WO2022071286A1

WO2022071286A1 - Liquid-crystal composition, liquid-crystal display element production method, and liquid-crystal display element

Info

Publication number: WO2022071286A1
Application number: PCT/JP2021/035557
Authority: WO
Inventors: 正人森内; 尚宏野田
Original assignee: 日産化学株式会社
Priority date: 2020-09-29
Filing date: 2021-09-28
Publication date: 2022-04-07
Also published as: TW202222810A; JPWO2022071286A1

Abstract

A liquid-crystal display element production method that includes a step in which a liquid-crystal composition comprising a liquid crystal and a radically polymerizable compound represented by formula (A) is brought into contact with a radical-generating film and, while in the contact state, the radically polymerizable compound is polymerized. (In formula (A), M indicates a radically-polymerizable compound, R₁ indicates a C1–10 aliphatic hydrocarbon group having a linear or branched structure, and the three Xs each independently indicate a hydrogen atom or formula (B). At least one of the three Xs indicates formula (B).) (In formula (B): Y indicates a single bond, –O–, –S–, or –NR–; R indicates a hydrogen atom or a C1–4 alkyl group; and * indicates a bonding site. R₂, R₃, and R₄ each independently indicate a C1–6 alkyl group or an aromatic hydrocarbon group that may have a substituent.)

Description

Liquid crystal composition, 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 not including a complicated process, and which 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 liquid crystal composition that can be used for them, and a radically polymerizable compound.

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 display. ..

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, while 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.

A different method from these is being studied to improve the response speed by narrowing the cell gap. Normally, the response speed of a liquid crystal display element tends to increase as the cell gap becomes narrower. However, on the other hand, there is a problem that the transmittance is lowered. To solve this problem, the use of a liquid crystal display having a large birefringence difference (Δn) can be mentioned. By setting the product (literation) of the cell gap D and Δn to be 300 nm to 400 nm (measurement wavelength 550 nm), the decrease in transmittance can be solved. However, when Δn is increased, basically only the parameters cannot be changed, and parameters such as Δε (dielectric constant anisotropy) and elastic modulus also change, so that the basic physical properties of the liquid crystal display may change significantly. Conceivable. For example, in the case of weak anchoring orientation, there is a possibility that the liquid crystal may be oriented in the vertical direction. Therefore, it is an important issue to obtain stable weak anchoring characteristics even if parameters such as Δn and Δε change.

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, and in narrowing the cell gap, a weak anchoring transverse electric field liquid crystal display element can be stably manufactured without generating a pretilt angle, and a low drive voltage can be produced. A method for manufacturing a liquid crystal display element that can manufacture a transverse electric field liquid crystal display element with a small decrease in VHR (voltage retention rate) even at high temperatures, and a method for manufacturing a liquid crystal display element, which can simultaneously realize the change in voltage and increase the response speed when the voltage is off. It is an object of the present invention to provide the liquid crystal display element, a liquid crystal composition that can be used for the liquid crystal display element, and a radically polymerizable compound.

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] A liquid crystal comprising a step of polymerizing the radically polymerizable compound in a state where the liquid crystal and the liquid crystal composition containing the radically polymerizable compound represented by the following formula (A) are in contact with a radical generating film. Method of manufacturing display element.

(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 formula (B), where at least one of the three Xs represents formula (B).)

(In the 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.)
[2] The method for producing a liquid crystal display element according to [1], wherein the aromatic hydrocarbon group which may have the substituent in the formula (B) is a phenyl group.
[3] The method for manufacturing a liquid crystal display element according to [1] or [2], wherein M in the formula (A) is 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, and 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.)
[4] The method for manufacturing a liquid crystal display element according to any one of [1] to [3], wherein the radical generation film is a radical generation film subjected to uniaxial orientation treatment.
[5] The method for manufacturing a liquid crystal display element according to any one of [1] to [4], wherein the step of performing the polymerization reaction is performed under no electric field conditions.
[6] The method for manufacturing a liquid crystal display element according to any one of [1] to [5], wherein the radical generating film is a film formed by immobilizing an organic group that induces radical polymerization.
[7] The radical-generating film is coated with a composition containing a compound having an organic group that generates a radical and a polymer, and cured to form a film, whereby the organic group that generates the radical is obtained. The method for manufacturing a liquid crystal display element according to any one of [1] to [5], which is obtained by immobilizing in a film.
[8] The method for producing a liquid crystal display element according to any one of [1] to [5], wherein the radical generating film is made of a polymer containing an organic group that induces radical polymerization.
[9] The polymer containing an organic group that induces radical polymerization is selected from a polyimide precursor, a polyimide, a polyurea, and a polyamide obtained by using a diamine component containing a diamine containing an organic group that induces radical polymerization. The method for manufacturing a liquid crystal display element according to [8], which is at least one kind of polymer.
[10] The organic group that induces radical polymerization is an organic group represented by the following formulas [X-1] to [X-18], [W], [Y], or [Z], [9]. The method for manufacturing a liquid crystal display element according to the above.

(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.)

(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 indicated.) 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. )
[11] The diamine containing an organic group that induces radical polymerization is a diamine having a structure represented by the following formula (6), the following formula (7), or the following formula (7'), [9] or [10] The method for manufacturing a liquid crystal display element according to [10].

(In formula (6), R ⁶ is a single bond, -CH _2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N. Represents (CH ₃ )-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-.
R ⁷ represents an alkylene group having 1 to 20 carbon atoms which is single-bonded or substituted 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. May be replaced with a group selected from -CH = CH-, a divalent carbocycle, and a divalent heterocycle, and any of the following groups, i.e., -O-, -COO-. , -OCO-, -NHCO-, -CONH-, or -NH- may be replaced by these groups provided they are not adjacent to each other;
R ⁸ represents a radical polymerization reactive group represented by a formula selected from the following formulas [X-1] to [X-18].

(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.)))

(In equations (7) and (7'), T ¹ and T ² are independently single-bonded, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, respectively. -NH-, -CH ₂ O-, -N (CH ₃ )-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-.
S 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 independently. It may be replaced with a group selected from -CH = CH-, a divalent carbocycle, and a divalent heterocyclic ring, and further, any of the following groups, that is, -O-, -COO-,. -OCO-, -NHCO-, -CONH-, or -NH- may be replaced by these groups provided that they are not adjacent to each other.
E is a single bond, -O-, -C (CH ₃ ) _2- , -NH-, -CO-, -NHCO-, -COO-,-(CH ₂ ) _m- , -SO _2- , -O. -(CH ₂ ) _m -O-, -OC (CH ₃ ) _2- , -CO- (CH ₂ ) _m- , -NH- (CH ₂ ) _m- , -SO _2- (CH ₂ ) _m -, -CONH- (CH ₂ ) _m- , -CONH- (CH ₂ ) _m -NHCO-, or -COO- (CH ₂ ) _m -OCO-, where m is an integer from 1 to 8.
J is an organic group represented by a formula selected from the following formulas [W], [Y] and [Z].

(In the formulas [W], [Y], and [Z], * represents a bond with T ² , Ar represents an organic group and / or a halogen atom as a substituent, phenylene, naphthylene, and Indicates an aromatic hydrocarbon group selected from the group consisting of biphenylylene, R ⁹ and R ¹⁰ independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q is described below. Represents either structure.

(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 indicated.) 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. )) In equation (7'), q is independently 0 or 1, at least one q is 1, and p represents an integer of 1 to 2. )
[12] A step of preparing a first substrate having the radical generation film 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 generating film on the first substrate faces the second substrate.
A step of filling the liquid crystal composition between the first substrate and the second substrate, and a step of causing the polymerization reaction.
The method for manufacturing a liquid crystal display element according to any one of [1] to [11], which comprises.
[13] The method for manufacturing a liquid crystal display element according to [12], wherein the second substrate is a second substrate having no radical generation film.
[14] The method for manufacturing a liquid crystal display element according to [12], wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial orientation.
[15] The method for manufacturing a liquid crystal display element according to [14], wherein the liquid crystal alignment film having uniaxial orientation is a liquid crystal alignment film for horizontal alignment.
[16] The method for manufacturing a liquid crystal display element according to any one of [12] to [15], wherein either the first substrate or the second substrate is a substrate having a comb tooth electrode.
[17] A liquid crystal composition comprising a liquid crystal display and a radically polymerizable compound represented by the following formula (A).

