WO2022092088A1

WO2022092088A1 - Composition for forming radical-generating film, radical-generating film, method for producing liquid crystal display element, and liquid crystal display element

Info

Publication number: WO2022092088A1
Application number: PCT/JP2021/039497
Authority: WO
Inventors: 一世三宅; 尚宏野田
Original assignee: 日産化学株式会社
Priority date: 2020-10-27
Filing date: 2021-10-26
Publication date: 2022-05-05
Also published as: TW202225271A; CN116507968A; KR20230095991A; JPWO2022092088A1

Abstract

Provided is a composition for forming a radical-generating film, which contains: a component (A), a polymer used as an alignment component of a liquid crystal aligning agent for in-plane switching; and a component (B), a polymer which contains a group represented by formula (1) and which has a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond. (In formula (1), * denotes a bonding position, and R¹ denotes a single bond, -CH₂-, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH₂O-, -N(CH₃)-, -CON(CH₃)-, or -N(CH₃)CO-.　R² denotes a single bond or a C1-20 alkylene group which is unsubstituted or substituted with a fluorine atom. One or more arbitrary -CH₂- or -CF₂- moieties in the alkylene group may each independently be substituted with a group selected from among -CH=CH-, an optionally substituted divalent carbon ring and an optionally substituted divalent heterocyclic ring. Furthermore, one or more arbitrary -CH₂- or -CF₂- moieties in the alkylene group may be substituted with the groups listed below, that is, may be substituted with at least one of -O-, -COO-, -OCO-, -NHCO-, -CONH- or -NH- as long as these are not adjacent to each other.　R³ denotes an organic group that induces radical polymerization.)

Description

Radical generation film forming composition, radical generation film, manufacturing method of liquid crystal display element, and liquid crystal display element

INDUSTRIAL APPLICABILITY The present invention is a method for manufacturing a liquid crystal display element, which can manufacture a weak anchoring film by an inexpensive method and a method that does not include a complicated process, and applies a technique for stabilizing a liquid crystal layer with a polymer. The present invention relates to a liquid crystal display element for realizing a further low voltage drive, a radical generation film forming composition that can be used for them, and a radical generation film.

In recent years, liquid crystal display elements have been widely used in mobile phones, computers, television displays, and the like. Liquid crystal display elements have characteristics such as thinness, light weight, and low power consumption, and are expected to be applied to further contents such as VR (Virtual Reality) and ultra-high-definition displays in the future. Various display modes such as TN (Twisted Nematic), IPS (In-Plane Switching), and VA (Vertical Indicator) have been proposed as display methods for liquid crystal displays, but the liquid crystal is oriented in a desired orientation in all modes. A film (liquid crystal alignment film) that induces IPS is used.

In particular, for products equipped with a touch panel such as tablet PCs, smartphones, and smart TVs, the IPS mode, which does not distort the display even when touched, is preferred. Liquid crystal display elements using Field Switching) and technologies using non-contact technology using optical orientation have come to be used.

However, FFS has a higher substrate manufacturing cost than IPS, and has a problem that a display defect peculiar to FFS mode called Vcom shift occurs. In addition, regarding photo-alignment, compared to the rubbing method, there are merits that the size of the element that can be manufactured can be increased and the display characteristics can be greatly improved. In the case of isomerized type, seizure due to insufficient alignment force, etc.) can be mentioned. At present, liquid crystal display element makers and liquid crystal alignment film makers are making various efforts to solve these problems.

On the other hand, in recent years, an IPS mode using weak anchoring has been proposed, and it has been reported that using this method enables improved contrast and significantly lower voltage drive compared to the conventional IPS mode. (See Patent Document 1).

Specifically, a liquid crystal alignment film having strong anchoring energy is used for the substrate on one side, and the substrate side provided with the electrode for generating a transverse electric field on one side has no liquid crystal alignment regulating force. This is a method of making a liquid crystal display element in IPS mode by performing various processes and using them.

In recent years, a technical proposal for a weak anchoring IPS mode that creates a weak state using a concentrated polymer brush or the like has been made (see Patent Document 2). This technology has realized a significant improvement in the contrast ratio and a significant reduction in the drive voltage.

On the other hand, there is a problem that the response speed, especially when the voltage is off, is significantly reduced. This is due to the effect of responding with a weaker electric field compared to the normal drive method because the drive voltage is low, and because the anchoring force of the alignment film is extremely small, it takes time to restore the liquid crystal. ..

As a method for solving this, a method of weakly anchoring only on the pixel electrode has been proposed (see Patent Document 3). It has been reported that this makes it possible to achieve both improvement in brightness and response speed.

Japanese Patent No. 40553530 Japanese Unexamined Patent Publication No. 2013-231757 Japanese Unexamined Patent Publication No. 2017-21166

By making the IPS comb tooth electrode weak anchoring only on the electrode, the response speed delay during driving is suppressed, but in order to make the weak anchoring state only on the electrode, different materials are used in very small areas. It is necessary to prepare difficult techniques such as painting separately, which may be a big issue for actual industrialization.
Furthermore, the material design for obtaining a weak anchoring state is significantly different from the design of the liquid crystal alignment film using conventional polyimide, and there are many unclear points about the design guidelines, and the characteristics such as coating film forming property and electrical characteristics are taken into consideration. Then, it is very difficult to develop, and it may take a long time to find a material that can be put into practical use. There are very few reports of materials that can obtain a weak anchoring state just by applying them, and the current situation is that they are far from the practical level.

If such a technical problem can be solved, it will be a great cost merit as a panel maker, and it is considered that it will be a merit for suppressing battery consumption and improving image quality.

The present invention has been made to solve the above-mentioned problems, can be easily manufactured, can simultaneously realize a low drive voltage and a high response speed when the voltage is off, and is also good black. A method for manufacturing a liquid crystal display element capable of producing a transverse electric field liquid crystal display element capable of displaying and suppressing seizure, the liquid crystal display element, a radical generation film forming composition that can be used for them, and radical generation. The purpose is to provide a membrane.

As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved, and have completed the present invention having the following gist.

That is, the present invention includes the following.
[1] Component (A): A polymer used as an alignment component of a liquid crystal aligning agent for driving a transverse electric field, and Component (B): a polymer containing a group represented by the following formula (1) and polymerized. Polymers with structural units derived from monomers with sex carbon-carbon unsaturated bonds,
A radical generation film forming composition containing.

(In formula (1), * represents a binding site, R ¹ is a single bond, -CH _2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-,- Represents CH ₂ O-, -N (CH ₃ )-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-.
R ² represents an alkylene group having 1 to 20 carbon atoms which is single-bonded, or unsubstituted or substituted with a fluorine atom, and one or more of any -CH _2- or -CF _2- of the alkylene group is independent of each other. It may be replaced with a group selected from -CH = CH-, a divalent carbocycle which may have a substituent, and a divalent heterocycle which may have a substituent. Further, one or more of any -CH _2- or -CF _2- of the alkylene group is one of the following groups, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH. -Or -NH- may be replaced by at least one of these groups, provided they are not adjacent to each other.
R ³ represents an organic group that induces radical polymerization. )
[2] The radical generation film-forming composition according to [1], wherein R ³ represents an organic group that induces radical polymerization represented by the following formula [W], [Y] or [Z].

(In the formulas [W], [Y] and [Z], * indicates a bond site, and Ar is a group consisting of phenylene, naphthylene, and biphenylylene which may have an organic group and / or a halogen atom as a substituent. Representing the aromatic hydrocarbon group of choice, R ⁹ and R ¹⁰ each independently represent an alkyl group with 1-10 carbon atoms or an alkoxy group with 1-10 carbon atoms, with R ⁹ and R ¹⁰ being alkyl groups. In the case, they may be bonded to each other at the ends to form a ring structure. Q represents any of the following structures.

(In the formula, R ¹¹ represents -CH _2- , -NR-, -O-, or -S-, R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bond. The site is shown.). S ³ represents a single bond, -O-, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms), or -S-. R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. )
[3] The radical generation film-forming composition according to [1] or [2], wherein the polymer as the component (A) is a polyimide precursor or a polyimide.
[4] The radical-generating film-forming composition according to any one of [1] to [3], wherein the polymer as the component (A) does not contain an organic group that induces radical polymerization.
[5] The radical-generating film-forming composition according to any one of [1] to [4], wherein the content of the component (B) is 0.1 to 20% by mass with respect to the component (A). ..
[6] A radical generating film obtained by using the radical generating film forming composition according to any one of [1] to [5].
[7] A step of preparing a first substrate having the radical generation film according to [6] and a second substrate which may have the radical generation film.
A step of arranging the first substrate and the second substrate facing each other so that the radical generation film on the first substrate faces the second substrate.
The step of filling a liquid crystal composition containing a liquid crystal and a radically polymerizable compound between the first substrate and the second substrate, and the liquid crystal composition in contact with the radical generating film, said. Steps to polymerize radically polymerizable compounds,
A method for manufacturing a liquid crystal display element including.
[8] The method for manufacturing a liquid crystal display element according to [7], wherein the second substrate is a second substrate having no radical generation film.
[9] The method for manufacturing a liquid crystal display element according to [7], wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial orientation.
[10] The method for manufacturing a liquid crystal display element according to [9], wherein the liquid crystal alignment film having uniaxial orientation is a liquid crystal alignment film for horizontal alignment.
[11] The method for manufacturing a liquid crystal display element according to any one of [7] to [10], wherein either the first substrate or the second substrate is a substrate having a comb tooth electrode.
[12] It has a first substrate, a second substrate arranged to face the first substrate, and a liquid crystal display filled between the first substrate and the second substrate.
The radically polymerizable compound is polymerized in a state where the liquid crystal composition containing the liquid crystal and the radically polymerizable compound is in contact with the radically generated film of the first substrate having the radically generated film according to [6]. A liquid crystal display element characterized by radical polymerization.

According to the present invention, it can be easily manufactured, a low drive voltage and a high response speed at the time of voltage off can be realized at the same time, and in addition, a good black display is possible, and a transverse electric field liquid crystal with good seizure suppression is possible. It is possible to provide a method for manufacturing a liquid crystal display element capable of manufacturing a display element, the liquid crystal display element, a radical generation film forming composition that can be used for the liquid crystal display element, and a radical generation film.

It is a schematic sectional drawing which shows an example of the transverse electric field liquid crystal display element of this invention. It is the schematic sectional drawing which shows the other example of the transverse electric field liquid crystal display element of this invention.

[Radical generation film forming composition]
The radical generation film forming composition of the present invention contains at least the following component (A) and the following component (B).
Component (A): Polymer used as an alignment component for a liquid crystal aligning agent for driving a transverse electric field Component (B): A polymer containing a group represented by the following formula (1) and having a polymerizable carbon-carbon non-constant. Polymers with structural units derived from monomers with saturated bonds

(In formula (1), * represents a binding site, R ¹ is a single bond, -CH _2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-,- Represents CH ₂ O-, -N (CH ₃ )-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-.
R ² represents an alkylene group having 1 to 20 carbon atoms which is single-bonded, or unsubstituted or substituted with a fluorine atom, and one or more of any -CH _2- or -CF _2- of the alkylene group is independent of each other. It may be replaced with a group selected from -CH = CH-, a divalent carbocycle which may have a substituent, and a divalent heterocycle which may have a substituent. Further, one or more of any -CH _2- or -CF _2- of the alkylene group is one of the following groups, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH. -Or -NH- may be replaced by at least one of these groups, provided they are not adjacent to each other.
R ³ represents an organic group that induces radical polymerization. )

By applying and curing such a composition to form a film, it is possible to obtain a radical generation film in which an organic group that induces radical polymerization is immobilized in the film.
Then, in the method for producing a liquid crystal display element of the present invention described later, a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is brought into contact with a radical generation film obtained by using the radical generation film forming composition of the present invention. In this state, the step of polymerizing the radically polymerizable compound is included. In this step, the present inventors have stated that a weak anchoring film is obtained by changing the surface of the radical-generating film by the polymerization reaction of the radically polymerizable compound using the radical generated by the radical-generating film. I'm guessing. However, whether the change in the surface of the radical-generating film due to such a step is a change in the radical-generating film itself or a change due to the formation of a polymerized layer of the radical-polymerizable compound on the radical-generating film. It is difficult to confirm. Therefore, it has not been possible to identify the result of such a step.

In the present invention, by performing the above steps, a weak anchoring transverse electric field liquid crystal display element can be stably manufactured, and it is possible to simultaneously realize a low drive voltage and a high response speed when the voltage is off, and in addition, seizure. It becomes possible to manufacture a transverse electric field liquid crystal display element having a good suppression of the voltage.

In the present invention, the "weak anchoring film" means that there is no force to regulate the orientation of liquid crystal molecules in the in-plane direction, or even if there is, it is weaker than the intramolecular force between liquid crystals. A film that is not uniaxially oriented in the direction. Further, the weak anchoring film is not limited to the solid film, but also includes a liquid film covering the solid surface. Normally, a liquid crystal display element uses a film that regulates the orientation of liquid crystal molecules, that is, a liquid crystal alignment film in pairs to align the liquid crystal, but even when the weak anchoring film and the liquid crystal alignment film are used in pairs, the liquid crystal is oriented. Can be made to. This is because the alignment restricting force of the liquid crystal alignment film is transmitted to the thickness direction of the liquid crystal layer by the intramolecular force between the liquid crystal molecules, and as a result, the liquid crystal molecules close to the weak anchoring film are also oriented. Therefore, when a liquid crystal alignment film for horizontal alignment is used as the liquid crystal alignment film, a horizontal alignment state can be created in the entire liquid crystal cell. Horizontal orientation refers to a state in which the major axes of liquid crystal molecules are arranged substantially parallel to the liquid crystal alignment film surface, and inclined orientation of about several degrees is also included in the category of horizontal orientation.

<Ingredient (B)>
The component (B) is a polymer containing a group represented by the following formula (1).
The component (B) is a polymer having a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond. In other words, the component (B) is a polymer obtained by utilizing the polymerization of the polymerizable carbon-carbon unsaturated bond of the monomer having a polymerizable carbon-carbon unsaturated bond.

Examples of the substituent in the divalent carbocycle which may have a substituent and the divalent heterocycle which may have a substituent include a halogen atom, an alkyl group, an alkoxy group and an amino group. Examples thereof include a hydroxy group and a carboxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like.
Examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms.
Examples of the alkoxy group include an alkoxy group having 1 to 6 carbon atoms.
The number of substituents in the divalent carbocycle and the divalent heterocycle is not particularly limited.

Examples of R ² include a divalent group represented by the following formula (1-1).

(In formula (1-1), * 1 represents a binding site with R ¹ , * 3 represents a binding site with R ³ , and R ⁴ represents a divalent carbocyclic ring that may have a substituent. Alternatively, it represents a divalent heterocycle which may have a substituent, m represents 0 or 1, and n represents an integer of 1 to 6).
The —C _n H _2n − (n represents an integer of 1 to 6) in the formula (1-1) may be a linear alkylene group or a branched alkylene group.

Examples of ^R4 include a divalent group represented by the following formula (1-2).

(In the formula (1-2), * 1 represents a binding site with R ¹ , * represents a binding site with —O—, k represents an integer of 0 to 4, and P represents a substituent. When k is 2 or more, P may be the same or different.)
The binding site * 1 and the binding site * may be at

positions

1 and 2, may be at

positions

1, 3, and may be at

positions

1, 4.
Examples of the substituent which is P include an amino group and the like.

