side chain represented by the formula (0), and the side chain (b-2) is When it is less than 100%, in the component (B), the side chain represented by the above formula (b), the liquid crystalline side chain, the side chain represented by the above formula (0), the side chain (b-2) ) Is the remaining part of each when the total content is less than 100%.

In addition, the ratio of these side chains can be controlled by adjusting the molar fraction of the monomer that gives each side chain when the side chain polymer is produced.

<< (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, it 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), 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.

[Preparation of polymer composition]
The polymer composition of the present invention contains a photosensitive side chain polymer as component (A), a specific (co) polymer as component (B), and an organic solvent as component (C). To do. In addition to the (A) component, the (B) component, and the (C) component, the polymer composition of the present invention further improves film thickness uniformity and surface smoothness when the polymer composition is applied. It can also contain a solvent, a compound, a compound for improving the adhesion between the liquid crystal alignment film and the substrate, and the like. And as long as the effect of this invention is not impaired, another additive can be contained.

The mixing ratio of the component (A) and the component (B) is preferably 1:99 to 99: 1 by mass ratio. More preferably 10:90 to 90:10, most preferably 20:80 to 80:20.

The method for preparing the polymer composition of the present invention is not particularly limited. As a preparation method, for example, (C) a solution of component (A) dissolved in a solvent and (B) component are mixed at a predetermined ratio to make a uniform solution, or at an appropriate stage of this preparation method In addition, there may be mentioned a method of further adding and mixing other additives as required.

In the preparation of the polymer composition of the present invention, a solution of a specific copolymer obtained by a polymerization reaction in a solvent can be used as it is. In this case, for example, the component (B) is added to the solution of the component (A) to obtain a uniform solution. At this time, a solvent may be further added for the purpose of adjusting the concentration. At this time, the solvent used in the production process of the component (A) and the solvent used for adjusting the concentration of the polymer composition may be the same or different.

The prepared polymer composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

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 is composed only of the above-described photosensitive side chain polymer that can exhibit liquid crystallinity as the component (A) and the specific polymer that is the component (B). However, other polymers may be mixed as long as the liquid crystal expression ability and the photosensitive performance are not impaired. 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.
Such other polymers are composed of, for example, poly (meth) acrylate, polyamic acid, polyimide, and the like, and include polymers that are not the component (A) or component (B) described above.

<Manufacturing method of substrate having liquid crystal alignment film> and <Manufacturing method of liquid crystal display element>
[I] A step of applying the polymer composition of the present invention on a substrate having a conductive film for driving a transverse 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];
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 photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range as component (A) on a substrate having a conductive film for driving a lateral electric field, component (B). A specific polymer and a polymer composition containing an organic solvent as component (C) are 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.

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 manufactured by the method of the present invention or the lateral electric field drive type liquid crystal display element having the substrate has excellent reliability, large screen and high definition. It can be suitably used for LCD TVs.
EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to this Example.

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).
MA3 (N-succinimidyl methacrylate) manufactured by Tokyo Chemical Industry Co., Ltd. was used.
MA9 (glycidyl methacrylate) and MA10 (hydroxybutyl acrylate glycidyl ether) were commercially available.

<Organic solvent>
THF: Tetrahydrofuran NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve

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

<Monomer Synthesis Example 1-1>
Synthesis of compound [MA4]

A solution of Compound [B] (25.00 g, 142 mmol) and THF (180 g) added to a 500 mL four-necked flask was cooled to 0 ° C. with stirring in a nitrogen atmosphere, and then Compound [A] (23.1 g, 149 mmol) in THF (20 g) was slowly added dropwise while paying attention to heat generation. After completion of the dropwise addition, the reaction temperature was returned to room temperature, and the reaction was continued. After confirming the completion of the reaction by HPLC, the reaction solution was concentrated and the precipitated solid was filtered and dried under reduced pressure at room temperature to give 45% of compound [MA4]. 0.9 g was obtained (yield 98%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 7.03 (2H, d), 6.85 (2H, d), 6.78 (1H, t), 6.56-6.54 (1H, m), 5.68-5.67 (1H, m), 4.11-4.09 (2H, m), 3.62-3.59 (2H, m), 3.43-3.41 (4H, m), 2.20 (3H, s), 1.91-1.84 (3H, m).

<Monomer Synthesis Example 1-2>
Synthesis of compound [MA5]

A solution of compound [C] (10.00 g, 43.4 mmol) and THF (60 g) added to a 300 mL four-necked flask was cooled to 0 ° C. with stirring in a nitrogen atmosphere, and then compound [A] (7. A solution of 07 g, 45.6 mmol) in THF (20 g) was slowly added dropwise while paying attention to heat generation. After completion of the dropwise addition, the reaction temperature was returned to room temperature, and the reaction was continued. After completion of the reaction was confirmed by HPLC, the reaction solution was concentrated, and the precipitated solid was filtered and dried under reduced pressure at room temperature to obtain 15 [MA5]. 0.3 g was obtained (yield 92%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 7.51 (2H, d), 7.08 (2H, d), 6.82 (1H, t), 6.06-6.05 (1H, m), 5.67-5.62 (1H, m), 4.11 (2H, t), 3.46-3.44 (4H, m), 3.36-3.31 (2H, m), 3.31-3.24 (4H, m), 1.86 (3H, s).