(In the 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.)
[18] The liquid crystal composition according to [17], wherein the aromatic hydrocarbon group which may have the substituent in the formula (B) is a phenyl group.
[19] The liquid crystal composition according to [17] or [18], wherein M in the formula (A) is 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, and 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.)
[20] 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 in a state where the liquid crystal composition containing the liquid crystal and the radically polymerizable compound represented by the following formula (A) is in contact with the radically polymerized film of the first substrate having the radically generated film. A liquid crystal display element characterized by having a polymerization reaction.

(In the 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.)
[21] The liquid crystal display element according to [20], wherein either the first substrate or the second substrate is a substrate having a comb tooth electrode.
[22] The liquid crystal display element according to [20] or [21], which is a low voltage drive horizontal electric field liquid crystal display element.
[23] A radically polymerizable compound represented by any of the following formulas (F-1) to (F-6).

According to the present invention, in narrowing the cell gap, a weak anchoring transverse electric field liquid crystal display element can be stably manufactured without generating a pretilt angle, and at the same time, the drive voltage can be lowered and the response speed when the voltage is turned off can be increased at the same time. A method for manufacturing a liquid crystal display element that can be realized and that can produce a transverse electric field liquid crystal display element with a small decrease in VHR even at high temperatures, the liquid crystal display element, a liquid crystal composition that can be used for them, and radical polymerizable. Compounds can be provided.

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.

INDUSTRIAL APPLICABILITY The present invention is an additive (with a specific structure) capable of suppressing the development of a pretilt angle due to the formation of a weak anchoring film and stably producing a highly reliable weak anchoring transverse electric field liquid crystal display element even in a narrow cell gap. It utilizes a radically polymerizable compound). For example, a step of preparing a cell having a liquid crystal composition containing a liquid crystal and a radically polymerizable compound having a specific structure between a first substrate having a radical generating film and a second substrate having a liquid crystal alignment film, and the above-mentioned step. It is a method for manufacturing a weak anchoring transverse electric field liquid crystal display element, which comprises a step of imparting sufficient energy to a cell to polymerize the radically polymerizable compound. Preferably, a step of preparing a first substrate having a radical generating film oriented by rubbing or photoalignment and a second substrate having a liquid crystal alignment film having no radical generating film so that the respective substrates face each other. A method for producing a liquid crystal cell, comprising a step of creating a cell and a step of filling a liquid crystal composition containing a liquid crystal and a radically polymerizable compound having a specific structure between the first substrate and the second substrate. For example, one substrate has an oriented radical generation film, the other substrate has a uniaxially oriented liquid crystal alignment film, and one of the substrates has a comb tooth for driving the liquid crystal. This is a method for manufacturing a low voltage drive transverse electric field liquid crystal display element, which is a substrate having electrodes.

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.

The applicant of the present application comprises a step of imparting sufficient energy to polymerize the radically polymerizable compound in a state where the liquid crystal composition containing the liquid crystal and the radically polymerizable compound is in contact with the radical generating film. A method for producing a zero-plane anchoring film is proposed (see claim 1 of International Publication No. 2019/004433). [0077] to [0086] of International Publication No. 2019/004433 exemplify the radically polymerizable compound used in the proposal.
By using the above-mentioned technology, the present inventors can stably manufacture a weak anchoring lateral electric field liquid crystal display element without generating a pretilt angle in a narrow cell gap, and can reduce the drive voltage and turn off the voltage. At the same time, it was possible to increase the response speed, and in addition, we made diligent studies to fabricate a transverse electric field liquid crystal display element with a small decrease in VHR even at high temperatures. As a result, by using a radically polymerizable compound having a specific structure among the radically polymerizable compounds, a weak anchoring transverse electric field liquid crystal display element can be stably manufactured without generating a pretilt angle even when the cell gap is narrowed, and the drive is low. It has been found that it is possible to simultaneously realize voltage conversion and 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 having a small decrease in VHR even at a high temperature.
Here, the radically polymerizable compound having a specific structure 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), but at least one of the three Xs represents the formula (B).)

(In the 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.)

In the method for producing a liquid crystal display element of the present invention, a radically polymerizable compound is polymerized in a state where the liquid crystal and the liquid crystal composition containing the radically polymerizable compound represented by the formula (A) are in contact with the radical generating film. Including the step of reacting. 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 lateral 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 response speed when the voltage is turned off. At the same time, it can be realized that the voltage can be increased, and in addition, a lateral electric field liquid crystal display element with a small decrease in VHR even at a high temperature can be manufactured. 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.
In addition, the radically polymerizable compound represented by the formula (A) -SiR ₂ R ₃ R ₄ contributes to the suppression of the generation of pretilt angle, the improvement of the response speed, and the high VHR at high temperature. The inventors are speculating.
In the present specification, the narrow cell gap means a cell gap of 3.5 μm or less.

[Radical generation film forming composition]
The radical-generating film-forming composition for forming a radical-generating film used in the present invention contains a polymer as a component and contains a group capable of generating radicals. At that time, the composition may contain a polymer to which a group capable of generating radicals is bonded, or a composition of a compound having a group capable of generating radicals and a polymer serving as a base resin. It may be a thing. By applying and curing such a composition to form a film, a radical generation film in which radical-generating groups are immobilized in the film can be obtained. The group capable of generating radicals is preferably an organic group that induces radical polymerization.

Examples of such an organic group that induces radical polymerization include organic groups represented by the following formulas [X-1] to [X-18], [W], [Y], and [Z].

(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. )

As the polymer, at least one polymer selected from the group consisting of a polyimide precursor, a polyimide, a polyurea, a polyamide, a polyacrylate, a polymethacrylate, and a polyorganosiloxane is preferable.

When a polymer having an organic group that induces radical polymerization is used to obtain a radical generation film used in the present invention, in order to obtain a polymer having a group capable of generating radicals, a methacrylic group is used as a monomer component. A monomer having a photoreactive side chain containing at least one selected from an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group and a cinnamoyl group, and a site that is decomposed by ultraviolet irradiation and generates a radical is a side chain. It is preferable to use the monomer contained in the above. On the other hand, the monomer that generates radicals has a problem that it spontaneously polymerizes, and becomes an unstable compound. Therefore, it has a radical generation site in terms of ease of synthesis. Polymers derived from diamines are preferred, and polyimide precursors such as polyamic acids and polyamic acid esters, polyimides, polyureas, polyamides and the like are more preferred.

The polymer containing an organic group that induces radical polymerization is at least one weight selected from a polyimide precursor, a polyimide, a polyurea, and a polyamide obtained by using a diamine component containing a diamine containing an organic group that induces radical polymerization. It is preferably coalesced.
The diamine containing an organic group that induces such radical polymerization is, specifically, for example, a diamine having a side chain that can generate radicals and can be polymerized, and has a structure represented by the following formula (6). Examples include, but are not limited to, having diamines.

(In formula (6), R ⁶ is a single bond, -CH _2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N. Represents (CH ₃ )-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-.
R ⁷ 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. May be replaced with a group selected from -CH = CH-, a divalent carbocycle, and a divalent heterocycle, and any of the following groups, i.e., -O-, -COO-. , -OCO-, -NHCO-, -CONH-, or -NH- may be replaced by these groups provided they are not adjacent to each other;
R ⁸ represents a radical polymerization reactive group represented by a formula selected from the following formulas [X-1] to [X-18].

The bonding position of the two amino groups (-NH ₂ ) in the formula (6) is not limited. Specifically, with respect to the bonding group of the side chain, 2,3 positions, 2,4 positions, 2,5 positions, 2,6 positions, 3,4 positions, 3, on the benzene ring. The position of 5 is mentioned. Of these, the 2,4 position, the 2,5 position, or the 3,5 position is preferable from the viewpoint of reactivity in synthesizing the polyamic acid. Considering the ease of synthesizing the diamine, the

positions

2, 4 or 3, 5 are more preferable.