R ³ is not particularly limited as long as it is an organic group that induces radical polymerization, and examples thereof include organic groups that induce radical polymerization represented by the following formulas [W], [Y], or [Z].

(In the formulas [W], [Y], and [Z], * indicates a bond site, and Ar is a group consisting of phenylene, naphthylene, and biphenylylene which may have an organic group and / or a halogen atom as a substituent. R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R ⁹ and R ¹⁰ are alkyl groups. In the case of, they may be bonded to each other at the ends to form a ring structure. Q represents any of the following structures.

(In the formula, R ¹¹ represents -CH _2- , -NR-, -O-, or -S-, R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bond. The site is shown.). S ³ represents a single bond, -O-, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms), or -S-. R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. )

Examples of the group represented by the formula (1) include the following groups.

(In the formula, * indicates the binding site.)

The method for producing the polymer as the component (B) is not particularly limited, and examples thereof include the following production methods (i), (ii), or a combination thereof.
(I): A monomer having a group represented by the formula (1) and a polymerizable carbon-carbon unsaturated bond is used, and if necessary, another monomer having a polymerizable carbon-carbon unsaturated bond is used in combination. Then, polymerization is carried out to obtain a polymer as the component (B).
(Ii): Polymerization is carried out using a monomer having a polymerizable carbon-carbon unsaturated bond and having no group represented by the formula (1) to obtain a polymer (B'), and then the polymer (B'). A compound having a group represented by the formula (1) is reacted with B') to obtain a polymer as a component (B).

The monomer having the group represented by the formula (1) and the polymerizable carbon-carbon unsaturated bond is particularly limited as long as it has the group represented by the formula (1) and the polymerizable carbon-carbon unsaturated bond. However, for example, a monomer represented by the following formula (2) can be mentioned.

(In the formula (2), R ¹ , R ² and R ³ are the same as R ¹ , R ² and R ³ in the formula (1), respectively. R ^a is the following formula [X-1]. -Represents a radically polymerizable group represented by any of [X-18].)
As ^Ra , the formula [X-1] or [X-2] is preferable.

(In formulas [X-1] to [X-18], * indicates a binding site, S ₁ and S ₂ independently represent -O-, -NR-, or -S-, respectively, and R is. Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (among the alkyl groups having 1 to 10 carbon atoms, a part of the _−CH2- group of the alkyl group having 2 to 10 carbon atoms is replaced with an oxygen atom. However, in _S2R or NR, when a part of the _−CH2 _- group of the alkyl group is replaced with an oxygen atom, the oxygen atom is directly bonded to S2 or N. No.). R ₁ and R ₂ independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.)

Examples of the monomer having a polymerizable carbon-carbon unsaturated bond include a monomer having a radically polymerizable group represented by any of the above formulas [X-1] to [X-18].
Other monomers having a polymerizable carbon-carbon unsaturated bond include, for example, methacrylates such as methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, lauryl methacrylate, and n-octyl methacrylate. Acrylate-based monomers; acrylate-based monomers such as methyl acrylate, ethyl acrylate, tert-butyl acrylate, benzyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, n-octyl acrylate; styrene, styrene derivative (eg, o- , M-, p-methoxystyrene, o-, m-, p-tert-butoxystyrene, o-, m-, p-chloromethylstyrene, etc.), vinyl esters (eg, vinyl acetate, vinyl propionate, benzoate) Vinyl acrylate, etc.), vinyl ketones (eg, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, etc.), N-vinyl compounds (eg, N-vinylpyrrolidone, N-vinylpyrrole, N-vinylcarbazole, N-vinyl, etc.) Indole, etc.), (meth) acrylic acid derivatives (eg, acrylonitrile, metaacrylonitrile, acrylamide, isopropylacrylamide, methacrylicamide, etc.), vinyl halides (eg, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloroprene, vinyl fluoride, etc.) ) And other vinyl monomers, but are not limited to these.

The number of polymerizable carbon-carbon unsaturated bonds in the monomer having a polymerizable carbon-carbon unsaturated bond used in the method for producing the polymer as the component (B) is not particularly limited and is one. It may be two, two or more.
However, from the viewpoint of solvent solubility, the number of polymerizable carbon-carbon unsaturated bonds in the monomer is preferably one.
That is, the number of polymerizable carbon-carbon unsaturated bonds in the monomer having the group represented by the formula (1) and the polymerizable carbon-carbon unsaturated bond is preferably one.
The number of polymerizable carbon-carbon unsaturated bonds in the other monomers having a polymerizable carbon-carbon unsaturated bond is preferably one.
The number of polymerizable carbon-carbon unsaturated bonds in the monomer having no group represented by the formula (1) and having a polymerizable carbon-carbon unsaturated bond is preferably one.

In the above (ii), as a method for obtaining a polymer (B') by carrying out polymerization using a monomer having a polymerizable carbon-carbon unsaturated bond and having no group represented by the formula (1), for example. , A method of polymerizing maleic acid alone or with other monomers.
Examples of other monomers include isobutylene and the like.
In the above (ii), the polymer (B') may be a commercially available product. Examples of commercially available products include ISOBAM-10 (manufactured by Kuraray Co., Ltd.) and the like.
In the above (ii), the polymer (B') is reacted with a compound having a group represented by the formula (1) to obtain a polymer as a component (B). Examples of the compound having a group represented by the formula (1) include a compound represented by the following formula (3).

(In formula (3), R ¹ , R ² , and R ³ are the same as R ¹ , R ² , and R ³ in formula (1), respectively. Rs is a hydrogen atom or 1 to 3 carbon atoms. Represents the alkyl group of.)
The reaction between the polymer (B') and the compound represented by the formula (3) is, for example, an ester bond formation reaction, an amide bond formation reaction, a urethane bond formation reaction, a urea bond formation reaction, or a carbon-carbon bond formation reaction. It can be carried out by utilizing a known bond formation reaction such as. The reaction temperature and reaction time in the reaction are not particularly limited.

The polymer (B) is, for example, a polymer (P) having at least one structural unit selected from the group consisting of the following formulas (m-1) and (m-2). Such a polymer (P) can be obtained, for example, by the above-mentioned production method (ii).

(R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 3 carbon atoms. R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Rs is. , A hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X represents a group represented by the formula (1).)

In the formulas (m-1) and (m-2), R ¹ and R ² are preferably independent hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, respectively, and R ¹ is a hydrogen atom and R. It is more preferable that ² is a hydrogen atom or an alkyl group having 1 carbon atom, and it is more preferable that R ¹ and R ² are hydrogen atoms.
R is preferably a hydrogen atom.
Rs is preferably a hydrogen atom.

The polymer (P) may contain one type of structural unit represented by the formulas (m-1) and (m-2) alone, or may contain two or more types. The total content of the structural units represented by the formulas (m-1) and (m-2) is preferably 5 to 80 mol%, preferably 10 to 50 mol%, based on the total structural units of the polymer (P). Is more preferable.

The polymer having a structural unit represented by the formula (m-1) is, for example, a primary or secondary polymer having a structural unit containing a maleic anhydride skeleton (maleic anhydride-based polymer). It can be obtained by reacting one or more kinds of amino compounds. In this reaction, the amino group of the primary or secondary amino compound is added to the carbonyl group of the maleic anhydride skeleton, and the ring-opening reaction proceeds, whereby the structural unit represented by the formula (m-1) is formed. Is obtained.

The polymer having a structural unit containing a maleic anhydride skeleton is preferably a maleic anhydride polymer containing a structural unit represented by the following formula (m) (hereinafter, also referred to as a structural unit (m)). , More preferably, a maleic anhydride copolymer (hereinafter, a copolymer) containing a structural unit (m) and a structural unit represented by the following formula (v) (hereinafter, also referred to as a structural unit (v)). (Mp).)

(R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 3 carbon atoms. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent hydrogen. Atom, alkyl group with 1 to 6 carbon atoms, -OC (= O) -R (R represents an alkyl group with 1 to 6 carbon atoms), -C (= O) -OR (R is 1 to 6 carbon atoms) Represents an alkyl group of 6), -OR (R represents an alkyl group having 1 to 6 carbon atoms), or a phenyl group.)

The structural unit (v) is, for example, ethylene, propylene, n-butene, isobutylene, n-pentene, n-hexene, acrylates and methacrylates to which an alkyl group having 1 to 4 carbon atoms is bonded (hereinafter, “1 to 4 carbon atoms”). 4 alkyl acrylates ”, also referred to as“ alkyl methacrylates having 1 to 4 carbon atoms ”), vinyl acetate, methyl vinyl ether, and

(R is hydrogen or an alkyl group having 1 to 6 carbon atoms, and the benzene ring may be optionally substituted with an alkyl group or a hydroxyl group having 1 to 4 carbon atoms.) It is obtained by polymerizing a monomer selected from.

Preferred examples of alkyl acrylates having 1 to 4 carbon atoms include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, and mixtures thereof. Preferred examples of alkyl methacrylates having 1 to 4 carbon atoms include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propylmethyl methacrylate, n-butyl methacrylate, and mixtures thereof. A mixture of alkyl methacrylates having 1 to 4 carbon atoms and alkyl acrylates having 1 to 4 carbon atoms may be used. Preferred examples of the styrene compound include styrene, α-methylstyrene, p-methylstyrene, tert-butylstyrene, and mixtures thereof. Mixtures with styrenic compounds, alkyl acrylates having 1 to 4 carbon atoms and / or methacrylates may be used. Of these, isobutylene or a mixture with isobutylene, 1-butene and 2-butene is particularly preferably used.

The structural unit (m) is preferably 10 to 50 mol%, more preferably 30 to 50 mol%, in all the structural units constituting the copolymer (Mp).
The molecular weight of the copolymer (Mp) is preferably 3,000 to 500,000, more preferably 8,000 to 150,000, with a weight average molecular weight.

Examples of the primary or secondary amino compound include compounds represented by the formula (3).

(In formula (3), R ¹ , R ² , and R ³ are the same as R ¹ , R ² , and R ³ in formula (1), respectively. Rs is a hydrogen atom or 1 to 3 carbon atoms. Represents the alkyl group of.)

The reaction of the polymer having a structural unit containing a maleic anhydride skeleton with a primary or secondary amino compound is preferably carried out in an organic solvent. Examples of the organic solvent used include alcohols, ethers, ketones, amides, esters, hydrocarbon compounds and the like. In the above reaction, the reaction temperature is preferably 30 to 120 ° C., and the reaction time is preferably 1 to 24 hours.
The reaction solution obtained by dissolving the polymer may be used as it is, or a method of pouring the reaction solution into a large amount of a poor solvent and drying the precipitate under reduced pressure, or distilling off the reaction solution under reduced pressure with an evaporator. The polymer contained in the reaction solution may be isolated and then subjected to preparation of the polymer composition by using a known isolation method such as the above-mentioned method.

The reaction amount of the primary or secondary amino compound is preferably 0.01 to 1.2 equivalents, preferably 0.1 to 1.2 equivalents, relative to the anhydrous group of the structural unit (m). More preferably, 0.1 to 1.0 equivalent is even more preferable.

A polymer having a structural unit represented by the formula (m-1) in which R is an alkyl group having 1 to 10 carbon atoms has, for example, a structural unit represented by the formula (m-1) in which R is hydrogen. It can be obtained by esterifying the polymer having it. Esterification can be carried out in the same manner as in the method of obtaining a polyamic acid ester from a polyamic acid.

The polymer having the structural unit represented by the formula (m-2) is obtained by ring-closing the polymer having the structural unit represented by the formula (m-1). The polymer (P) may contain a structural unit represented by the formula (m-1) in addition to the structural unit represented by the formula (m-2). As a method for obtaining a polymer having a structural unit represented by the formula (m-2), thermal imidization in which a solution of the polymer having the structural unit represented by the formula (m-1) is heated as it is, or a catalyst is added. Catalytic imidization can be mentioned. The temperature for thermal imidization in the solution is, for example, 100 to 400 ° C, preferably 120 to 250 ° C, and it is preferable to remove water generated by the imidization reaction from the system.

For catalytic imidization, a basic catalyst and, if necessary, an acid anhydride are added to a polymer solution having a structural unit represented by the formula (m-2), and the temperature is usually -20 to 250 ° C., preferably 0 to 0. This can be done by stirring at 180 ° C. The amount of the basic catalyst is, for example, 0.5 to 30 mol times, preferably 2 to 20 mol times, that of the amic acid group, and the amount of acid anhydride is, for example, 1 to 50 mol times, preferably 1 to 50 mol times that of the amic acid group. It is 3 to 30 mol times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine trioctylamine, N, N-dimethyl-4-aminopyridine and the like.

The polymer (P) may further have structural units other than the structural units represented by the formulas (m), (m-1), (m-2) and (v). Examples of the structural unit other than the structural unit represented by the formulas (m), (m-1), (m-2) and (v) include the following formulas (m-3) to (m-4) or. Structural units derived from other compounds having an ethylenic double bond can be mentioned.

(R ¹ , R ² , R, Rs are synonymous with the definitions in the above formulas (m-1) to (m-2). Y is a hydrogen atom or the above formulas (m-1) to (m-2). ) Represents a monovalent organic group other than X.

Specific examples of the monovalent organic group of Y in the formulas (m-3) to (m-4) include a carboxy group-containing monoamine such as p-aminobenzoic acid; an alicyclic group-containing monoamine such as cyclohexylamine; n. -Butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n- Alkyl group-containing monoamines such as tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine; or monovalent organic groups derived from aniline. Can be mentioned.

Examples of the other compounds having an ethylenic double bond include carboxy group-containing compounds such as acrylic acid, methacrylic acid, α-ethylacrylic acid, 2-hydroxyethyl (meth) acrylic acid, 4-vinylbenzoic acid, and maleic acid. Hydroxyl-containing compounds such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, N-methylol (meth) acrylamide; isooctyl acrylate, isodecyl acrylate, lauryl Long-chain alkyl group-containing compounds such as acrylates, decyl methacrylates and stearyl acrylates; alicyclic group-containing compounds such as cyclohexyl (meth) acrylates; benzene ring-containing compounds such as 2-phenoxyethyl acrylates and nonylphenyl acrylate ethoxylated; glycidyl ( Oxylanyl group-containing compounds such as meth) acrylate, methylglycidyl (meth) acrylate, 4- (glycidyloxy) butyl (meth) acrylate, 2-methacryloyloxyethyl isocyanate (Kalens MOI manufactured by Showa Denko Co., Ltd.), 2-[(3, 5-Dimethylpyrazoyl) carbonylamino] ethyl methacrylate (Carens MOI-BP manufactured by Showa Denko Co., Ltd.) and other compounds having an isocyanate group or a protected isocyanate group; ..

The polymer (P) may contain one type of structural unit represented by the formula (v) alone, or may contain two or more types. The content of the structural unit represented by the formula (v) is preferably 50 to 90 mol%, more preferably 30 to 70 mol%, based on all the structural units of the polymer (P).

When the polymer (B) is obtained by the above-mentioned production method (i) and when the polymer (B') is obtained by the above-mentioned production method (ii), for example, the polymerization is carried out in the presence of a radical polymerization initiator. Will be done.
As the radical polymerization initiator, a radical thermal polymerization initiator used in a general radical thermal polymerization reaction can be used. The radical thermal polymerization initiator is a compound that generates radicals by heating to a temperature higher than the decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), and hydroperoxides (peroxidation). Hydrogen, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.) Etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, etc.) Examples thereof include sodium persulfate, ammonium persulfate, etc.), azo-based compounds (azobisisobutyronitrile, 2,2'-di (2-hydroxyethyl) azobisisobutyronitrile, etc.). Such a radical thermal polymerization initiator may be used alone or in combination of two or more.