<Monomer Synthesis Example 1-3>
Synthesis of Compound [MA6]

A solution obtained by adding Compound [D] (25.00 g, 139 mmol) and THF (160 g) to a 500 mL four-necked flask was cooled to 0 ° C. with stirring in a nitrogen atmosphere, and then Compound [A] (21.50 g, 138 mmol) in THF (40 g) was slowly added dropwise, taking care of the exotherm. After completion of the dropwise addition, the reaction temperature was returned to room temperature and the reaction was continued. After confirming the completion of the reaction by HPLC, the reaction solution was concentrated to obtain 46.5 g of Compound [MA6] (yield 100%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 7.86-7.85 (1H, m), 7.02-7.01 (1H, m), 6.79 (1H, t), 6.65-6.63 (1H, m), 6.06- 6.02 (1H, m), 5.69-5.69 (1H, m), 4.10 (2H, t), 3.62-3.31 (10H, m), 1.88 (3H, s).

<Monomer Synthesis Example 1-4>
Synthesis of compound [MA7]

A solution of Compound [E] (25.00 g, 136 mmol) and THF (160 g) added to a 500 mL four-necked flask was cooled to 0 ° C. with stirring in a nitrogen atmosphere, and then Compound [A] (22.10 g, A solution of 142.5 mmol) in THF (40 g) was gradually added dropwise while paying attention to heat generation. After completion of the dropwise addition, the reaction temperature was returned to room temperature and the reaction was continued. After completion of the reaction was confirmed by HPLC, the reaction solution was concentrated and the precipitated solid was filtered and dried under reduced pressure at room temperature to obtain 42 [MA7]. 0.9 (yield 93%).
¹ H-NMR (400MHz, DMSO-d6, δppm): 76.79-6.76 (1H, t), 6.06-6.05 (1H, m), 5.67-5.65 (1H, m), 4.67 (1H, t), 4.09 ( 2H, t), 3.80-3.22 (9H, m), 2.06-1.76 (10H, m).

<Monomer Synthesis Example 1-5>
Synthesis of Compound [MA8]

A solution of Compound [F] (30.00 g, 319 mmol) and THF (200 g) added to a 500 mL four-necked flask was cooled to 0 ° C. with stirring under a nitrogen atmosphere, and then Compound [A] (51.92 g, 335 mmol) in THF (40 g) was slowly added dropwise, taking care of the exotherm. After completion of the dropwise addition, the reaction temperature was returned to room temperature, and the reaction was continued. After the completion of the reaction was confirmed by HPLC, the reaction solution was concentrated and the precipitated solid was filtered and dried under reduced pressure at room temperature to obtain 78 of compound [MA8]. .3 was obtained (yield 99%).
¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 9.04 (1H, s), 8.30-8.28 (2H, m), 7.38-7.36 (2H, m), 6.54 (1H, t), 6.08-6.07 ( 1H, m), 5.71-5.70 (1H, m), 4.15 (2H, t), 3.43-3.39 (2H, m), 1.89 (3H, s).

<Polymethacrylic acid synthesis example 1>
After MA1 (1.99 g, 6.0 mmol) and MA2 (2.75 g, 9.0 mmol) were dissolved in THF (19.50 g) and degassed with a diaphragm pump, AIBN (0.12 g, 0.8 mmol) was added and deaeration was performed again. Thereafter, the mixture was reacted at 50 ° C. for 18 hours to obtain a polymethacrylic acid solution. This polymer solution was added dropwise to methanol (500 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure in an oven at 40 ° C. to obtain a polymethacrylic acid powder.

36.0 g of NMP was added to 4.0 g of the obtained powder, and the mixture was stirred at room temperature for 3 hours. A polymethacrylic acid solution (M-1) having a solid content concentration of 10.0 wt% was obtained. The polymer was completely dissolved at the end of stirring.

<Synthesis Examples 2 to 11>
Using the composition shown in Table 1, polymer solutions of Synthesis Examples 2 to 11 were obtained using the same method as in Synthesis Example 1. All the polymethacrylic acid solutions have a solid content of 10.0 wt% in the NMP solvent.

<Examples 1 to 10 and Comparative Example 1>
The polymer solution and the solvent shown in Table 2 below were mixed to obtain a 6.0 wt% polymer solution.

<Examples 11 to 20 and Comparative Example 2>
The polymer solution and the solvent shown in Table 3 below were mixed to obtain a 6.0 wt% polymer solution.

<Examples 21 to 30 and Comparative Example 3>
The polymer solution and the solvent shown in Table 4 below were mixed to obtain a 6.0 wt% polymer solution.