Specific examples of the diamine having a photoreactive group including at least one selected from the group consisting of a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumaryl group, a styryl group and a cinnamoyl group are as follows. Examples include, but are not limited to, compounds.

(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.)

Among diamines containing organic groups that induce radical polymerization, diamines having a site that is decomposed by ultraviolet irradiation to generate radicals as a side chain have a structure represented by the following formula (7) or formula (7'). Diamines having, but are not limited to, may be mentioned.

(In equations (7) and (7'), T ¹ and T ² are independently single-bonded, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, respectively. -NH-, -CH ₂ O-, -N (CH ₃ )-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-.
S 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 independently. It may be replaced with a group selected from -CH = CH-, a divalent carbocycle, and a divalent heterocyclic ring, and further, any of the following groups, that is, -O-, -COO-,. -OCO-, -NHCO-, -CONH-, or -NH- may be replaced by these groups provided they are not adjacent to each other.
E is a single bond, -O-, -C (CH ₃ ) _2- , -NH-, -CO-, -NHCO-, -COO-,-(CH ₂ ) _m- , -SO _2- , -O. -(CH ₂ ) _m -O-, -OC (CH ₃ ) _2- , -CO- (CH ₂ ) _m- , -NH- (CH ₂ ) _m- , -SO _2- (CH ₂ ) _m -, -CONH- (CH ₂ ) _m- , -CONH- (CH ₂ ) _m -NHCO-, or -COO- (CH ₂ ) _m -OCO-, where m is an integer from 1 to 8.
J is an organic group represented by a formula selected from the following formulas [W], [Y] and [Z].

(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. )) In equation (7'), q is independently 0 or 1, at least one q is 1, and p represents an integer of 1 to 2. )

The bonding position of the two amino groups (-NH ₂ ) in the above formula (7) is not limited. Specifically, with respect to the bonding group of the side chain, 2,3 positions, 2,4 positions, 2,5 positions, 2,6 positions, 3,4 positions, 3, on the benzene ring. The position of 5 is mentioned. Of these, the 2,4 position, the 2,5 position, or the 3,5 position is preferable from the viewpoint of reactivity in synthesizing the polyamic acid.

In particular, in view of ease of synthesis, high versatility, characteristics, and the like, the structure represented by the following formula is most preferable, but the structure is not limited thereto.

(In the formula, n is an integer of 2 to 8.)

The bonding position of the amino group (-NH ₂ ) and the bonding group E on the benzene ring in the above formula (7') is not limited. The para position is preferable from the viewpoint of availability of raw materials, orientation quality when used as a liquid crystal display element, and black brightness.

In the diamines represented by the formulas (7) and (7'), the structures represented by the following formulas are most preferable in consideration of ease of synthesis, high versatility, characteristics and the like. Not limited to.

(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 above diamine can be used alone or in combination of two or more depending on the liquid crystal orientation when the radical generation film is formed, the sensitivity in the polymerization reaction, the voltage holding characteristic, the accumulated charge and the like.

As the diamine containing an organic group that induces such radical polymerization, it is preferable to use an amount of 5 to 50 mol% of the total diamine component used for synthesizing the polymer contained in the radical generation film forming composition. It is preferably 10 to 40 mol%, and particularly preferably 15 to 30 mol%.

When the polymer used for the radical polymerization film of the present invention is obtained from a diamine, other diamines other than the diamine containing an organic group that induces the radical polymerization are used as the diamine component as long as the effect of the present invention is not impaired. Can be used together. Specifically, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m- Phenylene diamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4- Diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3 , 3'-Dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 3,3'- Bis (Trifluoromethyl) -4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4 '-Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,3'- Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis (4-amino) Phenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4 , 4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) ) Amine, N-methyl (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2) , 3'-diaminodiphenyl) amine, 4,4'- Diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1 , 6-Diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 1,2-bis (4-amino) Phenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4) -Aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3 -Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1 , 3-bis (4-aminophenoxy) benzene, 4,4'-[1,4-phenylenebis (methylene)] dianiline, 4,4'-[1,3-phenylenebis (methylene)] dianiline, 3, 4'-[1,4-Benzenebis (methylene)] dianylin, 3,4'-[1,3-phenylenebis (methylene)] dianylin, 3,3'-[1,4-phenylenebis (methylene)] Dianiline, 3,3'-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone] ], 1,3-Phenylenebis [(4-aminophenyl) methanone], 1,3-Phenylenebis [(3-aminophenyl) methanone], 1,4-Phenylenebis (4-aminobenzoate), 1,4 -Phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-amino) Phenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N'-(1,4-phenylene) bis (4-aminobenzamide), N, N'-( 1 , 3-Phenylene) bis (4-aminobenzamide), N, N'-(1,4-phenylene) bis (3-aminobenzamide), N, N'-(1,3-phenylene) bis (3-amino) Benzamide), N, N'-bis (4-aminophenyl) terephthalamide, N, N'-bis (3-aminophenyl) terephthalamide, N, N'-bis (4-aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis (4-aminophenoxy) diphenyl sulfone, 2,2-bis [4- (4) 4-Aminophenoxy) Phenyl] Propane, 2,2-Bis [4- (4-Aminophenoxy) Phenyl] Hexafluoropropane, 2,2-Bis (4-Aminophenyl) Hexafluoropropane, 2,2-Bis ( 3-Aminophenyl) Hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) Hexafluoropropane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-amino) Phenyl) propane, 2,2-bis (3-amino-4-methylphenyl) propane, trans-1,4-bis (4-aminophenyl) cyclohexane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid Acid, bis (4-aminophenoxy) methane, 1,2-bis (4-aminophenoxy) ethane, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-Bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) Pentan, 1,6-bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7-bis (3) -Aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-Aminophenoxy) nonane, 1,10-bis (4-aminophenoxy) decane, 1,10-bis (3-aminophenoxy) decane, 1,11-bis (4-aminophenoxy) undecane, 1,11 -Bis (3-aminophenoxy) undecane, 1,12- Aromatic diamines such as bis (4-aminophenoxy) dodecane, 1,12-bis (3-aminophenoxy) dodecane; bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, etc. Alicyclic diamines; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1, Aliphatic diamines such as 9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane; 1,3-bis [2- (p-aminophenyl) ethyl] urea, 1, Diamine having a urea structure such as 3-bis [2- (p-aminophenyl) ethyl] -1-tert-butoxycarbonyl urea; Np-aminophenyl-4-p-aminophenyl (tert-butoxycarbonyl) amino Diamine having a nitrogen-containing unsaturated heterocyclic structure such as methylpiperidin; N-Boc such as N-tert-butoxycarbonyl-N- (2- (4-aminophenyl) ethyl) -N- (4-aminobenzyl) amine Examples thereof include diamines having a group (Boc represents a tert-butoxycarbonyl group).

The above other diamines may be used alone or in combination of two or more depending on the liquid crystal orientation when the radical generation film is formed, the sensitivity in the polymerization reaction, the voltage holding characteristics, the accumulated charge and the like. ..

The tetracarboxylic dianhydride that reacts with the above diamine component in the synthesis when the polymer is a polyamic acid is not particularly limited. Specifically, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-Anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyl Tetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenone tetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) Carboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) Propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4) -Dicarboxyphenyl) pyridine, 3,3', 4,4'-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 1,3-diphenyl-1,2,3,4- Cyclobutanetetracarboxylic acid, 4,4'-oxydiphthalic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetra Carboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, tetrahydrofuran-2,3,4,5-tetracarboxylic acid, 2- (3,4-) Dicarboxycyclohexyl) succinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo [3.3.0 ] Octane-2,4,6,8-tetracarboxylic acid, bicyclo [4.3.0] nonan-2,4,7,9-tetracarboxylic acid, bicyclo [4.4.0] decan-2,4 , 7,9-Tetracarboxylic Acid, Bicyclo [4.4.0] Decane-2,4,8,10-Tetracarboxylic Acid, Tricyclo [6.3.0.0 <2,6>] Undecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4- (2,5-dioxotetraaxial-3-yl) -1,2,3,4 -Tetrahydronaphthalene-1,2-dicarboxylic acid, bicyclo [2.2.2] octa-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl)- 3-Methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo [6.2.1.1 <3,6>. 0 <2,7>] Dodecane-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2: 3,5: 6 dicarboxylic acid, 1,2,4,5-cyclohexane Examples thereof include tetracarboxylic acid dianhydrides such as tetracarboxylic acid.