The polymer as the component (B) is produced, for example, in the presence of an organic solvent by the above (i), (ii) or a combination thereof.
The organic solvent used is not particularly limited as long as it dissolves the produced polymer. Further, even if the organic solvent does not dissolve the polymer, it may be mixed with the above solvent and used as long as the produced polymer does not precipitate.

Examples of the organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2 -Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methyl-ε-caprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphospho Luamide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve. Acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol- tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, Diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1,4-dioxane, n-hexane, n-pentane, n-octane. Tan, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-methoxypropionic acid Methyl, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglime, 4-hydroxy-4 -Methyl-2-pentanone, 2-ethyl-1-hexanol and the like can be mentioned. These organic solvents may be used alone or in combination.

In the above (i), the reaction temperature and reaction time of the polymerization reaction for obtaining the polymer as the component (B) are not particularly limited. Examples of the reaction temperature include 50 to 100 ° C. Examples of the reaction time include 1 to 48 hours.
In the above (ii), the reaction temperature and reaction time of the polymerization reaction for obtaining the polymer (B') are not particularly limited. Examples of the reaction temperature include 50 to 100 ° C. Examples of the reaction time include 1 to 48 hours.

The molecular weight of the polymer as the component (B) is not particularly limited, but the strength of the radical-generating film obtained by applying the radical-generating film-forming composition, the workability at the time of forming the coating film, the uniformity of the coating film, and the like can be determined. When considered, the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is preferably 1,000 to 1,000,000, more preferably 10,000 to 150,000.

The content of the polymer as the component (B) in the radical-generating film-forming composition is not particularly limited, but the content of the component (B) is determined from the viewpoints of liquid crystal orientation, film flatness, seal adhesion, and the like. The amount is preferably 0.01 to 50% by mass, more preferably 0.05 to 40% by mass, still more preferably 0.1 to 20% by mass, and 0.5 to 5% by mass with respect to the component (A). Is particularly preferable.

<Ingredient (A)>
The polymer [component (A)] used as the orientation component of the liquid crystal aligning agent for driving a transverse electric field is not particularly limited, and is, for example, a polyimide precursor, a polyimide, a polyurea, a polyamide, a polyacrylate, a polymethacrylate, a cellulose derivative, or a polyacetal. , Polystyrene or a derivative thereof, a poly (styrene-phenylmaleimide) derivative, a polyorganosiloxane, and the like, and at least one polymer selected from the group is preferable.
The component (A) is a polymer different from the component (B).

A preferred embodiment of the component (A) is a polymer selected from a polyamic acid obtained from a tetracarboxylic dianhydride component and a diamine component and an imidized product thereof.

Examples of the tetracarboxylic acid dianhydride component for obtaining a polyamic acid, which is a preferred embodiment of the component (A), include a compound represented by the following formula (A1).

In the formula (A1), A is a tetravalent organic group, preferably a tetravalent organic group having 4 to 30 carbon atoms.

The preferred structure of A is shown below, but the present invention is not limited thereto.

Of the above structures, (A-1) and (A-2) are preferable from the viewpoint of further improving the photo-orientation, and (A-4) is preferable from the viewpoint of improving the relaxation rate of the accumulated charge, and (A) is preferable. −15) to (A-17) are preferable from the viewpoint of further improving the liquid crystal orientation and improving the relaxation rate of the accumulated charge. The tetracarboxylic acid dianhydride component for obtaining the polyamic acid of the component (A) may be one kind of tetracarboxylic acid dianhydride, and two or more kinds of tetracarboxylic acid dianhydrides are used in combination. May be good.

<Diamine>
The diamine component used for the polymerization of the polyamic acid of the component (A) used in the radical generation film forming composition of the present invention consists of a diamine represented by the following formula (A2) and a diamine represented by the following formula (A3). It preferably contains at least one selected diamine.

A ₁ is a single bond, an alkylene group having 2 to 10 carbon atoms, or a group in which at least one of —CH _2- possessed by the alkylene group is replaced with —O— or —S— under non-contiguous conditions. ₂ is a halogen atom, a hydroxy group, an amino group, a thiol group, a nitro group, a phosphoric acid group, or a monovalent organic group having 1 to 20 carbon atoms independently, and a is 0 to 4 independently. When there are a plurality of A _2s , the structure of A ₂ may be the same or different. b and c are independently 1 or 2, and d is 0 or 1. )

The following are preferable specific examples of the diamine represented by the formula (A2), but the present invention is not limited thereto. Of these, formulas (A2-1), (A2-3), (A2-5) to (A2-7), and (A2-12) are particularly preferable.

The following are preferable specific examples of the diamine represented by the formula (A3), but the present invention is not limited thereto.

Further, from the viewpoint of improving the solvent solubility of the polyimide, and when the radical-generating film-forming composition of the present invention contains a polymer other than the component (A) and the component (B), the component (A) becomes a liquid crystal display. From the viewpoint that it tends to be unevenly distributed near the surface layer of the alignment film, it is preferable to use at least one of the diamines represented by the following formula (A4) as the other diamine.

In the formula (A4), Y ₁ is a divalent organic group containing the structure of the following formula (A5).

In the formula (A5), D represents a protecting group that is desorbed by heating and replaced with a hydrogen atom, and * represents a connection point with another structure. Preferred structures for D include the tert-butoxycarbonyl group.
Hereinafter, preferred specific examples of the diamine represented by the formula (A4) will be given, but the present invention is not limited thereto. Boc in the following structure represents a tert-butoxycarbonyl group.

Further, from the viewpoint of improving the relaxation rate of the accumulated charge, it is preferable to use at least one type of diamine represented by the following formula (A6).

In formula (A6), Y ₂ is a divalent organic group having a nitrogen atom bonded to an aromatic group or having a nitrogen-containing aromatic heterocycle.
The preferred structure of Y ₂ is shown below, but the present invention is not limited thereto.

The diamine used for the polymerization of the component (A) contained in the radical generation film forming composition of the present invention is a diamine other than the above formulas (A2) to (A6) as long as the effect of the present invention is not impaired (hereinafter referred to as “diamine”). It may also contain other diamines). Examples of other diamines are given below, but the present invention is not limited thereto.

m-phenylenediamine, 4- (2- (methylamino) ethyl) aniline, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diamino Naphthalene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) ) Propane, 1,3-bis (4-aminophenetyl) urea, etc.

The diamine component for obtaining the polyamic acid which is the component (A) may be one kind of diamine or two or more kinds of diamines may be used in combination.

Further, the polymer selected from the polyamic acid as the component (A) and the imidized product thereof may be used alone, or the polymer obtained by using the tetracarboxylic dianhydride component and the diamine component. It may be a mixture of each other. When the polymers are mixtures, the polymers are different from each other.

The polymer as the component (A) may contain an organic group that induces radical polymerization, or may not contain an organic group that induces radical polymerization. It is preferable to introduce it in the case of reducing the sensitivity in the formation of the polymer layer, that is, the irradiation amount of UV, improving the film hardness, etc., but in terms of liquid crystal orientation, response speed, storage stability, etc., an organic group that induces radical polymerization. It is considered preferable to introduce a small amount of the radical solution or not to have it, and it is important to combine them appropriately.

When a polymer containing an organic group that induces radical polymerization is used as the component (A), the organic group that induces radical polymerization is, for example, an organic group that induces radical polymerization in the polymer as the component (B). Can be mentioned.

When a polymer containing an organic group that induces radical polymerization is used as the component (A), in order to obtain a polymer having a group capable of generating radicals, as a monomer component, a methacrylic group, an acrylic group, a vinyl group, etc. Using a monomer having a photoreactive side chain containing at least one selected from an allyl group, a kumalyl group, a styryl group and a cinnamoyl group, or a monomer having a site that is decomposed by ultraviolet irradiation and generates a radical in the side chain. It is preferable to manufacture.
Specific examples of the monomer containing an organic group that induces radical polymerization are diamines that generate radicals and have a polymerizable side chain, and examples thereof include diamines having an organic group represented by the following formula (1). It can, but is not limited to.

(In formula (1), * represents a binding site, R ¹ is a single bond, -CH _2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-,- Represents CH ₂ O-, -N (CH ₃ )-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-.
R ² represents an alkylene group having 1 to 20 carbon atoms which is single-bonded, or unsubstituted or substituted with a fluorine atom, and one or more of any -CH _2- or -CF _2- of the alkylene group is independent of each other. It may be replaced with a group selected from -CH = CH-, a divalent carbocycle which may have a substituent, and a divalent heterocycle which may have a substituent. Further, one or more of any -CH _2- or -CF _2- of the alkylene group is one of the following groups, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH. -Or -NH- may be replaced by at least one of these groups, provided they are not adjacent to each other.
R ³ represents an organic group that induces radical polymerization. )
Specific examples include the diamines shown below.

(In the formula, J ¹ is a bonding group selected from a single bond, -O-, -COO-, -NHCO-, and -NH-, and J ² is a single bond, or unsubstituted or substituted with a fluorine atom. Represents an alkylene group having 1 to 20 carbon atoms.)

(In the equation, n is an integer of 2 to 8, and E is a single bond, -O-, -C (CH ₃ ) _2- , -NH-, -CO-, -NHCO-, -CONH-,-. COO-, -OCO-,-(CH ₂ ) _m- , -SO _2- , -O- (CH ₂ ) _m -O-, -OC (CH ₃ ) _2- , -C (CH ₃ ) ₂ -O-, -CO- (CH ₂ ) _m -,-(CH ₂ ) _m -CO-, -NH- (CH ₂ ) _m -,-(CH ₂ ) _m -NH-, -SO _2- (CH) ₂ ) _m -,-(CH ₂ ) _m -SO _2- , -CONH- (CH ₂ ) _m -,-(CH ₂ ) _m -NHCO-, -CONH- (CH ₂ ) _m -NHCO- or -COO -(CH ₂ ) _m -OCO-, where m is an integer of 1-8.)

The structure of the tetracarboxylic acid dialkyl ester to be reacted with the above diamine component in the synthesis when the polymer as the component (A) is a polyamic acid ester is not particularly limited, and specific examples thereof are given below.

Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1. , 3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2, 3,4-Cyclopentane tetracarboxylic acid dialkyl ester, tetrahydrofuran-2,3,4,5-tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 2- (3,4-) Dicarboxycyclohexyl) Succinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dialkyl ester, 1,2,3,4-butanetetracarboxylic acid dialkyl ester , Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3', 4,4'-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxyl Cyclopentyl acetate dialkyl ester, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 <2,5>] Nonan-3,4,7,8-tetracarboxylic acid-3,4: 7,8-dialkylester, hexacyclo [6.6.0.1 <2,7>. 0 <3,6>. 1 <9,14>. 0 <10,13>] Hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dialkylester, 4- (2,5-dioxotetrahydrofuran-3-yl) -1, Examples thereof include 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dialkyl ester.

Examples of the aromatic tetracarboxylic acid dialkyl ester include pyromellitic acid dialkyl ester, 3,3', 4,4'-biphenyltetracarboxylic acid dialkyl ester, 2,2', 3,3'-biphenyltetracarboxylic acid dialkyl ester, and the like. 2,3,3', 4'-biphenyltetracarboxylic acid dialkyl ester, 3,3', 4,4'-benzophenone tetracarboxylic acid dialkyl ester, 2,3,3', 4'-benzophenone tetracarboxylic acid dialkyl ester , Bis (3,4-dicarboxyphenyl) ether dialkyl ester, Bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl ester, 2,3,6 Examples thereof include 7-naphthalene tetracarboxylic acid dialkyl ester.

In the synthesis when the polymer as the component (A) is polyurea, the diisocyanate to be reacted with the above diamine component is not particularly limited and can be used depending on availability and the like. The specific structure of diisocyanate is shown below.

In the formula, R ₂ and R ₃ represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms.

The aliphatic diisocyanates shown in K-1 to K-5 are inferior in reactivity but have the advantage of improving solvent solubility, and the aromatic diisocyanates shown in K-6 to K-13 are highly reactive and heat resistant. However, there is a drawback that the solvent solubility is lowered. K-1, K-7, K-8, K-9, and K-10 are preferable in terms of versatility and characteristics, K-12 is preferable from the viewpoint of electrical characteristics, and K-13 is preferable from the viewpoint of liquid crystal orientation. Two or more kinds of diisocyanates can be used in combination, and it is preferable to apply various diisocyanates according to the desired characteristics.

In addition, some diisocyanates can be replaced with the tetracarboxylic acid dianhydride described above, and may be used in the form of a copolymer of polyamic acid and polyurea, and the polyimide and polyurea can be chemically imidized. It may be used in the form of a copolymer.

The structure of the dicarboxylic acid to be reacted in the synthesis when the polymer as the component (A) is polyamide is not particularly limited, but specific examples are as follows. Examples of the aliphatic dicarboxylic acid include malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, and 2,2-dimethylglutal. Examples thereof include dicarboxylic acids such as acids, 3,3-diethylsuccinic acid, adipic acid, sebacic acid and suberic acid.

Examples of the alicyclic dicarboxylic acid include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, and 1,3-cyclobutanedicarboxylic acid. Acid, 3,4-diphenyl-1,2-cyclobutane dicarboxylic acid, 2,4-diphenyl-1,3-cyclobutane dicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid Acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexane Dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-norbornene-1,4-dicarboxylic acid, 2-norbornen-2,3-dicarboxylic acid, bicyclo [2.2.2] octane-1,4-dicarboxylic acid, Bicyclo [2.2.2] octane-2,3-dicarboxylic acid, 2,5-dioxo-1,4-bicyclo [2.2.2] octanedicarboxylic acid, 1,3-adamantandicarboxylic acid, 4,8 -Dioxo-1,3-adamantan dicarboxylic acid, 2,6-spiro [3.3] heptane dicarboxylic acid, 1,3-adamantan diacetic acid, camphor acid and the like can be mentioned.

Examples of aromatic dicarboxylic acids include o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, and 2,5-dimethylterephthalic acid. Acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracendicarboxylic acid, anthraquinone-1 , 4-Dicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,5-biphenylenedicarboxylic acid, p-terphenyl-4,4 "-dicarboxylic acid, diphenylmethane-4,4' -Dicarboxylic acid, 1,2-bis (4-carboxyphenyl) ethane, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, diphenyl ether-4,4 '-Dicarboxylic acid, bibenzyl-4,4'-dicarboxylic acid, 4,4'-stilbendicarboxylic acid, trans-4,4'-dicarboxylic acid, 4,4'-carbonyldibenzoic acid, 4,4'-sulfonyl Dibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylene diacetic acid, 3,3'-p-phenylenedipropionic acid, 4-carboxykerhide acid, p-phenylenediacrylic acid, 3,3'- [4,4'-(methylenedi-p-phenylene)] dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene)] dipropionic acid, 4,4'-[4,4'-(4,4'-(oxydi-p-phenylene)] '-(Oxydi-p-phenylene)] dicarboxylic acid such as dibutyric acid, (isopropyridendi-p-phenylenedioxy) dibutyric acid, and bis (p-carboxyphenyl) dimethylsilane can be mentioned.

Examples of the dicarboxylic acid containing a heterocycle include 1,5- (9-oxofluorene) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4,5-thiazoledicarboxylic acid, and the like. 1,2,5-Thiadiazol-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2, Examples thereof include 5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, and 3,5-pyridinedicarboxylic acid.