[Production of liquid crystal cell]
Using the liquid crystal aligning agent (A1) obtained in Example 1, a liquid crystal cell was produced 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 of each electrode element in the short direction was 10 μm, and the distance between the electrode elements was 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 had a shape that bends and resembles a bold-faced koji. Each pixel was divided vertically with the central bent portion as a boundary, and had 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 were 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 was configured to be in the opposite direction.

The liquid crystal aligning agent (A1) obtained in Example 1 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 surface of the coating film was irradiated with ultraviolet rays of 313 nm through a polarizing plate at 1 mJ / cm ² and then heated on a hot plate at 150 ° C. for 10 minutes (primary firing). A substrate with a liquid crystal alignment film was obtained by heating (secondary firing) for 10 minutes on a plate. Similarly, when the irradiation amount of ultraviolet rays is 1 mJ / cm ² to 10 mJ / cm ² , it is 1 mJ / cm ² intervals, 10 mJ / cm ² to 100 mJ / cm ² is 10 mJ / cm ² intervals, and 100 mJ / cm ² or more. in 50 mJ / cm ² intervals to create different substrates, respectively. Further, a coating film was similarly formed on a glass substrate having a columnar spacer having 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 was prepared by injecting liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) into the empty cell by a reduced pressure injection method, sealing the injection port. Obtained.

Regarding the liquid crystal aligning agents (A2 to A33) obtained in Examples 2 to 30 and Comparative Examples 1 to 3, liquid crystal cells were prepared using the same method as A1.

(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 of the substrates with different ultraviolet irradiation amounts as described above, Tables 5 and 6 show the irradiation amount margins with good alignment.

(Voltage holding ratio (VHR) evaluation)
For evaluation of VHR, a voltage of 5 V was applied to the obtained liquid crystal cell at a temperature of 70 ° C. for 60 μs, a voltage after 1667 ms was measured, and how much the voltage was held was calculated as a voltage holding ratio.
The voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technica.

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

As shown in Tables 5, 6, and 7, Examples 1 to 30 according to the present invention have a common component (A) and no comparison with Comparative Examples 1, 2, and 3 that contain no component (B). It was found that the voltage holding ratio (VHR) was high.

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 polymer having a side chain represented by the following formula (b):

[In the formula (b),
A and B are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, or — Represents 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;
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;
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;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
l3 is 0 or 1;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
The dashed line indicates that the bond may be a single bond or a double bond;
b 1 and b 2 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and b 1 and b 2 together form a cyclic or chain structure having 2 to 5 carbon atoms. A saturated or unsaturated divalent hydrocarbon group may be formed, and the hydrocarbon group in which b 1 and b 2 are combined may be further substituted with a substituent b 3 , and b 3 Represents one or a plurality of substituents which are the same or different and are selected from a hydroxy group, a carboxyl group, a nitro group, a cyano group, a halogen group, an alkyl group and an alkoxy group. ]
And (C) a polymer composition containing an organic solvent.
The polymer composition according to claim 1, wherein the component (A) has a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofleece transition.
The polymer composition according to claim 1 or 2, wherein L in the formula (b) is an oxygen atom.
The polymer composition according to claim 1 or 2, wherein the component (A) and / or the component (B) further has a side chain represented by the following formula (0).

[Where:
A and B are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, or — Represents 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;
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;
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;
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;
G represents the following formulas (G-1), (G-2), (G-3) and (G-4)

(In the formula, a broken line represents a bond, R 50 represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a phenyl group, and when there are a plurality of R 50, they are the same or different from each other. T is an integer of 1 to 7, J represents O, S, NH or NR 51 , and R 51 represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group. Group.]
The component (A) and / or the component (B) further has a side chain (b-2) having a group selected from a pyridyl group, an amide group, and a urethane group. The polymer composition described in 1.
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 polymer composition according to any one of claims 1 to 5, which has any one kind of 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 polymer composition according to any one of claims 1 to 5, which has any one type of 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 polymer composition according to any one of claims 1 to 5, which has any one type of 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 polymer composition according to any one of claims 1 to 5, 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 polymer composition according to any one of claims 1 to 5, 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 polymer composition according to any one of claims 1 to 5, which has any one type of photosensitive side chain selected from the group consisting of:
The component (A) is represented by the 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 polymer composition according to any one of claims 1 to 5, 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 polymer composition according to any one of claims 1 to 12, which has any one liquid crystalline side chain selected from the group consisting of:
Applying the polymer composition according to any one of claims 1 to 13 on 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 a liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements by which alignment control ability was provided by having.
The board | substrate which has the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements manufactured by the method of Claim 14.
A lateral electric field drive type liquid crystal display element comprising the substrate according to claim 15.
Preparing a substrate (first substrate) according to claim 15;
[I ′] A step of applying the polymer composition according to any one of claims 1 to 13 on the second 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 ′];
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 17.