Of course, one or two or more types of tetracarboxylic dianhydride may be used in combination depending on the liquid crystal orientation when the radical generating film is formed, the sensitivity in the polymerization reaction, the voltage holding property, the accumulated charge, and the like. ..

The structure of the tetracarboxylic acid dialkyl ester to be reacted with the above diamine component in the synthesis when the polymer is a polyamic acid ester is not particularly limited, but 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-tricarboxycyclopentylacetic acid Dialkyl ester, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 <2,5>] nonane- 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 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, 2,3,6,7 -Naphthalene tetracarboxylic acid dialkyl ester and the like can be mentioned.

In the synthesis when the polymer 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 the 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 they may be used in the form of a copolymer of polyamic acid and polyurea. 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 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, 1,4- (2-norbornen) dicarboxylic acid, 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- Examples thereof include dioxo-1,3-adamantan dicarboxylic acid, 2,6-spiro [3.3] heptane dicarboxylic acid, 1,3-adamantan diacetic acid, camphor acid and the like.

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, 1,4 -Anthraquinone dicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 4,4 "-terphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4 , 4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-bibenzyldicarboxylic acid, 4,4'-Stylbenzicarboxylic acid, 4,4'-transicarboxylic acid, 4,4'-carbonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 4,4'-dithiodibenzoic acid, p- Phenylene diacetic acid, 3,3'-p-phenylenedipropionic acid, 4-carboxycarboxylic acid, p-phenylenediacrylic acid, 3,3'-[4,4'-(methylenedi-p-phenylene)] dipropion Acid, 4,4'-[4,4'-(oxydi-p-phenylene)] dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene)] dibutyric acid, (isopropyry Examples thereof include dicarboxylic acids such as dendi-p-phenylenedioxy) dibutyric acid and bis (p-carboxyphenyl) dimethylsilane.

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, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4 '-Diphenylpropandicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis (phenyl) propandicarboxylic acid, 4,4-terphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2, 5-Ppyridinedicarboxylic acid or acid dihalide thereof and the like are preferably used. Some of these compounds have isomers, but they may be mixtures containing them. Further, two or more kinds of compounds may be used in combination. The dicarboxylic acids used in the present invention are not limited to the above-mentioned exemplary compounds.

It is selected from the raw material diamine (also referred to as "diamine component") and the raw material tetracarboxylic acid dianhydride (also referred to as "tetracarboxylic acid dianhydride component"), tetracarboxylic acid diester, diisocyanate and dicarboxylic acid. A known synthetic method can be used to obtain a polyamic acid, a polyamic acid ester, a polyurea, or a polyamide by reaction with a component. Generally, it is a method of reacting a diamine component with one or more components selected from a tetracarboxylic dianhydride component, a tetracarboxylic acid diester, a diisocyanate and a dicarboxylic acid in an organic solvent.

The reaction between the diamine component and the tetracarboxylic 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-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoramide, γ-Butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cell solve, ethyl cell solve, 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 monoethyl ether, dipropylene glycol monomethyl 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, dioxane, n-hexane, n-pentane, n-octane, diethyl Ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 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 dianhydride component is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be reacted individually in sequence, or may be reacted individually, and have 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 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 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 used in the present invention is not limited to the above-mentioned method, and when synthesizing a polyamic acid, the above-mentioned tetracarboxylic acid dianhydride is used in the same manner as a 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. In addition, when synthesizing polyurea, diamine and diisocyanate may be reacted. When producing a polyamic acid ester or polyamide, a diamine and a component selected from a tetracarboxylic acid diester and a dicarboxylic acid are induced into an acid halide in the presence of a known condensing agent or by a known method. , Diamine may be reacted.

Further, polyimide can be obtained by ring-closing (imidizing) the polyamic acid. The imidization rate 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 ratio of the polyimide in the present invention is preferably 30% or more because the voltage retention rate can be increased, and on the other hand, from the viewpoint of whitening characteristics, that is, from the viewpoint of suppressing the precipitation of the polymer in the varnish, 80 % Or less is 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 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 cellsolve, 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.

When the radical generation film is composed of a polymer containing an organic group that induces radical polymerization, the radical generation film-forming composition used in the present invention is other than a polymer containing an organic group that induces radical polymerization. It may contain other polymers. At that time, the content of the other polymer in all the components of the polymer is preferably 5 to 95% by mass, more preferably 30 to 70% by mass.

The molecular weight of the polymer contained in the radical generation film forming composition is GPC (GPC) when the strength of the radical generation film obtained by applying the radical generation film, 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.

As a polymer in the case where the radical generation film used in the present invention is immobilized in the film by applying a composition of a compound having a radical-generating group and a polymer and curing the film to form a film. , A polyimide precursor produced according to the above production method, and a polymer selected from the group consisting of polyimide, polyurea, polyamide, polyacrylate, polymethacrylate and the like, and containing an organic group that induces the above radical polymerization. At least one polymer obtained by using the diamine component in which the diamine to be used is 0 mol% of the total diamine component used for synthesizing the polymer contained in the radical generation film forming composition may be used. Examples of the compound having a group that generates a radical to be added at that time include the following.

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 compounds (azobisisobutyronitrile, and 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 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, 4- [P-N, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s- Triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-Mercaptobenzothiazole, 3,3'-carbonylbis (7-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) Phenylphenone, 3,3', 4,4'-tetra (tert-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -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)- Examples thereof include 1- (2-benzoyl) etanone. These compounds may be used alone or in admixture of two or more.

Even when the radical generation film is made of a polymer containing an organic group that induces radical polymerization, the group that generates the above radical is used for the purpose of promoting radical polymerization when energy is applied. The compound may be contained.

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, N-bis (oxyethylene) ) -3-Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene Glycol Diglycidyl Ether, Neopentyl Glycol Diglycidyl Ether, 1,6-Hexanediol Diglycidyl Ether, Glycerin Diglycidyl Ether, 2,2-Dibromo Neopentyl Glycol Diglycidyl Ether, 1,3,5,6-Tetra Glycidyl-2,4-hexanediol, N, N, N', N'-tetraglycidyl-m-xylene 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, etc. ..

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 is added. May be 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 changing the electrical 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, for example, by using the above-mentioned 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. Further, this cured film can be subjected to alignment processing by rubbing, polarization, light of a specific wavelength, or the like, and by processing an ion beam or the like, and UV (ultraviolet rays) are applied to the liquid crystal display element after filling the liquid crystal as a PSA alignment film. ) 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 butylate 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.

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 radically polymerizable compound of the present invention is represented by the following formula (A).

The aliphatic hydrocarbon group in R1 has ₁ to 10 carbon atoms, may have 1 to 8 carbon atoms, may have 1 to 6 carbon atoms, and may have 1 to 4 carbon atoms. May be good.

The alkyl group having 1 to 6 carbon atoms in R ₂ , R ₃ and R ₄ may be, for example, an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 4 carbon atoms. good. These alkyl groups may have a linear structure or a branched structure.

The aromatic hydrocarbon groups in R ₂ , R ₃ and R ₄ 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, two, or three. May be.
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 there are two or more groups represented by the formula (B), the groups represented by the two or more formulas (B) have the same structure. It may be present 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 the 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 ₄ . Two 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. There may be.

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, and 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.)