The above-mentioned various dicarboxylic acids may have an acid dihalide or an anhydrous structure. It is particularly preferable that these dicarboxylic acids are dicarboxylic acids capable of giving a polyamide having a linear structure from the viewpoint of maintaining the orientation of the liquid crystal molecules. Among these, terephthalic acid, isoterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, 1,2-bis (4-carboxyphenyl) ethane , 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, p-terphenyl-4,4 "-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,5-pyridinedicarboxylic acids, acid dihalides thereof, etc. are preferably used. Some of these compounds have isomers, but they may be a mixture containing them, and two or more kinds of compounds may be used. The dicarboxylic acids used in the present invention are not limited to the above-mentioned exemplary compounds.

A known synthetic method can be used to obtain a polyamic acid by a reaction between a diamine component and a tetracarboxylic acid dianhydride component. Generally, it is a method of reacting a diamine component and a tetracarboxylic acid dianhydride component in an organic solvent.

The reaction between the diamine component and the tetracarboxylic acid dianhydride component is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.

The organic solvent used in the above reaction is not particularly limited as long as it dissolves the produced polymer. Further, even if the organic solvent does not dissolve the polymer, it may be mixed with the above solvent and used as long as the produced polymer does not precipitate. Since the water content in the organic solvent inhibits the polymerization reaction and further causes the produced polymer to be hydrolyzed, it is preferable to use a dehydrated and dried organic solvent.

Examples of the organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2 -Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methyl-ε-caprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, phosphoramide, γ -Buchirolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carvi Thor, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, Dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono Acetate 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, amylacetate, butylbutyrate, butyl ether, diisobutylketone, methylcyclohexene, propyl ether, dihexyl ether, 1,4-dioxane, n-hexane, n-pentane, n-octane, diethyl Luether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3 -Methylethyl ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglime, 4-hydroxy-4-methyl- Examples thereof include 2-pentanone and 2-ethyl-1-hexanol. These organic solvents may be used alone or in combination.

When the diamine component and the tetracarboxylic acid dianhydride component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid dianhydride component is used as it is or is organic. A method of adding a tetracarboxylic acid dianhydride component dispersed or dissolved in a solvent, conversely a method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride component is dispersed or dissolved in an organic solvent, a method of adding a tetracarboxylic acid dianhydride component and a diamine component. Examples thereof include a method of adding alternately, and any of these methods may be used. When the diamine component or the tetracarboxylic acid dianhydride component is composed of a plurality of types of compounds, the reaction may be carried out in a premixed state, may be reacted individually in sequence, or may be further reacted individually with a low molecular weight. The bodies may be mixed and reacted to form a high molecular weight compound.

The temperature at which the diamine component and the tetracarboxylic acid dianhydride component are reacted can be selected from any temperature, and is, for example, in the range of -20 to 100 ° C, preferably -5 to 80 ° C. The reaction can be carried out at any concentration, for example, the total amount of the diamine component and the tetracarboxylic acid dianhydride component is 1 to 50% by mass, preferably 5 to 30% by mass with respect to the reaction solution. ..

The ratio of the total number of moles of the tetracarboxylic acid dianhydride component to the total number of moles of the diamine component in the above polymerization reaction can be arbitrarily selected according to the molecular weight of the polyamic acid to be obtained. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced. The preferred range is 0.8 to 1.2.

The method for synthesizing the polymer as the component (A) is not limited to the above method, and when synthesizing a polyamic acid, the above-mentioned tetracarboxylic acid dianhydride is similar to the general method for synthesizing a polyamic acid. Alternatively, a tetracarboxylic acid having a corresponding structure or a tetracarboxylic acid derivative such as a tetracarboxylic acid dihalide can be used and reacted by a known method to obtain the corresponding polyamic acid.

Further, polyimide can be obtained by ring-closing (imidizing) the polyamic acid. The imidization ratio as used herein is the ratio of the imide group to the total amount of the imide group and the carboxy group derived from the tetracarboxylic acid dianhydride. In polyimide, the imidization ratio does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose. The imidization rate of the polyimide is preferably 30% or more because the voltage retention rate can be increased, while 80% or less is set from the viewpoint of whitening characteristics, that is, from the viewpoint of suppressing the precipitation of the polymer in the varnish. preferable.

The temperature at which the polyamic acid is thermally imidized in the solution is usually 100 to 400 ° C, preferably 120 to 250 ° C, and it is preferable to remove the water generated by the imidization reaction from the outside of the system.

The catalytic imidization of the polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to the solution of the polyamic acid and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is usually 0.5 to 30 mol times, preferably 2 to 20 mol times the amount of the amic acid group, and the amount of the acid anhydride is usually 1 to 50 mol times, preferably 1 to 50 mol times the amic acid group. It is 3 to 30 mol times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like, and among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like, and among them, acetic anhydride is preferable because it facilitates purification after the reaction is completed. The imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, the reaction temperature, the reaction time, and the like.

When recovering the produced polymer from the reaction solution of the polymer, the reaction solution may be put into a poor solvent and precipitated. Examples of the poor solvent used for precipitate formation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water and the like. The polymer put into a poor solvent and precipitated can be collected by filtration and then dried at room temperature or by heating under normal pressure or reduced pressure. Further, by re-dissolving the polymer recovered by precipitation in an organic solvent and repeating the operation of re-precipitation recovery 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 the efficiency of purification is further improved.

The molecular weight of the polymer as the component (A) is GPC when the strength of the radical generation film obtained by applying the radical generation film forming composition, the workability at the time of forming the coating film, the uniformity of the coating film, etc. are taken into consideration. The weight average molecular weight measured by the (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

<< Photosensitive side-chain acrylic polymer that develops liquid crystallinity in a predetermined temperature range >>
One of the preferred embodiments of the component (A) is a photosensitive side-chain acrylic polymer that exhibits liquid crystallinity in a predetermined temperature range.
The side chain acrylic polymer preferably reacts with light in the wavelength range of 250 to 400 nm and exhibits liquid crystallinity in the temperature range of 100 to 300 ° C.
The side chain acrylic polymer preferably has a photosensitive side chain that reacts to light in the wavelength range of 250 to 400 nm.
The side chain acrylic polymer preferably has a mesogen group because it exhibits liquid crystallinity in a temperature range of 100 to 300 ° C.

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

The structure of the acrylic polymer has, for example, a main chain and a side chain bonded to the main chain, and the side chain contains a mesogen component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group. It has a structure having a photosensitive group bonded to the tip and undergoing a cross-linking reaction and an isomerization reaction in response to light, and a main chain and a side chain bonded to the main chain, and the side chain also serves as a mesogen component. Moreover, it can be a structure having a phenylbenzoate group that undergoes a photofreeze rearrangement reaction.

More specific examples of the structure of the photosensitive side-chain acrylic polymer that develops liquidity in a predetermined temperature range include hydrocarbons, (meth) acrylates, itaconates, fumarate, maleates, α-methylene-γ-. A main chain composed of at least one selected from the group consisting of radically polymerizable groups such as butyrolactone, styrene, vinyl, maleimide, and norbornen, and a side chain composed of at least one of the following formulas (31) to (35). It is preferable that the structure has.

In the formula, Ar ₁ to Ar ₅ independently represent a divalent substituent obtained by removing two hydrogen atoms from a benzene ring, a naphthalene ring, a pyrrole ring, a furan ring, a thiophene ring, or a pyridine ring.
One of q1 and q2 is 1 and the other is 0.
Y ₁ to Y ₂ represent CH = CH, CH = N, N = CH or CC (however, the carbon-carbon bond is a triple bond).
S ₁ to S ₃ independently represent a single bond, a linear or branched alkylene group having 1 to 18 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, a phenylene group or a biphenylylene group, or a single bond or ether. Represents one or more bonds selected from a bond, ester bond, amide bond, urea bond, urethane bond, amino bond, carbonyl group or a combination thereof, or via the one or more bonds. A linear or branched alkylene group having 1 to 18 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, a phenylene group, a biphenylylene group, or a combination thereof of 2 or more and 10 or less sites are bonded to each other. The structure may be such that a plurality of the substituents are linked via the bond.
R ³¹ is a hydrogen atom, a hydroxy group, a mercapto group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylamino group having 1 to 8 carbon atoms or a dialkyl group having 2 to 16 carbon atoms. Representing an amino group, the benzene ring and / or the naphthalene ring is substituted with one or more identical or different substituents selected from a halogen atom, a cyano group, a nitro group, a carboxy group and an alkoxycarbonyl group having 2 to 11 carbon atoms. You may. At that time, the alkyl group having 1 to 10 carbon atoms may be linear, branched, cyclic, or may have a structure in which they are combined, and the hydrogen atom of the alkyl group may be substituted with a halogen atom.

The photosensitive side chain acrylic polymer that exhibits liquid crystallinity in a predetermined temperature range, which is a kind of the component (A) of the present application, can contain a liquid crystal side chain.
As a mesogen group having a liquid crystal side chain, even if it is a group having a mesogen structure by itself such as a biphenyl structure or a phenylbenzoate structure, a group having a mesogen structure by hydrogen bonding between the side chains such as benzoic acid. May be. The following structure is preferable as the mesogen group contained in the side chain.

<<< Manufacturing method of photosensitive side chain polymer >>>
The photosensitive side chain type acrylic polymer that exhibits liquid crystallinity in the above-mentioned predetermined temperature range can be obtained by polymerizing the photoreactive side chain monomer having the above-mentioned photosensitive side chain and the liquid crystal side chain monomer. Can be done.

[Photoreactive side chain monomer]
The photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at a side chain portion of the polymer when the polymer is formed.
As the photoreactive group of the side chain, the structures represented by the above formulas (31) to (35) are preferable.
As a more specific example of the photoreactive side chain monomer, a polymerizable group selected from the following PG1 to PG6 and a photosensitive side chain consisting of at least one of the above formulas (31) to (35) are bonded. It is preferably a structure.

In the formula, M ¹ represents a hydrogen atom or a methyl group.

[Liquid crystal side chain monomer]
The liquid crystal side chain monomer is a monomer in which a polymer derived from the monomer exhibits liquidity and the polymer can form a mesogen group at a side chain site.
More specific examples of the liquid crystal side chain monomer include radical polymerizable groups such as hydrocarbons, (meth) acrylates, itaconates, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide and norbornene. It is preferable that the structure has a polymerizable group composed of at least one selected from the above group and a side chain having at least one of the above-mentioned "mesogen groups having a liquid crystal side chain".

As the liquid crystal side chain monomer, a monomer in which a liquid crystal side chain selected from the following formulas (1) to (12) is bonded to a polymerizable group selected from the above formulas PG1 to PG6 is preferable.

In equations (1) to (12), A3 and ^A4 are independently single ^- bonded, -O-, -CH _2- , -C (= O) -O-, and -OC (= O). )-, -C (= O) NH-, -NHC (= O)-, -CH = CH-C (= O) O-, or -OC (= O) -CH = CH-, representing R ¹¹ -NO ₂ , -CN, halogen atom, phenyl group, naphthyl group, biphenylyl group, furanyl group, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, carbon number of 1 Represents an alkyl group to 12 or an alkoxy group having 1 to ¹² carbon atoms, and R12 is a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, and a monovalent group having 5 to 8 carbon atoms. Represents a group selected from the group consisting of an alicyclic hydrocarbon group and a group obtained by combining these, and the hydrogen atom bonded to these is -NO ₂ , -CN, a halogen atom, and an alkyl having 1 to 5 carbon atoms. It may be substituted with a group or an alkoxy group having ¹ to 5 carbon atoms, and R13 is a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen atom. , Phenyl group, naphthyl group, biphenylyl group, furanyl group, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, alkyl group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms. Represents 12 alkoxy groups, E represents -C (= O) O- or -OC (= O)-, d represents an integer of 1 to 12, and k1 to k5 are independent of each other. , 0 to 2, but the sum of k1 to k5 in each equation is 2 or more, and k6 and k7 are independently integers of 0 to 2, but in each equation, k6 and k7. The sum is 1 or more, m1, m2 and m3 are independently integers of 1 to 3, n is 0 or ¹ , and Z1 and Z2 ^are independently and single-coupled, respectively. , -C (= O)-, -CH ₂ O-, -CH = N- or -CF _2- .

The side chain type acrylic polymer which is one aspect of the component (A) can be obtained by the polymerization reaction of the photoreactive side chain monomer exhibiting the liquid crystal property described above. Further, it can be obtained by copolymerizing a photoreactive side chain monomer that does not exhibit liquidity and a liquid crystal side chain monomer, or by copolymerizing a photoreactive side chain monomer that exhibits liquidity and a liquid crystal side chain monomer. can. Furthermore, it can be copolymerized with other monomers as long as the liquid crystallinity is not impaired.

Examples of other monomers include industrially available radical polymerization-reactive monomers.
Specific examples of other monomers include unsaturated carboxylic acids, acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic acid anhydrides, styrene compounds and vinyl compounds.
Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate and 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-tricyclo [5.2.1.0 <2,6>] decylacrylate, and 8-ethyl-8-tricyclo [5.2.1.0 <2]. , 6>] Decyl acrylate and the like.
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 and 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-methyl-8-tricyclo [5.2.1.0 <2,6>] decylmethacrylate, and 8-ethyl-8-tricyclo [5.2.1.0 <2]. , 6>] Decyl methacrylate and the like. (Meta) 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, propyl vinyl ether and the like.
Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene and the like.
Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

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

As the polymerization initiator for radical polymerization, a known radical polymerization initiator such as AIBN (azobisisobutyronitrile) or a known compound such as a reversible addition-cleaving chain transfer (RAFT) polymerization reagent shall be used. Can be done.

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

The organic solvent used for the polymerization reaction of the photosensitive side chain acrylic polymer that develops liquid crystallinity in a predetermined temperature range is not particularly limited as long as the produced polymer can be dissolved. Specific examples are given below.
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-ε-caprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, Phosphoramide, γ-butylollactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbi Thor, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether. , Diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol. Monoacetate Monopropyl ether, 3-Methyl-3-methoxybutyl acetate, Tripropylene glycol methyl ether, 3-Methyl-3-methoxybutanol, Diisopropyl ether, Ethylisobutyl ether, Diisobutylene, Amilacetate, Butylbutyrate, Butyl ether, Diisobutylketone, methylcyclohexene, propyl ether, dihexyl ether, 1,4-dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, acetic acid. Methyl, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Propylene Onic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglime, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3 -Ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like can be mentioned.
These organic solvents may be used alone or in combination. Further, even if the solvent does not dissolve the produced polymer, it may be mixed with the above-mentioned organic solvent and used as long as the produced polymer does not precipitate.
Further, in radical polymerization, oxygen in an organic solvent causes an inhibition of the polymerization reaction, so it is preferable to use an organic solvent degassed to the extent possible.

The polymerization temperature at the time of radical polymerization can be selected from any temperature of 30 to 150 ° C., but is preferably in the range of 50 to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution becomes too high, making uniform stirring difficult. Therefore, the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial reaction can be carried out at a high concentration and then an organic solvent can be added.
In the above-mentioned radical polymerization reaction, when the ratio of the radical polymerization initiator is large with respect to the monomer, the molecular weight of the obtained polymer is small, and when the ratio is small, the molecular weight of the obtained polymer is large. It is preferably 0.1 to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added at the time of polymerization.

When recovering the produced polymer from the reaction solution of the photosensitive side-chain polymer that can exhibit liquidity obtained by the above reaction, the reaction solution is put into a poor solvent and their weights are increased. The coalescence may be precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water and the like. The polymer which has been put into a poor solvent and precipitated can be collected by filtration and then dried at room temperature or by heating under normal pressure or reduced pressure. Further, by re-dissolving the polymer recovered by precipitation in an organic solvent and repeating the operation of re-precipitation recovery 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 the efficiency of purification is further improved.

The molecular weight of the photosensitive side-chain acrylic polymer that exhibits liquidity in a predetermined temperature range, which is one aspect of the component (A) of the present invention, is the strength of the obtained coating film and the workability at the time of forming the coating film. In consideration of the uniformity of the coating film, the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is preferably 2,000 to 1,000,000, preferably 5,000 to 100,000. Some are more preferred.

<Other ingredients>
The radical generating film-forming composition may contain other components such as a radical generating agent and an organic solvent in addition to the component (A) and the component (B).
Examples of the radical generator include a compound that generates a radical by heat, a compound that generates a radical by light, and the like.

The compound that generates radicals by heat is a compound that generates radicals by heating to a temperature higher than the decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), and hydroperoxides (peroxidation). Hydrogen, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.) Etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, etc.) Examples thereof include sodium persulfate, ammonium persulfate, etc.) and azo radical compounds (azobisisobutyronitrile, and 2,2'-bis (2-hydroxyethyl) azobisisobutyronitrile, etc.). Such a radical thermal polymerization initiator may be used alone or in combination of two or more.

The compound that generates radicals with light 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 and 2-hydroxy. -2-Methylpropiophenone, 2-Hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthron, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-( 4-Molholinophenyl) -butanone-1, 4-ethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di (tert-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (3,4'-tri ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphinoxide, 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'-Methtylyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 1, 3-Bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p- Dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (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-hydroxycyclohexylphenylketone, bis (5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl ) Titanium, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tert-hexylperoxycarbonyl) benzophenone, 3,3'-di ( Methylcarbonyl) -4,4'-di (tert-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di (tert-butylperoxycarbonyl) benzophenone, 4,4'- Di (methoxycarbonyl) -3,3'-di (tert-butylperoxycarbonyl) benzophenone, 2- (3-methyl-3H-benzothiazole-2-iriden) -1-naphthalen-2-yl-etanone, or 2 -(3-Methyl-1,3-benzothiazole-2 (3H) -iriden) -1- (2-benzoyl) etanone and the like can be mentioned. These compounds may be used alone or in admixture of two or more.

The radical generating film forming composition can contain a polymer component, and if necessary, an organic solvent that dissolves or disperses a radical generating agent or other contained components. Such an organic solvent is not particularly limited, and examples thereof include organic solvents as exemplified in the above-mentioned synthesis of polyamic acid. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like are soluble. It is preferable from the viewpoint of. In particular, N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is preferable, but two or more kinds of mixed solvents may be used.

Further, it is preferable to use a solvent that improves the uniformity and smoothness of the coating film by mixing it with an organic solvent having high solubility of the components contained in the radical generation film forming composition.

Examples of the solvent for improving the uniformity and smoothness of the coating material include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve (ethylene glycol monobutyl ether), methyl cellosolve acetate, butyl cellosolve acetate, and ethyl cellosolve acetate. Butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert- Butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 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 , Ethylisobutyl ether, diisobutylene, amylacetate, butylbutyrate, butyl ether, diisobutylketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, lactic acid. Ethyl, n-propyl lactate, n-butyl lactate, isoamyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3- Methyl ethyl 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 diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, Examples thereof include dipropylene glycol, 2- (2-ethoxypropanol) propanol, 2-ethyl-1-hexanol and the like. A plurality of types of these solvents may be mixed. When these solvents are used, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total amount of the solvent contained in the radical generation film forming composition.

The radical generation film forming composition may contain components other than the above. Examples thereof include compounds that improve the film thickness uniformity and surface smoothness when the radical generation film forming composition is applied, compounds that improve the adhesion between the radical generation film forming composition and the substrate, and radical generation film formation. Examples thereof include compounds that further improve the film strength of the composition.

Examples of the compound that improves the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant. More specifically, for example, Ftop EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Megafuck F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (manufactured by 3M), Asahi. Examples thereof include Guard AG710 (manufactured by AGC), Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical). When these surfactants are used, the ratio of their use is preferably 0.01 to 2 parts by mass, more preferably 0, with respect to 100 parts by mass of the total amount of the polymer contained in the radical generation film forming composition. It is 0.01 to 1 part by mass.

Specific examples of the compound that improves the adhesion between the radical generation film forming composition and the substrate include a functional silane-containing compound and an epoxy group-containing compound. 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- (3-triethoxysilylpropyl) triethylenetetramine, N- (3-trimethoxysilylpropyl) triethylenetetramine, 10-trimethoxysilyl-1,4,7- Triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl- 3-Aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, Polyethylene Glycol Diglycidyl Ether, Propyl Glycol Diglycidyl Ether, Tripropylene Glycol Diglycidyl Ether, Polypropylene Glycol Diglycidyl Ether, Neopentyl Glycol Diglycidyl Ether, 1,6-Hexanediol Diglycidyl Ether, Glycerin Diglycidyl Ether, Dibromo Neopentyl Glycoldiglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N', N'-tetraglycidyl-m-xylylene diamine, 1,3-bis (N, N-Diglycidylaminomethyl) cyclohexane, N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- ( N, N-diglycidyl) Aminopropyltrimethoxysilane and the like can be mentioned.

Further, in order to further increase the film strength of the radical generation film, a phenol compound such as 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane or tetra (methoxymethyl) bisphenol may be added. good. When these compounds are used, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the polymer contained in the radical generation film forming composition. Is.

Further, in addition to the above, the radical generating film forming composition includes a dielectric or a conductive material for the purpose of changing the electric properties such as the dielectric constant and the conductivity of the radical generating film as long as the effect of the present invention is not impaired. Substances may be added.

[Radical generation membrane]
The radical generation film of the present invention can be obtained by using the above radical generation film forming composition. For example, a cured film obtained by applying the radical generation film forming composition used in the present invention to a substrate and then drying and firing it can be used as it is as a radical generation film. In addition, this cured film can be subjected to orientation processing by rubbing, polarization, light of a specific wavelength, or the like, or by processing an ion beam, etc., and the liquid crystal display element after filling the liquid crystal is irradiated with UV (ultraviolet rays). Is also possible.

The substrate on which the radical generation film forming composition is applied is not particularly limited as long as it is a highly transparent substrate, but a substrate on which a transparent electrode for driving a liquid crystal display is formed is preferable.

Specific examples include glass plates, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, and tri. Examples thereof include a substrate in which a transparent electrode is formed on a plastic plate such as acetyl cellulose, diacetyl cellulose, acetate butyrate cellulose or the like.

For the substrate that can be used for the IPS liquid crystal display element, electrode patterns such as standard IPS comb tooth electrodes and PSA fishbone electrodes and protrusion patterns such as MVA can also be used.

Further, in a high-performance element such as a TFT type element, an element such as a transistor is used between an electrode for driving a liquid crystal display and a substrate.

When a transmissive liquid crystal display element is intended, it is common to use a substrate as described above, but when a reflective liquid crystal display element is intended, silicon is used only on one side of the substrate. An opaque substrate such as a wafer can also be used. At that time, a material such as aluminum that reflects light can be used for the electrodes formed on the substrate.

Examples of the method for applying the radical-generating film-forming composition include a spin coating method, a printing method, an inkjet method, a spray method, a roll coating method, and the like, but the transfer printing method is widely used industrially from the viewpoint of productivity. It is also suitably used in the present invention.

The step of drying after applying the radical generation film forming composition is not always necessary, but if the time from application to firing is not constant for each substrate or if it is not fired immediately after coating, it is dried. It is preferable to include the process. The drying is not particularly limited as long as the solvent is removed to the extent that the shape of the coating film is not deformed by transporting the substrate or the like, and the drying means thereof is not particularly limited. For example, a method of drying on a hot plate having a temperature of 40 to 150 ° C., preferably 60 to 100 ° C. for 0.5 to 30 minutes, preferably 1 to 5 minutes can be mentioned.

The coating film formed by applying the radical generation film forming composition by the above method can be fired to form a cured film. At that time, the firing temperature can be usually any temperature of 100 to 350 ° C., but is preferably 140 to 300 ° C., more preferably 150 to 230 ° C., and further preferably 160 to 220 ° C. The firing time is usually any time of 5 to 240 minutes. It is preferably 10 to 90 minutes, more preferably 20 to 90 minutes. For heating, a generally known method, for example, a hot plate, a hot air circulation oven, an IR (infrared) type oven, a belt furnace, or the like can be used.

The thickness of this cured film can be selected as needed, but preferably 5 nm or more, more preferably 10 nm or more, because the reliability of the liquid crystal display element is improved. Further, when the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, the power consumption of the liquid crystal display element does not become extremely large, which is preferable.

Although the first substrate having a radical generating film can be obtained as described above, the radical generating film can be subjected to uniaxial orientation treatment. Examples of the method for performing the uniaxial alignment treatment include a photoalignment method, an orthorhombic vapor deposition method, rubbing, and a uniaxial alignment treatment using a magnetic field.

When the orientation treatment is performed by the rubbing treatment in one direction, for example, the substrate is moved so that the rubbing cloth and the film come into contact with each other while rotating the rubbing roller around which the rubbing cloth is wound. When the photo-alignment method is used, the alignment process can be performed by irradiating the entire surface of the film with polarized UV having a specific wavelength and heating the film as necessary.
In the case of the first substrate of the present invention in which the comb tooth electrode is formed, the direction is selected by the electrical properties of the liquid crystal, but when a liquid crystal having positive dielectric anisotropy is used, the rubbing direction is the comb tooth electrode. It is preferable that the direction is substantially the same as the extending direction of.

As a step of creating a weak anchoring part and a strong anchoring part, there is a method of irradiating radiation with an arbitrary pattern via a photomask or the like. This is a step of irradiating the radical generation membrane with radiation in advance to eliminate the radical generation site and prevent a weak anchoring state. Examples of the radiation used in this step include polarized light or light having a specific wavelength, an ion beam, and the like. It is particularly preferable to irradiate light having a wavelength having the highest absorbance at the portion corresponding to the photoradical generation site.

The second substrate of the present invention may or may not have a radical generation film. The second substrate is preferably a substrate having a conventionally known liquid crystal alignment film.

In the present invention, the first substrate may be a substrate having a comb tooth electrode, and the second substrate may be a facing substrate. Further, in the present invention, the second substrate may be a substrate having a comb tooth electrode, and the first substrate may be a facing substrate.

[LCD cell]
The liquid crystal cell of the present invention comprises a substrate having the radical generating film (first substrate) and a substrate having a known liquid crystal alignment film (second substrate) after forming a radical generating film on the substrate by the above method. Is obtained by arranging the radical generating film and the liquid crystal alignment film so as to face each other, sandwiching a spacer, fixing with a sealing agent, and injecting and sealing a liquid crystal composition containing a liquid crystal and a radically polymerizable compound. Be done. At that time, the size of the spacer used is usually 1 to 30 μm, but preferably 2 to 10 μm. Further, by making the rubbing direction of the first substrate parallel to the rubbing direction of the second substrate, it can be used in the IPS mode and the FFS mode, and if the rubbing directions are arranged so as to be orthogonal to each other, the twist nematic mode can be used. Can be used for.
The IPS substrate, which is a comb tooth electrode substrate used in the IPS (In-Plane Switching) mode, includes a base material, a plurality of linear electrodes formed on the base material, and arranged in a comb tooth shape, and a base. It has a liquid crystal alignment film formed on the material so as to cover the linear electrodes.
The FFS substrate, which is a comb tooth electrode substrate used in the FFS (Friend Field Switching) mode, is insulated from the base material, the surface electrode formed on the base material, and the insulating film formed on the surface electrode. It has a plurality of linear electrodes formed on the film and arranged in a comb-teeth shape, and a liquid crystal alignment film formed on the insulating film so as to cover the linear electrodes.

The method of injecting a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is not particularly limited, and a vacuum method of injecting a mixture containing the liquid crystal and the polymerizable compound after depressurizing the inside of the produced liquid crystal cell, polymerization with the liquid crystal. Examples thereof include a dropping method in which a mixture containing a sex compound is dropped and then sealed.

<Radical polymerizable compound and liquid crystal composition>
The polymerizable compound used together with the liquid crystal in the production of the liquid crystal display element of the present invention is not particularly limited as long as it is a radically polymerizable compound, and is, for example, a compound having one or two or more polymerizable reactive groups in one molecule. be. It is preferably a compound having one polymerizable reactive group in one molecule (hereinafter, may be referred to as "a compound having a monofunctional polymerizable group", "a compound having a monofunctional polymerizable group", etc.). .. The polymerizable reactive group is preferably a radically polymerizable reactive group, for example, a vinyl bond.

At least one of the radically polymerizable compounds is preferably a compound having compatibility with liquid crystal and having one polymerizable reactive group in one molecule, that is, a compound having a monofunctional radically polymerizable group.

The radically polymerizable polymerizable group M of the radically polymerizable compound is preferably a polymerizable group selected from the following structures.

(In the formula, * indicates a binding site. R ^b represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR ^c- , -S-, an ester bond and an amide bond. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ^d represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

The radically polymerizable compound has an unsaturated bond capable of performing radical polymerization in the presence of an organic radical, and is, for example, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, lauryl methacrylate, and the like. Methacrylate monomers such as n-octyl methacrylate; acrylate monomers such as tert-butyl acrylate, benzyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, n-octyl acrylate; styrene, styrene derivatives (eg, o). -, M-, p-methoxystyrene, o-, m-, p-tert-butoxystyrene, o-, m-, p-chloromethylstyrene, etc., vinyl esters (eg, vinyl acetate, vinyl propionate, etc.) Vinyl benzoate, etc.), vinyl ketones (eg, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, etc.), N-vinyl compounds (eg, N-vinylpyrrolidone, N-vinylpyrrole, N-vinylcarbazole, N- Vinyl indols, etc.), (meth) acrylic acid derivatives (eg, acrylonitrile, metaacrylonitrile, acrylamide, isopropylacrylamide, methacrylicamide, etc.), vinyl halides (eg, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloroprene, vinyl fluoride, etc.) Etc.), but are not limited to these. These various radically polymerizable monomers may be used alone or in combination of two or more. Further, it is preferable that these have compatibility with the liquid crystal.

Further, as the radically polymerizable compound, a compound represented by the following formula (Z) is also preferable.

(In the formula (Z ^{), Ra and R b} ^each independently represent a linear alkyl group having 2 to 8 carbon atoms, and E is a single bond, —O—, —NR ^c −, —S—, an ester bond, And a bonding group selected from an amide bond. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

A more preferable example of the radically polymerizable compound used in the present invention is represented by the following formula (A).

(In the formula (A), M represents a radically polymerizable polymerizable group, and R ₁ to R ₃ are independent single bonds or alkylene groups having 1 to 6 carbon atoms in which a bonding group may be inserted. , Ar represents an aromatic hydrocarbon group which may have a substituent, and X ₁ and X ₂ each independently have a hydrogen atom or an aromatic hydrocarbon group which may have a substituent. May be combined with the carbon atoms bonded to R ₁ X ₁ and R ₂ X ₂ and R ₁ X ₁ and R ₂ X ₂ to form a ring, however, R ₁ X ₁ , R. The total number of carbon atoms of ₂ X ₂ and R ₃ is 1 or more.)