Examples of the radically polymerizable compound represented by the formula (A) include radically polymerizable compounds satisfying the following (1) to (3).
(1): In the formula (A), M represents the following structure (C) or structure (D), and R ₁ represents an aliphatic hydrocarbon group having a linear or branched structure having 1 to 10 carbon atoms. Each X independently represents a hydrogen atom or formula (B). However, at least one of the three Xs represents equation (B).
(2): In the formula (B), Y represents —O— and * indicates a binding site. _R2 , R3 _, and _R4 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.
(3): It is not a radically polymerizable compound represented by the following formula (E).

(In the structure (C) and the structure (D), * indicates a binding site.)

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.

Other radically polymerizable compounds have unsaturated bonds capable of performing radical polymerization in the presence of organic radicals, and are, for example, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, lauryl. Methacrylate monomers such as methacrylate, n-octyl methacrylate; acrylate monomers such as tert-butyl 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, benzoate) Vinyl acid acid, 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. Further, it is preferable that these have compatibility with the liquid crystal.

Further, as the other radically polymerizable compound, a compound represented by the following formula (1) is also preferable.

(In the formula (1 ^{), 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.)

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 (1), 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.

<Liquid crystal display element>
A liquid crystal display element can be manufactured using the liquid crystal cell thus obtained.
The liquid crystal display element has, for example, a first substrate, a second substrate arranged to face the first substrate, and a liquid crystal filled between the first substrate and the second substrate. Then, the liquid crystal display element is subjected to radical polymerization in a state where the liquid crystal and the liquid crystal composition containing the radically polymerizable compound represented by the formula (A) are brought into contact with the radical generating film of the first substrate having the radical generating film. It is made by polymerizing a sex compound.
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.

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-5: Compounds represented by the following formulas (DA-1) to (DA-5), respectively.

(Tetracarboxylic dianhydride)
TC-1 to TC-3: Compounds represented by the following formulas (TC-1) to (TC-3), respectively.

(Additive)
Add-1 to Add-11: Compounds represented by the following formulas (Add-1) to (Add-11), respectively. Addd-C1 to Add-C3: The following formulas (Add-C1) to (Add-C3, respectively). ): Compound represented by the following formula (AD-1)

(solvent)
THF: tetrahydrofuran CH ₂ Cl ₂ : dichloromethane CHCl ₃ : chloroform DMF: N, N-dimethylformamide NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve GBL: γ-butyrolactone (reaction tester)
TEA: Triethylamine DMAP: 4-Dimethylaminopyridine (Other)
BHT: 2,6-di-tert-butyl-p-cresol MEHQ: 4-methoxyphenol

<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).

<Measurement of imidization rate>
20 mg of polyimide powder is placed in an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Kagaku Co., Ltd.), and 1.0 mL of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05 mass% tetramethylsilane (TMS) mixture) is added. It was added and ultrasonically applied to completely dissolve it. This solution was measured by proton NMR at 500 MHz with a Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) “AVANCE III” (manufactured by BRUKER).
The chemical imidization rate is determined by using a proton derived from a structure that does not change before and after imidization as a reference proton, and the peak integrated value of this proton and the proton derived from the NH group of the amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It was calculated by the following formula using the peak integrated value. In the formula, x is the integrated proton peak value derived from the NH group of the amic acid, y is the integrated peak value of the reference proton, and α is the integrated value of the amic acid in the case of a polyamic acid (imidization rate is 0%). The number ratio of the reference protons to one proton of the NH group.
Imidization rate (%) = (1-α · x / y) × 100

<< Synthesis example Synthesis of additives for weak anchoring IPS >>
The products described in the following synthetic examples were identified by ¹ H-NMR analysis (analytical conditions are as follows).
Device: Fourier transform type superconducting nuclear magnetic resonance device (FT-NMR) "AVANCE III" (manufactured by BRUKER) 500 MHz.
Solvent: CDCl ₃ (deuterated chloroform) or DMSO-d ₆ (deuterated dimethyl sulfoxide).
Reference substance: Tetramethylsilane (TMS) (δ0.0 ppm for ¹ H).

(First step)
2-Bromoethanol (12.96 g: 103.73 mmol), Imidazole (7.06 g: 103.73 mmol), Trisopropylsilyl Chloroform (10.00 g: 51.87 mmol), and CHCl ₃ in a 300 mL four-necked flask equipped with a stir bar. (200 mL) was weighed and stirred at room temperature (20 ° C.) for 12 hours. After confirming the completion of the reaction by HPLC, the reaction solution was concentrated using a rotary evaporator, heptane (200 mL) was added, and the reaction solution 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 10/1 (volume ratio)), and the target product (9.19 g: yield 63%, colorless) is obtained by distilling off the solvent and vacuum drying. Clear liquid) was obtained.

(Second step)
A 300 mL four-necked flask equipped with a stirrer was obtained in the first step (2-Bromoethoxy) triisopropylsilane (9.00 g: 32.68 mmol), Potassium methyllate (4.77 g: 38.39 mmol), BHT (0.07 g). : 0.32 mmol) and DMF (200 mL) were weighed and stirred at 80 ° C. for 24 hours. After confirming the completion of the reaction by HPLC, the reaction solution was poured into 200 mL of heptane and 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 10/1 (volume ratio)), and the target product is Add-1 (8.80 g: yield) by distilling off the solvent and vacuum drying. A rate of 96%, pale yellow liquid) was obtained. ¹ It was confirmed by 1 H-NMR measurement that it was the target product.
^{1 1} H-NMR (500 MHz) in DMSO-d ₆ : 6.03 (1H), 5.67 (1H), 4.20-4.18 (2H), 3.91-3.89 (2H), 1 .88 (3H), 1.09-1.00 (21H)

(First step)
2-Bromoethanol (16.58 g: 132.70 mmol), Imidazole (9.03 g: 132.70 mmol), tert-butyldimethylchloroform (10.00 g: 66.35 mmol), and CHCl in a 300 mL four-necked flask equipped with a stir bar. ₃ (200 mL) was weighed and stirred at room temperature (20 ° C.) for 12 hours. After confirming the completion of the reaction by HPLC, the reaction solution was concentrated using a rotary evaporator, heptane (200 mL) was added, and the reaction solution 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 10/1 (volume ratio)), and the target product (7.30 g: yield 46%, colorless) is obtained by distilling off the solvent and vacuum drying. Clear liquid) was obtained.

(Second step)
A 300 mL four-necked flask equipped with a stirrer, obtained in the first step (2-bromoethoxy) (tert-butyl) dimethyllane (7.00 g: 29.26 mmol), Potassium methyllate (4.36 g: 35.11 mmol),. BHT (0.06 g: 0.29 mmol) and DMF (200 mL) were weighed and stirred at 80 ° C. for 24 hours. After confirming the completion of the reaction by HPLC, the reaction solution was poured into 200 mL of heptane and 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 10/1 (volume ratio)), and the target product is Add-2 (5.80 g: yield) by distilling off the solvent and vacuum drying. A rate of 86%, a pale yellow liquid) was obtained. ¹ It was confirmed by 1 H-NMR measurement that it was the target product.
^{1 1} H-NMR (500 MHz) in DMSO-d ₆ : 6.03 (1H), 5.69 (1H), 4.16-4.14 (2H), 3.82-3.80 (2H), 1 .88 (3H), 0.85 (9H), 0.04 (6H)

(First step)
2-Bromoethanol (18.19 g: 145.53 mmol), Imidazole (9.91: 145.53 mmol), tert-Butyldiphenylchloroform (10.00 g: 36.38 mmol), and CHCl in a 300 mL four-necked flask equipped with a stir bar. ₃ (400 mL) was weighed and stirred at room temperature (20 ° C.) for 12 hours. After confirming the completion of the reaction by HPLC, the reaction solution was concentrated using a rotary evaporator, heptane (200 mL) was added, and the reaction solution 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 10/1 (volume ratio)), and the target product (9.78 g: yield 74%, colorless) is obtained by distilling off the solvent and vacuum drying. Clear liquid) was obtained.