By using the radically polymerizable compound represented by the formula (A), a weak anchoring transverse electric field liquid crystal display element can be stably manufactured without generating a pretilt angle in a narrow cell gap, and the drive voltage can be lowered and the voltage can be reduced. At the same time, it is possible to increase the response speed at the time of turning off, and in addition, it becomes possible to manufacture a lateral electric field liquid crystal display element with a small decrease in VHR even at a high temperature. The present inventors consider how the radically polymerizable compound represented by the formula (A) contributes to this as follows.
The radically polymerizable compound M represented by the formula (A) contributes to the radical polymerization of the radically polymerizable compound. As a result, a weak anchoring film can be formed, and a low drive voltage can be realized.
Further, Ar (an aromatic hydrocarbon group which may have a substituent) of the radically polymerizable compound represented by the formula (A) suppresses the generation of the pretilt angle, improves the response speed, and at high temperature. The inventors speculate that it contributes to high VHR.
Further, in the formula (A), M and Ar are not too close to each other, and there is a group [-C (R ₁ X ₁ ) (R ₂ X ₂ ) R _3- ] having a certain size between M and Ar. The present inventors speculate that this has the effect of further increasing the response speed.
In the present specification, the narrow cell gap means a cell gap of 3.5 μm or less.

In the formula (A), the alkylene group having 1 to 6 carbon atoms in which the linking group is inserted is a divalent group in which the linking group is inserted between carbons in the alkylene group having 1 to 6 carbon atoms. Alternatively, it means a divalent group in which a bonding group is inserted between an alkylene group having 1 to 6 carbon atoms and a carbon atom bonded to the alkylene group.
Examples of the bonding group include a carbon-carbon unsaturated bond, an ether bond (-O-), an ester bond (-COO- or -OCO-), an amide bond (-CONH- or -NHCO-), and the like. Examples of the unsaturated bond include a carbon-carbon double bond, and an alkylene group having 1 to 6 carbon atoms into which a bonding group is inserted has a carbon-carbon double bond inside, not at the end thereof. It is preferable to have a bond.
Examples of the alkylene group having 1 to 6 carbon atoms into which the bonding group may be inserted include an alkylene group having 1 to 6 carbon atoms and an oxyalkylene group having 1 to 6 carbon atoms. The oxygen atom in the oxyalkylene group having 1 to 6 carbon atoms is bonded to, for example, the carbon atom bonded to M, R ₁ , R ₂ and R ₃ in the formula (A).
The alkylene group having 1 to 6 carbon atoms may be a linear alkylene group, a branched alkylene group, or a cyclic alkylene group.

In the formula (A), examples of the aromatic hydrocarbon group which may have a substituent include a phenyl group and a naphthyl group which may have a substituent.
Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl halide group having 1 to 4 carbon atoms, a halogenated alkoxy group having 1 to 4 carbon atoms, and the like. Can be mentioned. The halogenation in the alkyl halide group and the halogenated alkoxy group may be total halogenation or partial halogenation. Examples of the halogen atom include a fluorine atom and a chlorine atom.

In the formula (A), examples of R ₁ include a single bond and an alkylene group having 1 to 6 carbon atoms. Specific examples of the alkylene group having 1 to 6 carbon atoms include a linear alkylene group having 1 to 6 carbon atoms.
In the formula (A), examples of R ₂ include a single bond and an alkylene group having 1 to 6 carbon atoms. Specific examples of the alkylene group having 1 to 6 carbon atoms include a linear alkylene group having 1 to 6 carbon atoms.
In the formula (A), examples of R ₃ include a single bond and an alkylene group having 1 to 6 carbon atoms. Specific examples of the alkylene group having 1 to 6 carbon atoms include a linear alkylene group having 1 to 6 carbon atoms.
In the formula (A), examples of X ₁ include a hydrogen atom and a phenyl group.
In the formula (A), examples of X ₂ include a hydrogen atom and a phenyl group.
In the formula (A), _Ar includes, for example, a phenyl group and the like.

In the formula (A), the total number of carbon atoms of R ₁ X ₁ , R ₂ X ₂ and R ₃ is not particularly limited as long as it is 1 or more, but it may be 2 or more.
Further, the total carbon number of R ₁ , R _2, and R ₃ may be, for example, 18 or less, 15 or less, or 10 or less.
When X ₁ and X ₂ are hydrogen atoms, the total carbon number of R ₁ , R _2, and R ₃ is not particularly limited as long as it is 1 or more, but it may be 2 or more.
In the case of an aromatic hydrocarbon group in which at least one of X ₁ and X ₂ may have a substituent, the total number of carbon atoms of R ₁ , R ₂ and R ₃ may be 0.

As a ring formed by combining R ₁ X ₁ and R ₂ X ₂ and carbon atoms bonded to R ₁ X ₁ and R ₂ X ₂ , for example, a bonding group may be inserted into the ring having 3 carbon atoms. 13 hydrocarbon rings can be mentioned. The binding group is as described above.

Examples of the radically polymerizable compound contained in the formula (A) and the formula (A-1) include the following radically polymerizable compounds.

Examples of the radically polymerizable compound represented by the formula (A) include radically polymerizable compounds represented by the following formulas (A-1) to (A-3).

In the formula, M represents a radically polymerizable polymerizable group.
R ₁ to R ₃ represent alkylene groups having 1 to 6 carbon atoms, each of which may have a single bond or a bonding group inserted independently.
Ar, Ar ₁ and Ar ₂ each represent an aromatic hydrocarbon group which may have a substituent independently.
R ₁₁ and R ₁₂ each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms to which a bonding group may be inserted.
In formula (A-1), the carbon atoms bonded to R ₁₁ and R ₁₂ and R ₁₁ and R ₁₂ may form a ring together.
In the formula (A-1), the total number of carbon atoms of R ₁₁ , R ₁₂ and R ₃ is 1 or more, and may be 2 or more. Further, the total number of carbon atoms may be 18 or less, 15 or less, or 10 or less.
In the formula (A-2), the total number of carbon atoms of R ₁ , R ₁₂ and R ₃ is not particularly limited and may be 0. The total number of carbon atoms may be, for example, 18 or less, 15 or less, or 10 or less.
In the formula (A-3), the total number of carbon atoms of R ₁ , R ₂ and R ₃ is not particularly limited and may be 0. The total number of carbon atoms may be, for example, 18 or less, 15 or less, or 10 or less.
Note that R ₁₁ is a case where X ₁ is a hydrogen atom in R ₁ X ₁ . R ₁₂ is the case where X ₂ is a hydrogen atom in R ₂ X ₂ .

A further preferred example of the radically polymerizable compound used in the present invention is represented by the following formula (A').

(In the formula (A'), M represents a radically polymerizable polymerizable group, R ₁ represents a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the three Xs are independent of each other. Represents a hydrogen atom or the following formula (B'), where at least one of the three Xs represents the formula (B').)

(In formula (B'), Y represents a single bond, -O-, -S-, or -NR-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bond site. R ₂ , R ₃ and R ₄ each independently represent an aromatic hydrocarbon group which may have an alkyl group or a substituent having 1 to 6 carbon atoms.)

By using the radically polymerizable compound represented by the formula (A'), a weak anchoring transverse electric field liquid crystal display element can be stably manufactured without generating a pretilt angle in a narrow cell gap, and the drive voltage can be lowered. At the same time, it is possible to increase the response speed when the voltage is off, and in addition, it is possible to manufacture a lateral electric field liquid crystal display element with a small decrease in VHR even at a high temperature. The present inventors consider how the radically polymerizable compound represented by the formula (A') contributes to this as follows.
The radically polymerizable compound M represented by the formula (A') contributes to the radical polymerization of the radically polymerizable compound. As a result, a weak anchoring film can be formed, and a low drive voltage can be realized.
Further, it is said that the radically polymerizable compound represented by the formula (A') -SiR ₂ R ₃ R ₄ contributes to the suppression of the generation of the pretilt angle, the improvement of the response speed, and the high VHR at high temperature. The inventors speculate.

The aliphatic hydrocarbon group in R ₁ of the formula (A') has 1 to 10 carbon atoms, may have 1 to 8 carbon atoms, may have 1 to 6 carbon atoms, or may have 1 to 6 carbon atoms. It may be 1 to 4.

The alkyl group having 1 to 6 carbon atoms in R ₂ , R ₃ and R ₄ of the formula (A') may be, for example, an alkyl group having 1 to 5 carbon atoms or having 1 to 4 carbon atoms. It may be an alkyl group. These alkyl groups may have a linear structure or a branched structure.

The aromatic hydrocarbon groups in _R2 , R3 _, and _R4 of the formula (A') may be unsubstituted or the hydrogen atom may be substituted with a substituent.
Examples of the substituent of the aromatic hydrocarbon group which may have a substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen having 1 to 4 carbon atoms. Examples thereof include an alkylated group and an alkoxy halide group having 1 to 4 carbon atoms. The halogenation in the alkyl halide group and the halogenated alkoxy group may be total halogenation or partial halogenation. Examples of the halogen atom include a fluorine atom and a chlorine atom.
Examples of the aromatic hydrocarbon group in the aromatic hydrocarbon group which may have a substituent include a phenyl group and a naphthyl group.
The number of substituents in the aromatic hydrocarbon group is not particularly limited.

In the radically polymerizable compound represented by the formula (A'), the number of groups represented by the formula (B') is one or more, and may be one or two. There may be three.
In the radically polymerizable compound represented by the formula (A'), the three Xs are independent of each other. Therefore, in the radically polymerizable compound represented by the formula (A'), when the number of groups represented by the formula (B') is two or more, the group represented by two or more formulas (B') is. It may have the same structure or may have a different structure.

In formula (B'), at least one of R ₂ , R ₃ , and R ₄ may be an aromatic hydrocarbon group which may have a substituent. Therefore, in formula (B'), one of R ₂ , R ₃ , and R ₄ may be an aromatic hydrocarbon group which may have a substituent, or R ₂ , R ₃ , and R. Two of ₄ may be aromatic hydrocarbon groups which may have a substituent, and three of R ₂ , R ₃ and R ₄ may be an aromatic hydrocarbon group which may have a substituent. It may be.

Examples of the radically polymerizable compound represented by the formula (A') include radically polymerizable compounds satisfying the following (I) to (III).
(I): In the formula (A'), M represents the following structure (C') or structure (D'), and R ₁ is an aliphatic hydrocarbon group having a linear or branched structure having 1 to 10 carbon atoms. Each of the three Xs independently represents a hydrogen atom or formula (B'). However, at least one of the three Xs represents the equation (B').
(II): In the formula (B'), Y represents —O— and * represents a binding site. R ₂ , R ₃ and R ₄ each independently represent an aromatic hydrocarbon group which may have an alkyl group or a substituent having 1 to 6 carbon atoms. However, at least one of R ₂ , R ₃ and R ₄ represents an aromatic hydrocarbon group which may have a substituent.
(III): It is not a radically polymerizable compound represented by the following formula (E').

Examples of the radically polymerizable compound contained in the formula (A') include the following radically polymerizable compounds.

The liquid crystal composition contains at least the liquid crystal and the radically polymerizable compound.
The content of the radically polymerizable compound in the liquid crystal composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 1% by mass or more, based on the total mass of the liquid crystal and the radically polymerizable compound. It is 10% by mass or less, more preferably 5% by mass or less.

Further, in the liquid crystal composition, in addition to the above radically polymerizable compound, a plurality of compounds having other monofunctional radically polymerizable groups (hereinafter, may be referred to as “other radically polymerizable compounds”) are used in combination. May be.

At least one of the radically polymerizable compounds contained in the liquid crystal composition has a compound having a polymerizable unsaturated bond in one molecule, which is compatible with the liquid crystal, that is, a monofunctional radically polymerizable group. It is preferably a compound.

As the radically polymerizable compound represented by the formula (Z), E in the formula has an ester bond (bond represented by —C (= O) —O— or —O—C (= O) −). Those are preferable from the viewpoints of ease of synthesis, compatibility with liquid crystal, and polymerization reactivity, and specifically, compounds represented by the following structures are preferable, but are not particularly limited.

Further, it is preferable that the liquid crystal composition contains a radically polymerizable compound in which the Tg of the polymer obtained by polymerizing the radically polymerizable compound is 100 ° C. or lower.

These various radically polymerizable monomers may be used alone or in combination of two or more. Further, it is preferable that these have compatibility with the liquid crystal.

The polymer obtained by polymerizing a radically polymerizable compound preferably has a Tg of 100 ° C. or lower, more preferably 0 ° C. or lower.

The liquid crystal generally refers to a substance exhibiting both solid and liquid properties, and typical liquid crystal phases include nematic liquid crystal and smectic liquid crystal, but the liquid crystal that can be used in the present invention is not particularly limited. One example is 4-pentyl-4'-cyanobiphenyl.

Next, sufficient energy is given to the liquid crystal cell into which the mixture (liquid crystal composition) containing the liquid crystal and the radically polymerizable compound is introduced to carry out the polymerization reaction of the radically polymerizable compound. This can be done, for example, by applying heat or UV irradiation, and the radically polymerizable compound is polymerized in situ to exhibit the desired properties. Of these, UV irradiation is preferable because it enables oriented patterning and allows the polymerization reaction to occur in a shorter time.

Also, heating may be performed during UV irradiation. The heating temperature at the time of UV irradiation is preferably in a temperature range in which the introduced liquid crystal exhibits liquid crystal properties, is usually 40 ° C. or higher, and is preferably heated at a temperature lower than a temperature at which the liquid crystal changes to an isotropic phase.

Here, as the UV irradiation wavelength in the case of UV irradiation, it is preferable to select the wavelength having the best reaction quantum yield of the reactive polymerizable compound, and the UV irradiation amount is usually 0.01 to 30 J / cm ² . However, preferably, it is 10 J / cm ² or less, and the smaller the UV irradiation amount, the more the reliability deterioration due to the destruction of the members constituting the liquid crystal display can be suppressed, and the UV irradiation time can be reduced, so that the manufacturing process can be performed. It is suitable because it improves tact.

Further, it is preferable that the heating in the case of polymerizing only by heating instead of UV irradiation is performed in a temperature range in which the temperature at which the polymerizable compound reacts and is lower than the decomposition temperature of the liquid crystal display. Specifically, it is 100 to 150 ° C.

When giving sufficient energy to polymerize the radically polymerizable compound, it is preferable that no voltage is applied and the state is in an electric field-free state.

[Manufacturing method of liquid crystal display element and liquid crystal display element]
A liquid crystal display element can be manufactured using the liquid crystal cell thus obtained.
The method for manufacturing a liquid crystal display element includes, for example, the following steps (1) to (4).
(1) A step of preparing a first substrate having a radical generating film of the present invention and a second substrate which may have a radical generating film (2) The radical generating film in the first substrate faces the second substrate. (3) A step of filling a liquid crystal composition containing a liquid crystal display and a radically polymerizable compound between the first substrate and the second substrate.
(4) A step in which a radically polymerizable compound is polymerized in a state where the liquid crystal composition is in contact with a radical generating film. The liquid crystal display element is, for example, a first substrate and a second arranged facing the first substrate. It has a substrate and a liquid crystal display filled between the first substrate and the second substrate. Then, the liquid crystal display element polymerizes the radically polymerizable compound in a state where the liquid crystal composition containing the liquid crystal and the radically polymerizable compound is brought into contact with the radical generating film of the first substrate having the radical generating film of the present invention. Let me.
The liquid crystal display element can be made into a reflective liquid crystal display element by, for example, providing a reflective electrode, a transparent electrode, a λ / 4 plate, a polarizing film, a color filter layer, or the like in the liquid crystal cell according to a conventional method. Further, a transmissive liquid crystal display element can be obtained by providing the liquid crystal cell with a backlight, a polarizing plate, a λ / 4 plate, a transparent electrode, a polarizing film, a color filter layer and the like according to a conventional method, if necessary.

The second substrate may be a second substrate having no radical generation film.
The second substrate may be a substrate coated with a liquid crystal alignment film having uniaxial orientation. The liquid crystal alignment film having uniaxial orientation may be a liquid crystal alignment film for horizontal alignment.

In the method for manufacturing a liquid crystal display element and the liquid crystal display element, for example, one of the first substrate and the second substrate is a substrate having a comb tooth electrode.

FIG. 1 is a schematic cross-sectional view showing an example of a transverse electric field liquid crystal display element of the present invention, and is an example of an IPS mode liquid crystal display element.
In the transverse electric field liquid crystal display element 1 illustrated in FIG. 1, the liquid crystal 3 is sandwiched between the comb tooth electrode substrate 2 provided with the liquid crystal alignment film 2c and the opposed substrate 4 provided with the liquid crystal alignment film 4a. The comb tooth electrode substrate 2 is formed on the base material 2a and the base material 2a, and is formed so as to cover the plurality of linear electrodes 2b arranged in a comb tooth shape and the linear electrodes 2b on the base material 2a. It also has a liquid crystal alignment film 2c. The facing substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b. The liquid crystal alignment film 2c is, for example, a weak anchoring film obtained by chemically changing a radical generation film. The liquid crystal alignment film on the comb-shaped electrode substrate side is obtained, for example, by polymerizing a radically polymerizable compound in a state where a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is in contact with a radical generating film.
In the lateral electric field liquid crystal display element 1, when a voltage is applied to the linear electrodes 2b, an electric field is generated between the linear electrodes 2b as shown by the electric lines of force L.

FIG. 2 is a schematic cross-sectional view showing another example of the transverse electric field liquid crystal display element of the present invention, and is an example of an FFS mode liquid crystal display element.
In the transverse electric field liquid crystal display element 1 illustrated in FIG. 2, the liquid crystal 3 is sandwiched between the comb tooth electrode substrate 2 provided with the liquid crystal alignment film 2h and the opposed substrate 4 provided with the liquid crystal alignment film 4a. The comb tooth electrode substrate 2 is formed on the base material 2d, the surface electrode 2e formed on the base material 2d, the insulating film 2f formed on the surface electrode 2e, and the insulating film 2f, and has a comb tooth shape. It has a plurality of arranged linear electrodes 2g and a liquid crystal alignment film 2h formed on the insulating film 2f so as to cover the linear electrodes 2g. The facing substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b. The liquid crystal alignment film 2h is, for example, a weak anchoring film obtained by chemically changing a radical generating film. The liquid crystal alignment film on the comb-shaped electrode substrate side is obtained, for example, by polymerizing a radically polymerizable compound in a state where a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is in contact with a radical generating film.
In the lateral electric field liquid crystal display element 1, when a voltage is applied to the surface electrode 2e and the linear electrode 2g, an electric field is generated between the surface electrode 2e and the linear electrode 2g as shown by the electric lines of force L.

The present invention will be specifically described below with reference to examples, but the present invention is not construed as being limited to these examples. The abbreviations of the compounds and the measuring method of each characteristic are as follows.

(Diamine)
DA-1 to DA-4: Compounds represented by the following formulas (DA-1) to (DA-4).

(Tetracarboxylic dianhydride)
TC-1: A compound represented by the following formula (TC-1)

(Additive)
Add-1: Compounds represented by the following formulas (Add-1) Addd-P1 to Add-P3: Compounds represented by the following formulas (Add-P1) to (Add-P3), respectively.

(solvent)
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve THF: Tetrahydrofuran (reaction reagent)
TEA: Triethylamine AIBN: Azobisisobutyronitrile DMAP: 4-Dimethylaminopyridine

<Viscosity measurement>
For the viscosity of the polyamic acid solution, etc., use an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), sample volume 1.1 mL (milliliter), cone rotor TE-1 (1 ° 34', R24), temperature 25. Measured at ° C.
<Measurement of molecular weight>
For the molecular weight of the polyimide precursor and polyimide, use a room temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko), a column (GPC KD-803, GPC KD-805) (manufactured by Showa Denko). Using, it was measured as follows.
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as an additive, lithium bromide monohydrate (LiBr · H ₂ O) is 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, tetrahydrofuran (THF) is 10 mL / L)
Flow rate: 1.0 mL / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (Tosoh) and polyethylene glycol (molecular weight; about) 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).

In a 300 mL four-necked flask equipped with a stirrer, 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one (20.0 g: 89.2 mmol), THF (200 g), And TEA (10.8 g: 107 mmol) were added, and methanol (10.3 g: 98.1 mmol) was slowly added dropwise while stirring under an ice bath, and after the addition was completed, the temperature was returned to room temperature and the reaction was carried out for 12 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (100 mL) was added and the precipitate was removed by filtration, washed with pure water (100 ml) and saturated brine (100 ml), and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was removed by filtration, and then the solvent was removed with a rotary evaporator to obtain a crude product. Purification is performed by column chromatography (developing solvent: ethyl acetate / hexane = 2/8 volume ratio), and the target product (21.6 g: yield 83.0%, colorless transparent viscous material) is obtained by removing the solvent. rice field.

In a 50 mL eggplant flask with a stirrer, 2- (4- (2-hydroxy-2-methylpropanoyl) fluoroxy) ethyl methyllate (2.00 g: 6.84 mmol) obtained in Synthesis Example 1 and AIBN (5. 6 mg: 0.03 mmol) and NMP (8.0 g) were weighed, subjected to nitrogen substitution three times, and then reacted at 60 ° C. for 24 hours with stirring. After completion of the reaction, NMP (13.3 g) and BCS (10.0 g) were added to obtain a polymer solution (Add-P1) used in the present invention. The molecular weight of this polymer was number average molecular weight (Mn): 16,200 and weight average molecular weight (Mw): 37,200.

In an eggplant flask with a 50 mL branch equipped with a stirrer, 2- (4- (2-hydroxy-2-methylpropanoyl) phenoxy) ethylthyllylate (2.00 g: 6.84 mmol) obtained in Synthesis Example 1 and methylmethryllate (0. 68 g: 6.84 mmol), AIBN (11.2 mg: 0.06 mmol), and NMP (10.7 g) were weighed, subjected to nitrogen substitution three times, and then reacted at 60 ° C. for 24 hours with stirring. After completion of the reaction, NMP (17.9 g) and BCS (13.4 g) were added to obtain a polymer solution (Add-P2) used in the present invention. The molecular weight of this polymer was Mn: 13,800 and Mw: 34,500.

DA-4 (6.43 g: 19.5 mmol), DMAP (21.5 mg: 0.17 mmol), and NMP (37.7 g) were weighed and stirred in a 200 mL eggplant flask with a stirrer. After dissolution, ISOBAM-10 (manufactured by Kuraray, 3.00 g) was added, and the mixture was reacted at room temperature for 24 hours. After completion of the reaction, NMP (62.9 g) and BCS (47.2 g) were added and stirred to obtain a polymer solution (Add-P3) used in the present invention.
ISOBAM-10 is a copolymer of isobutylene and maleic anhydride.

<Synthesis Example 5 Photo-Orientation Agent>
DA-2 (3.42 g: 14.0 mmol) and DA-3 (1.55 g: 6.0 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen introduction tube, and NMP (42.0 g) was weighed. ), Stir and dissolve in a nitrogen atmosphere, then add TC-1 (4.21 g: 18.8 mmol) and NMP (10.0 g) in an ice bath while keeping the temperature below 10 ° C., and add 24 at room temperature. By reacting for a time, a polyamic acid solution (PAA-1) having a viscosity of about 710 mPa · s and a solid content concentration of 15% by mass was obtained. The molecular weight of this polyamic acid was Mn: 15,500 and Mw: 41,800.

<Synthesis Example 6 Ref radical generation photoaligning agent>
DA-1 (1.08 g: 10.0 mmol) and DA-4 (3.30 g: 10.0 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen introduction tube, and NMP (49.2 g) was weighed. ), Stir and dissolve in a nitrogen atmosphere, then add TC-1 (4.30 g: 19.2 mmol) and NMP (10.0 g) in an ice bath while keeping the temperature below 10 ° C., and add 24 at room temperature. By reacting for a time, a polyamic acid solution (PAA-2) having a viscosity of about 280 mPa · s and a solid content concentration of 12% by mass was obtained. The molecular weight of this polyamic acid was Mn: 13,500 and Mw: 39,200.

(First step)
Hydrocinnamaldydide (25.0 g: 0.186 mol) and THF (300 mL) were weighed and dissolved in a 500 mL four-necked flask equipped with a stir bar. After cooling this solution to -78 ° C in a dry ice-methanol bath, add n-propylmagnesium bromide (1.5 mol / L THF solution, 186 mL: 0.279 mol) so that the internal temperature does not exceed -70 ° C. The mixture was added dropwise, and after the addition was completed, the temperature was returned to room temperature and the mixture was stirred for 18 hours. After confirming the completion of the reaction by HPLC, the reaction solution was cooled to 0 ° C., 1N hydrochloric acid aqueous solution (100 mL) was added, and quenching was performed. Ethyl acetate (200 mL) was added to this reaction solution, and the mixture was washed 3 times with pure water (100 mL) using a separating funnel. After washing, the product was dehydrated with magnesium sulfate and distilled off with a rotary evaporator to obtain a crude product. Further vacuum drying gave Add-1a (30.0 g: yield 89%, colorless and transparent liquid).

(Second step)
Add-1a (30.0 g: 0.168 mol), TEA (25.5 g: 0.252 mol), and THF (300 mL) were weighed and dissolved in a 500 mL four-necked flask equipped with a stir bar. After cooling this solution to 0 ° C. in an ice bath, a methylyloyl chloride (21.1 g: 0.201 mol) was gently added dropwise while keeping the internal temperature at 5 ° C. or lower, and the mixture was returned to room temperature and stirred for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to this reaction solution, and 3 times with a 10% aqueous solution of potassium carbonate (100 mL) and 3 times with pure water (100 mL) using a separating funnel. Washed. After washing, the product was dehydrated with magnesium sulfate and distilled off with a rotary evaporator to obtain a crude product. Purification is performed by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 9/1 (volume ratio)), and by distilling off the solvent and vacuum drying, Add-1 (35.6 g: yield 86). %, A colorless transparent liquid) was obtained. ¹ It was confirmed by 1 H-NMR measurement that it was the target product. BHT (for 0.01 mol%) was added and used as a polymerization inhibitor.
^{1 1} H-NMR (500 MHz) in DMSO-d ₆ : 7.28-7.15 (5H), 6.02 (1H), 5.64 (1H), 4.90-4.88 (1H), 2 .62-2.55 (2H), 1.90-1.85 (2H + 3H), 1.59-1.54 (2H), 1.30-1.28 (2H), 0.88-0.86 (3H) [ppm]

<< Preparation of liquid crystal alignment agent >>
<Preparation Example 1 Preparation of liquid crystal alignment agent AL-1>
Weigh 20.0 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 5 above into a 50 mL Erlenmeyer flask equipped with a stirrer, add NMP (15.0 g) and BCS (15.0 g), and add room temperature. The liquid crystal alignment agent (AL-1) was obtained by stirring with the mixture for 1 hour.

<Preparation Example 2 Preparation of Photoradical Generation Film Forming Composition AL-2>
In a 50 mL Erlenmeyer flask equipped with a stirrer, weigh 20.0 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 6 above, add NMP (8.0 g) and BCS (12.0 g), and add room temperature. The photoradical generation film-forming composition (AL-2) was obtained by stirring with the mixture for 1 hour.

<Example 1 Preparation of photoradical generation film forming composition AL-3>
Weigh 19.0 g of the liquid crystal alignment agent (AL-1) obtained in Preparation Example 1 above into a 50 mL Erlenmeyer flask equipped with a stirrer, add Add-P1 (1.0 g), and stir at room temperature for 1 hour. As a result, the photoradical generation film forming composition (AL-3) used in the present invention was obtained.

<Example 2 Preparation of photoradical generation film forming composition AL-4>
Weigh 19.9 g of the liquid crystal alignment agent (AL-1) obtained in Preparation Example 1 above into a 50 mL Erlenmeyer flask equipped with a stirrer, add Add-P1 (0.1 g), and stir at room temperature for 1 hour. As a result, the photoradical generation film forming composition (AL-4) used in the present invention was obtained.

<Example 3 Preparation of photoradical generation film forming composition AL-5>
Weigh 19.0 g of the liquid crystal alignment agent (AL-1) obtained in Preparation Example 1 above into a 50 mL Erlenmeyer flask equipped with a stirrer, add Add-P2 (1.0 g), and stir at room temperature for 1 hour. As a result, the photoradical generation film forming composition (AL-5) used in the present invention was obtained.

<Example 4 Preparation of photoradical generation film forming composition AL-6>
Weigh 19.0 g of the liquid crystal alignment agent (AL-1) obtained in Preparation Example 1 above into a 50 mL Erlenmeyer flask equipped with a stirrer, add Add-P2 (0.1 g), and stir at room temperature for 1 hour. As a result, the photoradical generation film forming composition (AL-6) used in the present invention was obtained.

<Example 5 Preparation of photoradical generation film forming composition AL-7>
Weigh 19.0 g of the liquid crystal alignment agent (AL-1) obtained in Preparation Example 1 above into a 50 mL Erlenmeyer flask equipped with a stirrer, add Add-P3 (1.0 g), and stir at room temperature for 1 hour. As a result, the photoradical generation film forming composition (AL-7) used in the present invention was obtained.

<Example 6 Preparation of photoradical generation film forming composition AL-8>
Weigh 19.9 g of the liquid crystal alignment agent (AL-1) obtained in Preparation Example 1 above into a 50 mL Erlenmeyer flask equipped with a stirrer, add Add-P3 (0.1 g), and stir at room temperature for 1 hour. As a result, the photoradical generation film forming composition (AL-8) used in the present invention was obtained.

<Example 7 Preparation of photoradical generation film forming composition AL-9>
Weigh 19.0 g of SE-6414 (manufactured by Nissan Chemical Industries, Ltd., solid content concentration: 6.0% by mass) into a 50 mL Erlenmeyer flask equipped with a stirrer, add Add-P1 (1.0 g), and add 1 at room temperature. By stirring for a time, the photoradical generation film forming composition (AL-9) used in the present invention was obtained.

<Example 8 Preparation of photoradical generation film forming composition AL-10>
19.9 g of SE-6414 is weighed in a 50 mL Erlenmeyer flask equipped with a stirrer, Addd-P1 (0.1 g) is added, and the mixture is stirred at room temperature for 1 hour to form a photoradical generation film used in the present invention. The composition (AL-10) was obtained.

<Preparation of Example 9 Photoradical Generation Film Forming Composition AL-11>
19.0 g of SE-6414 is weighed in a 50 mL Erlenmeyer flask equipped with a stirrer, Addd-P2 (1.0 g) is added, and the mixture is stirred at room temperature for 1 hour to form a photoradical generation film used in the present invention. The composition (AL-11) was obtained.