(Second step)
A 300 mL four-necked flask equipped with a stirrer, (2-bromoethoxy) (tert-butyl) diphenylsilane (9.78: 26.91 mmol), Potassium methyllate (4.00 g: 32.29 mmol), obtained in the first step. BHT (0.057 g: 0.26 mmol) and DMF (200 mL) were weighed and stirred at 80 ° C. for 24 hours. After confirming the completion of the reaction by HPLC, the reaction solution was poured into 200 mL of heptane and 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 20/1 (volume ratio)), and the target product is Addd-3 (6.55 g: yield) by distilling off the solvent and vacuum drying. A rate of 34%, a pale yellow liquid) was obtained. ¹ It was confirmed by 1 H-NMR measurement that it was the target product.
^{1 1} H-NMR (500 MHz) in DMSO-d ₆ : 7.63-7.62 (4H), 7.48-7.41 (6H), 6.03 (1H), 5.70-5.71 ( 1H), 4.25-4.27 (2H), 3.87-3.89 (2H), 1.89 (3H), 0.98 (9H)

(First step)
In a 300 mL four-necked flask equipped with a stirrer, 2- (Trimethylylyl) ethanol (10.00 g: 84.6 mmol), Pyridine (13.38 g: 169.1 mmol), Metacrylloid (11.50 g: 110.0 mmol), And THF (100 mL) was weighed and stirred at room temperature (20 ° C.) for 12 hours. After confirming the completion of the reaction by HPLC, the reaction solution was concentrated using a rotary evaporator, heptane (200 mL) was added, and the reaction solution 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 10/1 (volume ratio)), and the target product is Add-4 (12.00 g: yield) by distilling off the solvent and vacuum drying. A rate of 76%, a pale yellow liquid) was obtained. ¹ It was confirmed by 1 H-NMR measurement that it was the target product.
^{1 1} H-NMR (500 MHz) in CDCl ₃ : 6.06 (1H), 5.51 (1H), 4.21-4.24 (2H), 1.92 (3H), 1.00-1.03 (2H), 0.03-0.05 (9H)

(First step)
In a 300 mL four-necked flask equipped with a stirrer, 3- (Trimethylsylyl) -1-propanol (5.00 g: 37.8 mmol), Pyridine (5.98 g: 75.6 mmol), and Methacryloyl chloride (5.14 g: 49.). 1 mmol) and THF (50 mL) were weighed and stirred at room temperature (20 ° C.) for 12 hours. After confirming the completion of the reaction by HPLC, the reaction solution was concentrated using a rotary evaporator, heptane (200 mL) was added, and the reaction solution 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 20/1 (volume ratio)), and the target product is Add-5 (6.56 g: yield) by distilling off the solvent and vacuum drying. A rate of 87%, a pale yellow liquid) was obtained. ¹ It was confirmed by 1 H-NMR measurement that it was the target product.
^{1 1} H-NMR (500MHz) in CDCl ₃ : 6.08 (1H), 5.52 (1H), 4.06-4.09 (2H), 1.92 (3H), 1.61-1.67 (2H), 0.48-0.52 (2H), 0.01 (9H)

(First step)
3-Chloro-1-propanol (68.79 g: 727.6 mmol), Imidazole (49.53 g: 727.6 mmol), tert-Butyldiphenylchloroform (50.00 g: 181.9 mmol) in a 1 L 4-neck flask equipped with a stir bar. ) And CHCl ₃ (300 mL) were weighed and stirred at room temperature (20 ° C.) for 12 hours. After confirming the completion of the reaction by HPLC, the reaction solution was concentrated using a rotary evaporator, heptane (400 mL) was added, and the reaction solution 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 10/1 (volume ratio)), and the target product (42.79 g: yield 71%, light) is obtained by distilling off the solvent and vacuum drying. A yellow transparent liquid) was obtained.

(Second step)
In a 500 mL four-necked flask equipped with a stirrer, tert-butyl (3-chloropropoxy) diphenylsilane (14.55 g: 43.7 mmol), Potassium methyllate (8.14 g: 65.6 mmol), Potassium obtained in the first step. (0.73 g: 4.4 mmol), BHT (0.096 g: 0.44 mmol), and DMF (150 mL) were weighed and stirred at 80 ° C. for 24 hours. After confirming the completion of the reaction by HPLC, the reaction solution was poured into heptane (600 mL) and 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 50/1 (volume ratio)), and the target product is Add-6 (14.54 g: yield) by distilling off the solvent and vacuum drying. (Yield 87%, yellow liquid) was obtained. ¹ It was confirmed by 1 H-NMR measurement that it was the target product.
^{1 1} H-NMR (500 MHz) in DMSO-d ₆ : 7.60-7.62 (4H), 7.40-7.46 (6H), 5.96 (1H), 5.64 (1H), 4 .22-4.25 (2H), 3.73-3.75 (2H), 1.88-1.90 (2H), 1.84 (3H), 0.99 (9H)

(First step)
2-Bromoethanol (45.46 g: 363.8 mmol), Imidazole (24.77 g: 363.8 mmol), tert-Butyldiphenyl chloroform (25.00 g: 91.0 mmol), and CHCl in a 1 L 4-neck flask equipped with a stir bar. ₃ (150 mL) was weighed and stirred at room temperature (20 ° C.) for 12 hours. After confirming the completion of the reaction by HPLC, the reaction solution was concentrated using a rotary evaporator, heptane (200 mL) was added, and the reaction solution was washed 3 times with pure water (200 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 10/1 (volume ratio)), and the target product (23.93 g: yield 72%, light) is obtained by distilling off the solvent and vacuum drying. Yellow liquid) was obtained.

(Second step)
A 500 mL four-necked flask equipped with a stirrer was provided with (2-bromoethoxy) (tert-butyl) diphenylsilane (20.18 g: 55.6 mmol), Potassium acrylicate (9.18 g: 83.3 mmol), obtained in the first step. BHT (1.23 g: 5.6 mmol) and DMF (200 mL) were weighed and stirred at 80 ° C. for 24 hours. After confirming the completion of the reaction by HPLC, the reaction solution was poured into 600 mL of heptane and washed 3 times with pure water (300 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 50/1 (volume ratio)), and the target product is Add-7 (13.88 g: yield) by distilling off the solvent and vacuum drying. 70%, yellow liquid) was obtained. ¹ It was confirmed by 1 H-NMR measurement that it was the target product.
^{1 1} H-NMR (500 MHz) in DMSO-d ₆ : 7.62-7.64 (4H), 7.41-7.49 (6H), 6.31-6.35 (1H), 6.16- 6.21 (1H), 5.96-5.98 (1H), 4.26-4.27 (2H), 3.86-3.88 (2H), 0.99 (9H)

(First step)
3-Bromo-1-propanol (47.34 g: 340.6 mmol), Imidazole (23.19 g: 340.6 mmol), tert-Budyldiphenyl chloroformirane (20.00 g: 85.2 mmol) in a 500 mL four-necked flask equipped with a stir bar. ) And CHCl ₃ (150 mL) were weighed and stirred at room temperature (20 ° C.) for 12 hours. After confirming the completion of the reaction by HPLC, the reaction solution was concentrated using a rotary evaporator, heptane (150 mL) was added, and the reaction solution was washed 3 times with pure water (200 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 10/1 (volume ratio)), and the target product (20.35 g: yield 63%, yellow) is obtained by distilling off the solvent and vacuum drying. Liquid) was obtained.