<Example 10 Preparation of photoradical generation film forming composition AL-12>
19.9 g of SE-6414 is weighed in a 50 mL Erlenmeyer flask equipped with a stirrer, Addd-P2 (0.1 g) is added, and the mixture is stirred at room temperature for 1 hour to form a photoradical generation film used in the present invention. The composition (AL-12) was obtained.

<Preparation of Example 11 Photoradical Generation Film Forming Composition AL-13>
19.0 g of SE-6414 is weighed in a 50 mL Erlenmeyer flask equipped with a stirrer, Addd-P3 (1.0 g) is added, and the mixture is stirred at room temperature for 1 hour to form a photoradical generation film used in the present invention. The composition (AL-13) was obtained.

<Example 12 Preparation of photoradical generation film forming composition AL-14>
19.9 g of SE-6414 is weighed in a 50 mL Erlenmeyer flask equipped with a stirrer, Addd-P3 (0.1 g) is added, and the mixture is stirred at room temperature for 1 hour to form a photoradical generation film used in the present invention. The composition (AL-14) was obtained.

<Preparation Example 3 Preparation of Photoradical Generation Film Forming Composition AL-15>
In a 50 mL Erlenmeyer flask equipped with a stirrer, 10.0 g of the liquid crystal alignment agent (AL-1) obtained in Preparation Example 1 and the photoradical generation film forming composition (AL-) obtained in Preparation Example 2 were added. Weighing 10.0 g of 2) and stirring at room temperature for 1 hour, a photoradical generating film-forming composition (AL-15) to be compared was obtained.

<Preparation Example 4 Preparation of Photoradical Generation Film Forming Composition AL-16>
In a 50 mL Erlenmeyer flask equipped with a stirrer, 10.0 g of SE-6414 and 10.0 g of the photoradical generation film-forming composition (AL-2) obtained in Preparation Example 2 above were weighed and weighed at room temperature for 1 hour. By stirring, a photoradical generating film-forming composition (AL-16) to be compared was obtained.

<Creation of liquid crystal display element>
The method for producing a liquid crystal cell for evaluating the liquid crystal orientation and the electro-optic response is shown below.
First, a substrate with electrodes was prepared. The substrate is a non-alkali glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. An ITO (Indium-Tin-Oxide) electrode having a comb-shaped pattern such that the electrode width is 3 μm, the distance between the electrodes is 6 μm, and the angle is 10 ° with respect to the long side of the substrate is formed on the substrate. The first pixel and the second pixel are formed. The size of each pixel is 5 mm in length and about 5 mm in width. Hereinafter referred to as an IPS board.
Next, the photoradical generation film forming compositions AL-2 to AL-16 obtained by the above method, the liquid crystal alignment agent AL-1, and the liquid crystal alignment agent SE-6414 for horizontal alignment (Nissan Chemical Industries, Ltd.). Is filtered through a filter having a pore size of 1.0 μm, and then the prepared IPS substrate and the back surface ITO substrate having an ITO film formed on the back surface and having a columnar spacer having a height of 3.0 μm (hereinafter referred to as It was applied and filmed on the facing substrate) by the spin coating method. Then, it was dried on a hot plate at 80 ° C. for 80 minutes and then fired at 230 ° C. for 20 minutes to obtain a coating film having a film thickness of 100 nm. The coating film on the IPS substrate side was oriented along the direction of the comb teeth, and the coating film on the opposite substrate side was oriented in the direction orthogonal to the comb teeth electrode. In the alignment process, the rubbing method is used for AL-2, AL-9 to AL-14, AL-16 and SE-6414, and the rubbing device manufactured by Iinuma Gauge and the rubbing cloth (YA-20R) manufactured by Yoshikawa Kako Co., Ltd. , A rubbing roller (diameter 10.0 cm), a stage feed rate of 30 mm / s, a roller rotation speed of 700 rpm, and a pushing pressure of 0.4 mm. In AL-1, AL-2, AL-3 to AL-8, and AL-15, the photoalignment method is used, and all of them use a UV exposure apparatus manufactured by Ushio, Inc., and the extinction ratio is about 26: 1. The linearly polarized UV was irradiated with polarized UV so that the irradiation amount was 300 mJ / cm ² with the wavelength of 254 nm as a reference, and heated at 230 ° C. for 20 minutes to perform the alignment treatment.
After that, using the above two types of substrates, the combinations shown in Tables 1 and 3 below are combined so that their orientation directions are parallel to each other, and the surroundings are sealed leaving the liquid crystal injection port, and the cell gap is about. An empty cell of 3.0 μm was prepared. A liquid crystal composition obtained by mixing 2.0% by mass of the additive Add-1 in this empty cell is used, and a liquid crystal composition without additives is used in some of the display elements (Comparative Examples 1 and 6) to be compared. After vacuum injection at room temperature, the injection port was sealed to obtain an anti-parallel oriented liquid crystal cell. The liquid crystal mixture used was MLC-3019 (manufactured by Merck & Co., Ltd.).

The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element. After that, the obtained liquid crystal cell was heat-treated at 120 ° C. for 10 minutes, and UV (UV lamp: FLR40SUV32 / A-1) was applied using a UV-FL irradiation device manufactured by Toshiba Lighting & Technology Corporation in a state where no voltage was applied. Irradiation for 30 minutes was performed to obtain a liquid crystal display element.

<Evaluation of liquid crystal orientation>
Using a polarizing microscope, the polarizing plate was set to cross Nicol, the liquid crystal cell was fixed in the state where the brightness was the smallest, and the liquid crystal cell was rotated by 1 ° from the state, and the alignment state of the liquid crystal was observed. When no misalignment such as unevenness or domain was observed or when it was very slight, it was defined as "good", and when it was clearly observed, it was defined as "poor" and evaluated.
In addition, a photodiode is attached to the same polarizing microscope, connected to an electrometer via a current-voltage conversion amplifier, and the voltage is monitored under the condition where the brightness is the smallest under the cross Nicol. u.) Was measured.

<Measurement of VT curve and drive threshold voltage, maximum luminance voltage, transmittance evaluation>
A white LED backlight and a luminance meter are set so that the optical axes are aligned, and a liquid crystal cell (liquid crystal display element) with a polarizing plate is set between them so that the luminance is minimized, and the voltage is applied to 8V at 1V intervals. The VT curve was measured by applying and measuring the luminance at voltage. From the obtained VT curve, the value of the voltage (Vmax) at which the brightness was maximized was estimated. Further, the maximum transmittance (Tmax) was estimated by comparing the maximum transmitted luminance in the VT curve with the transmitted luminance at the time of parallel Nicol set to 100% via the liquid crystal cell to which no voltage was applied.

<Measurement of response time (Ton, Toff)>
Using the device used in the above VT curve measurement, connect the luminance meter to the oscilloscope, and the response speed (Ton) when the voltage that maximizes the brightness is applied and the response speed (Toff) when the voltage is returned to 0V. ) Was measured.

<Burn-in evaluation>
A rectangular wave voltage (60 Hz) that maximizes the brightness is applied to the first pixel region of each liquid crystal cell, a state is created in which no voltage is applied to the other second pixel region, and the battery is driven at 60 ° C. for 168 hours for aging. Was done. Burn-in was evaluated by comparing the brightness of the first pixel and the second pixel after aging. The smaller the difference in brightness, the better.

Table 2 shows the evaluation results of Examples and Comparative Examples in the liquid crystal display element manufactured by the photo-alignment method.

In Examples 13 to 18, Comparative Example 2, and Comparative Example 4, a photoradical generation film was used for the IPS substrate and a photoalignment film was used for the facing substrate, respectively, and Examples 19 to 24 and Comparative Example 3 were used. , And Comparative Example 5 use a photoalignment film for the IPS substrate and a photoradical generation film for the opposing substrate, and Comparative Example 1 uses a photoalignment film for both substrates.
Comparing Comparative Example 4 and Comparative Example 5, seizure tends to be improved by using the photoradical generation film as the opposed substrate. However, the photoradical generation film obtained by using the radical generation film forming composition of the present invention can be obtained. All of the used ones have good seizure.
When the photoradical generation film obtained by using the radical generation film forming composition of the present invention is used, the black brightness is smaller than that of any of the comparative examples, and the transmittance is higher than that of the strong anchoring liquid crystal display element of Comparative Example 1. From the significant improvement, it can be seen that good weak anchoring IPS characteristics are obtained when the photoradical generation film obtained by using the radical generation film forming composition of the present invention is used. Although a slight decrease (prolongation) in response time due to weak anchoring was observed, it was within the permissible range, and the response was compared with Comparative Example 2 and Comparative Example 3 in which the photoradical generation film of the polyimide single material was used. The time and seizure were greatly improved, and the photoradical generation film obtained by using the radical generation film forming composition of the present invention was used as compared with Comparative Example 4 and Comparative Example 5, which are blend materials of polyimides. In this case, it can be seen that the black brightness level, response time, and burn-in are also improved. Further, in the case of a non-polyimide-based polymer such as the radical generation film forming composition of the present invention, the effect is obtained when the blend material of polyimides has a blend ratio (solid content ratio) of 1: 1. A sufficient effect can be obtained by adding a small amount (for example, about 0.5% by mass to 5% by mass) with respect to the solid content. This is because the polymer used as an orientation component of a liquid crystal alignment agent for driving a transverse electric field such as polyamic acid or polyimide and a polymer having a significantly different structure have poor compatibility, so layer separation may easily occur during film formation. It is presumed that the photoradic generating groups were efficiently unevenly distributed on the film surface in a sea-island shape, and as a result, it became possible to induce weak anchoring orientation without impairing the liquid crystal orientation.

Table 4 shows the results of the liquid crystal display element manufactured by the rubbing method.

In Examples 25 to 30, Comparative Example 7, and Comparative Example 9, a photoradical generating film was used for the IPS substrate and a rubbing alignment film was used for the facing substrate, respectively, and Examples 31 to 36 and Comparative Example 8 were used. , And Comparative Example 10 used a rubbing alignment film for the IPS substrate and a photoradical generating film for the opposing substrate, and Comparative Example 6 used a rubbing alignment film for both substrates.
In the liquid crystal display element manufactured by rubbing, the same result as that of the liquid crystal display element manufactured by photo-alignment was obtained. Further, basically, an alignment component in which an organic group that induces radical polymerization is introduced into a side chain is unsuitable for a horizontally oriented film, and it is difficult to obtain good liquid crystal orientation. However, the technique of the present invention is an alignment component. Since an organic group that directly induces radical polymerization is not introduced into the product, it is considered that weak anchoring can be achieved while maintaining good liquid crystal orientation. It is considered that the response speed (Toff) could be improved because the region of the anchoring energy state having a moderately strong state could be left for the above-mentioned reason.
According to this study, it is possible to produce a photoradical generation film necessary for the production of weak anchoring IPS by adding a small amount of a non-polyimide compound having a photoradical generation site introduced into a normal liquid crystal alignment film, and rubbing. It was found that both the liquid crystal alignment film for light alignment and the liquid crystal alignment film for photoalignment had the same effect, and good weak anchoring characteristics could be obtained regardless of the composition of the liquid crystal alignment film.

According to the present invention, it can be easily manufactured, a low drive voltage and a high response speed at the time of voltage off can be realized at the same time, and in addition, a good black display is possible, and a transverse electric field liquid crystal with good seizure suppression is possible. A display element can be provided, and a liquid crystal display element with good reliability can be obtained. Therefore, the liquid crystal display element obtained by the method of the present invention is useful as a horizontal electric field drive type liquid crystal display element.

1 Transverse electric field liquid crystal display element 2 Comb tooth electrode substrate

2a Base material

2b Linear electrode 2c Liquid crystal alignment film 2d Base material 2e Surface electrode 2f Insulation film 2g Linear electrode 2h Liquid crystal alignment film 3 Liquid crystal 4 Opposing substrate 4a Liquid crystal alignment film 4b base Material L Electric power wire

Claims

Component (A): A polymer used as an alignment component of a liquid crystal alignment agent for driving a transverse electric field, and Component (B): a polymer containing a group represented by the following formula (1) and having a polymerizable carbon- Polymers with structural units derived from monomers with carbon unsaturated bonds,
A radical generation film forming composition containing.

(In formula (1), * represents a binding site, R 1 is a single bond, -CH 2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-,- Represents CH 2 O-, -N (CH 3 )-, -CON (CH 3 )-, or -N (CH 3 ) CO-.
R 2 represents an alkylene group having 1 to 20 carbon atoms which is single-bonded, or unsubstituted or substituted with a fluorine atom, and one or more of any -CH 2- or -CF 2- of the alkylene group is independent of each other. It may be replaced with a group selected from -CH = CH-, a divalent carbocycle which may have a substituent, and a divalent heterocycle which may have a substituent. Further, one or more of any -CH 2- or -CF 2- of the alkylene group is one of the following groups, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH. -Or -NH- may be replaced by at least one of these groups, provided they are not adjacent to each other.
R 3 represents an organic group that induces radical polymerization. )
The radical generation film forming composition according to claim 1, wherein R 3 represents an organic group that induces radical polymerization represented by the following formula [W], [Y] or [Z].

(In the formulas [W], [Y] and [Z], * indicates a bond site, and Ar is a group consisting of phenylene, naphthylene, and biphenylylene which may have an organic group and / or a halogen atom as a substituent. Representing the aromatic hydrocarbon group of choice, R 9 and R 10 each independently represent an alkyl group with 1-10 carbon atoms or an alkoxy group with 1-10 carbon atoms, with R 9 and R 10 being alkyl groups. In the case, they may be bonded to each other at the ends to form a ring structure. Q represents any of the following structures.

(In the formula, R 11 represents -CH 2- , -NR-, -O-, or -S-, R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bond. The site is shown.). S 3 represents a single bond, -O-, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms), or -S-. R 12 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. )
The radical generation film-forming composition according to claim 1 or 2, wherein the polymer as the component (A) is a polyimide precursor or a polyimide.
The radical-generating film-forming composition according to any one of claims 1 to 3, wherein the polymer as the component (A) does not contain an organic group that induces radical polymerization.
The radical generating film forming composition according to any one of claims 1 to 4, wherein the content of the component (B) is 0.1 to 20% by mass with respect to the component (A).
A radical generation film obtained by using the radical generation film forming composition according to any one of claims 1 to 5.
The step of preparing the first substrate having the radical generation film according to claim 6 and the second substrate which may have the radical generation film.
A step of arranging the first substrate and the second substrate facing each other so that the radical generation film on the first substrate faces the second substrate.
The step of filling a liquid crystal composition containing a liquid crystal and a radically polymerizable compound between the first substrate and the second substrate, and the liquid crystal composition in contact with the radical generating film, said. Steps to polymerize radically polymerizable compounds,
A method for manufacturing a liquid crystal display element including.
The method for manufacturing a liquid crystal display element according to claim 7, wherein the second substrate is a second substrate having no radical generation film.
The method for manufacturing a liquid crystal display element according to claim 7, wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial orientation.
The method for manufacturing a liquid crystal display element according to claim 9, wherein the liquid crystal alignment film having uniaxial orientation is a liquid crystal alignment film for horizontal alignment.
The method for manufacturing a liquid crystal display element according to any one of claims 7 to 10, wherein either one of the first substrate and the second substrate is a substrate having a comb tooth electrode.
It has a first substrate, a second substrate arranged facing the first substrate, and a liquid crystal display filled between the first substrate and the second substrate.
The radically polymerizable compound is polymerized in a state where the liquid crystal composition containing the liquid crystal and the radically polymerizable compound is in contact with the radically generated film of the first substrate having the radically generated film according to claim 6. A liquid crystal display element characterized by radical polymerization.