(Second step)
A 500 mL four-necked flask equipped with a stirrer, obtained in the first step (3-bromopoxy) (tert-butyl) diphenylsilane (19.26 g: 51.0 mmol), Potassium acrylicate (6.75 g: 61.2 mmol),. BHT (1.12 g: 5.1 mmol) and DMF (200 mL) were weighed and stirred at 80 ° C. for 24 hours. After confirming the completion of the reaction by HPLC, the reaction solution was poured into heptane (600 mL) and washed 3 times with pure water (500 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 50/1 (volume ratio)), and the target product is Add-8 (13.63 g: yield) by distilling off the solvent and vacuum drying. A rate of 73%, yellow liquid) was obtained. ¹ It was confirmed by 1 H-NMR measurement that it was the target product.
^{1 1} H-NMR (500 MHz) in DMSO-d ₆ : 7.60-7.63 (4H), 7.41-7.48 (6H), 6.27-6.31 (1H), 6.11- 6.17 (1H), 5.92-5.94 (1H), 4.24-4.26 (2H), 3.72-3.75 (2H), 1.87-1.90 (2H) , 0.99 (9H)

(First step)
In a 500 mL four-necked flask equipped with a stirrer, 1,4-Butanediol (49.57 g: 550.0 mmol), Imidazole (14.86 g: 218.3 mmol), tert-Butyldiphenylchloroform (15.00 g: 54.6 mmol), And CHCl ₃ (100 mL) were weighed and stirred at room temperature (20 ° C.) for 12 hours. After confirming the completion of the reaction by HPLC, the reaction solution was concentrated using a rotary evaporator, heptane (200 mL) was added, and the reaction solution was washed 3 times with pure water (200 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 10/1 (volume ratio)), and the target product (16.78 g: yield 93%, transparent) is obtained by distilling off the solvent and vacuum drying. Liquid) was obtained.

(Second step)
4-((tert-butyldiphenylsyll) oxy) butan-1-ol (15.75 g: 47.9 mmol), Methacrylchloro chloride (6.01 g: 57) obtained in the first step in a 500 mL four-necked flask equipped with a stir bar. .5 mmol), Pyridine (5.70 g: 72.1 mmol), and THF (150 mL) were weighed and stirred at room temperature (20 ° C.) for 24 hours. After confirming the completion of the reaction by HPLC, the reaction solution was poured into heptane (500 mL) and washed 3 times with pure water (500 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 50/1 (volume ratio)), and the target product is Add-9 (8.92 g: yield) by distilling off the solvent and vacuum drying. (Yield 43%, transparent liquid) was obtained. ¹ It was confirmed by 1 H-NMR measurement that it was the target product.
^{1 1} H-NMR (500 MHz) in CDCl ₃ : 7.65-7.67 (4H), 7.36-7.44 (6H), 6.07 (1H), 5.53 (1H), 4.13 -4.16 (2H), 3.68-3.70 (2H), 1.93 (3H), 1.75-1.79 (2H), 1.63-1.67 (2H), 1. 05 (9H)

(First step)
In a 500 mL four-necked flask equipped with a stirrer, 1,5-Pentanediol (50.00 g: 480.0 mmol), Imidazole (13.07 g: 192.0 mmol), tert-Butyldiphenylchloroform (13.19 g: 48.0 mmol), And CHCl ₃ (90 mL) were weighed and stirred at room temperature (20 ° C.) for 12 hours. After confirming the completion of the reaction by HPLC, the reaction solution was concentrated using a rotary evaporator, heptane (200 mL) was added, and the reaction solution was washed 3 times with pure water (200 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 10/1 (volume ratio)), and the target product (15.00 g: yield 91%, transparent) is obtained by distilling off the solvent and vacuum drying. Liquid) was obtained.

(Second step)
5-((tert-butyldiphenylsylly) oxy) pentan-1-ol (15.00 g: 43.8 mmol), Methacrylchloro chloride (5.49 g: 52) obtained in the first step in a 500 mL four-necked flask equipped with a stir bar. .6 mmol), Pyridine (5.20 g: 65.7 mmol), and THF (150 mL) were weighed and stirred at room temperature (20 ° C.) for 24 hours. After confirming the completion of the reaction by HPLC, the reaction solution was poured into 500 mL of heptane and washed 3 times with pure water (500 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 50/1 (volume ratio)), and the target product is Add-10 (14.31 g: yield) by distilling off the solvent and vacuum drying. (Yield 80%, transparent liquid) was obtained. ¹ It was confirmed by 1 H-NMR measurement that it was the target product.
^{1 1} H-NMR (500 MHz) in CDCl ₃ : 7.64-7.66 (4H), 6.34-7.40 (6H), 6.07 (1H), 5.52 (1H), 4.10 -4.13 (2H), 3.64-3.67 (2H), 1.93 (3H), 1.62-1.68 (2H), 1.56-1.60 (2H), 1. 44-1.49 (2H), 1.03 (9H)

(First step)
1,2,3-Propanetriol (4.60 g: 50.0 mmol), TEA (12.10 g: 119.6 mmol), DMAP (0.37 g: 3.0 mmol), in a 500 mL four-necked flask equipped with a stir bar. tert-Butyldiphenylchlorosirane (30.20 g: 109.9 mmol) and CHCl ₃ (120 mL) were weighed and stirred at room temperature (20 ° C.) for 12 hours. After confirming the completion of the reaction by HPLC, the reaction solution was concentrated using a rotary evaporator, heptane (200 mL) was added, and the reaction solution was washed 3 times with pure water (200 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 10/1 (volume ratio)), and the target product (23.73 g: yield 83%, light) is obtained by distilling off the solvent and vacuum drying. Yellow liquid) was obtained.

(Second step)
2,2,10,10-tetramethyl-3,3,9,9-tetraphenyl-4,8-dioxa-3,9-disilandecan-6 obtained in the first step in a 500 mL four-necked flask equipped with a stir bar. -Ol (21.09 g: 37.1 mmol), Metacidlyl chloride (15.51 g: 148.4 mmol), Pyridine (14.66 g: 185.3 mmol), 4-Dimethylaminopyridine (1.81 g: 14.8 mmol), and THF. (200 mL) was weighed and stirred at room temperature (20 ° C.) for 24 hours. After confirming the completion of the reaction by HPLC, the reaction solution was poured into 500 mL of heptane and washed 3 times with pure water (500 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 50/1 (volume ratio)), and the target product is Add-11 (20.61 g: yield) by distilling off the solvent and vacuum drying. (Yield 88%, transparent liquid) was obtained. ¹ It was confirmed by 1 H-NMR measurement that it was the target product.
^{1 1} H-NMR (500 MHz) in CDCl ₃ : 7.62-7.65 (8H), 7.38-7.42 (4H), 7.31-7.36 (8H), 6.11 (1H) 5.56 (1H), 5.15-5.19 (1H), 3.89-3.90 (4H), 1.93 (3H), 1.00 (18H)

(First step)
In a 200 mL four-necked flask equipped with a stirrer, 3-Bromo-1-propanol (10.93 g: 78.6 mmol), TEA (7.96 g: 78.6 mmol), DMAP (0.96 g: 7.8 mmol), Trityl chloride (10.96 g: 39.3 mmol) and CHCl ₃ (100 mL) were weighed and stirred at room temperature (20 ° C.) for 12 hours. After confirming the completion of the reaction by HPLC, the reaction solution was concentrated using a rotary evaporator, ethyl acetate (500 mL) was added, and the reaction solution was washed 3 times with pure water (400 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 100/1 (volume ratio)), and the target product (8.06 g: yield 54%, white color) is obtained by distilling off the solvent and vacuum drying. Solid) was obtained.

(Second step)
A 200 mL four-necked flask equipped with a stirrer was obtained in the first step ((3-bromopropoxy) methaneriyl) tribenzen (8.06 g: 21.1 mmol), Potassium methacrylate (3.14 g: 25.3 mmol), MEHQ ( 0.26 g: 2.1 mmol) and DMF (80 mL) were weighed and stirred at 80 ° C. for 24 hours. After confirming the completion of the reaction by HPLC, the reaction solution was poured into ethyl acetate (400 mL) and washed 3 times with pure water (500 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. Purification is performed by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 50/1 (volume ratio)), and the target product is Addd-C3 (5.91 g: yield) by distilling off the solvent and vacuum drying. 73%, white solid) was obtained. ¹ It was confirmed by 1 H-NMR measurement that it was the target product.
^{1 1} H-NMR (500 MHz) in DMSO-d ₆ : 7.31-7.38 (12H), 7.24-7.27 (3H), 5.90 (1H), 5.62 (1H), 4 .22-4.24 (2H), 3.05-3.08 (2H), 1.89-1.91 (2H), 1.80 (3H)

<< Synthesis of polyamic acid / polyimide >>
<Synthesis Example 13>
DA-1 (1.08 g: 10.00 mmol) and DA-3 (3.30 g: 10.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen introduction tube, and NMP (24.9 g) was weighed. ), Stir and dissolve in a nitrogen atmosphere, then add TC-2 (2.50 g: 10.00 mmol) in an ice bath while keeping the temperature below 10 ° C, and react at 50 ° C for 6 hours under a nitrogen atmosphere. rice field. After returning to room temperature, TC-1 (1.84 g: 9.40 mmol) and NMP (10.0 g) were added and reacted at room temperature for 18 hours to have a viscosity of about 1120 mPa · s and a solid content concentration of 20 mass. % Polyamic acid solution (PAA-1) was obtained. The molecular weight of this polyamic acid was a number average molecular weight: 11200 and a weight average molecular weight: 31360.
The polyamic acid solution (PAA-1) (40.0 g) obtained above was weighed in a 300 mL eggplant flask equipped with a stirrer and a nitrogen introduction tube, NMP (74.3 g) was added, and the mixture was stirred at room temperature for a while. After that, anhydrous acetic acid (5.61 g: 54.98 mmol) and pyridine (2.90 g, 36.65 mmol) were added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere and then reacted at 50 ° C. for 3 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was slowly poured into methanol (500 mL) cooled to 10 ° C. or lower to precipitate a solid, and the mixture was stirred for 10 minutes. The precipitate was separated by filtration, and the slurry was washed again with methanol (200 mL) for 30 minutes twice in total, and the solid was vacuum dried at 80 ° C. to obtain the desired polyimide powder (SPI-1) (7.04 g). , 88% yield) was obtained. The imidization ratio of this polyimide was 57%, the molecular weight was a number average molecular weight: 10400, and a weight average molecular weight: 29120.

<Synthesis Example 14>
DA-2 (3.42 g: 14.00 mmol) and DA-4 (4.11 g: 6.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen introduction tube, and NMP (56.8 g) was weighed. ), Stir and dissolve in a nitrogen atmosphere, then add TC-3 (4.26 g: 19.00 mol) 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 680 mPa · s and a solid content concentration of 15% by mass was obtained. The molecular weight of this polyamic acid was a number average molecular weight: 17200 and a weight average molecular weight: 48160.

<Synthesis Example 15>
DA-2 (3.42 g: 14.00 mmol) and DA-5 (1.55 g: 6.00 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-3 (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-3) 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 a number average molecular weight: 15500 and a weight average molecular weight: 41800.

<< Preparation of liquid crystal alignment agent >>
<Preparation Example 1 Preparation of Radical Generation Film Forming Composition AL-1>
2.0 g of the polyimide powder (SPI-1) obtained in Synthesis Example 13 was weighed in a 50 mL Erlenmeyer flask equipped with a stirrer, NMP (18.0 g) was added, and the mixture was stirred at room temperature for 12 hours to dissolve. .. After confirming that all the solids have melted, NMP (8.0 g), BCS (12.0 g), and AD-1 (0.20 g) are added, and the mixture is stirred at room temperature for 1 hour to be used in the present invention. A liquid crystal alignment agent and a radical generating film forming composition (AL-1) was obtained.

<Preparation Example 2 Preparation of Radical Generation Film Forming Composition AL-2>
In a 50 mL Erlenmeyer flask equipped with a stirrer, 15.0 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 14 is weighed, NMP (16.5 g) and BCS (13.5 g) are added, and room temperature is reached. The liquid crystal aligning agent and radical generating film-forming composition (AL-2) used in the present invention was obtained by stirring with the mixture for 1 hour.

<Preparation Example 3 Preparation of liquid crystal alignment agent AL-3>
In a 50 mL Erlenmeyer flask equipped with a stirrer, 15.0 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 15 was weighed, NMP (16.5 g) and BCS (13.5 g) were added, and room temperature was reached. The liquid crystal alignment agent (AL-3) used in the present invention was obtained by stirring with the mixture for 1 hour.

<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. And form a pixel. The size of each pixel is 10 mm in length and about 5 mm in width. Hereinafter referred to as an IPS board.
Next, the radical generation film forming composition AL-1 and AL-2 obtained by the above method, the liquid crystal alignment agent AL-3, and the liquid crystal alignment agent SE-6414 for horizontal alignment (manufactured by Nissan Chemical Industries, Ltd.). ) Is filtered through a filter having a pore size of 1.0 μm, and then the prepared IPS substrate and a glass 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 a facing substrate). It was coated and filmed 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 polyimide film on the IPS substrate side was oriented along the direction of the comb teeth, and the polyimide film on the opposite substrate side was oriented in the direction orthogonal to the comb tooth electrode. In the alignment process, the rubbing method is used for AL-1 and SE-6414, and a rubbing device manufactured by Iinuma Gauge, a rubbing cloth (YA-20R) manufactured by Yoshikawa Kako, a rubbing roller (diameter 10.0 cm), and a stage. The feed rate was 30 mm / s, the roller rotation speed was 700 rpm, and the pushing pressure was 0.3 mm. In both AL-2 and AL-3, a UV exposure device manufactured by Ushio, Inc. is used so that the irradiation amount of linearly polarized UV having an extinction ratio of about 26: 1 is 300 mJ / cm ² based on the wavelength of 254 nm. Was irradiated with polarized UV and heated at 230 ° C. for 20 minutes to perform alignment treatment.
After that, using the above two types of substrates, a radical generation alignment film is used on the IPS substrate side for the display element to be the target of the embodiment and some display elements to be compared (Comparative Examples 2 to 4, 6 to 8). A part of the display elements to be compared (Comparative Example 1) using a combination of AL-1 or AL-2 and those provided with the liquid crystal alignment film SE-6414 or AL-3 on the facing substrate side. In Comparative Example 5), SE-6414 or AL-3 was used for both substrates. The cells were combined so that their orientation directions were parallel to each other, and the periphery was sealed leaving the liquid crystal injection port, to prepare an empty cell having a cell gap of about 3.0 μm. A liquid crystal mixture obtained by adding 2% by mass of (Add-1) to (Add-11) obtained in the above synthesis example to this empty cell, and a liquid crystal mixture without addition or (Add-C1) to ((Add-C1) to ( A liquid crystal mixture containing 2% by mass of Addd-C3) was used, and each was vacuum-injected at room temperature, and then the injection port was sealed to obtain an anti-parallel oriented liquid crystal cell. As the liquid crystal mixture used, LC-A (manufactured by DIC Corporation, Δn: 0.130, Δε: 4.4) was used. As Add-C1 to Add-C2, those purchased from Tokyo Chemical Industry were used.
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 uneven orientation 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 to monitor the black brightness (V: a. 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 brightness is the smallest, and the voltage is applied to 8V at 1V intervals. The VT curve was measured by applying and measuring the brightness at the 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.

<Measurement of voltage retention rate (VHR)>
The voltage retention rate at room temperature was measured. By applying a voltage of 4 V for 60 μs to the prepared liquid crystal display element at a temperature of 23 ° C. and measuring the voltage after 16.7 ms, how much the voltage could be maintained was calculated as the voltage retention rate.
In addition, the voltage retention rate at high temperature was measured. A voltage of 1 V was applied to the prepared liquid crystal display element at a temperature of 70 ° C. for 60 μs, and the voltage after 1667 ms was measured to measure how much the voltage could be maintained as the voltage retention rate.
A VHR-1 voltage holding rate measuring device manufactured by Toyo Corporation was used for measuring the voltage holding rate.

<Contents of polymer>
Table 1 shows the compositions of the polymers synthesized in Synthesis Examples 13 to 15.

<Contents of liquid crystal alignment agent or radical generation film forming composition>
Table 2 shows the compositions of the liquid crystal alignment agent or the radical-generating film-forming composition prepared in Preparation Examples 1 to 3.

<LCD cell contents (rubbing)>
Table 3 shows the contents of Examples and Comparative Examples of the liquid crystal cells subjected to the alignment treatment by the rubbing method.

<Characteristic evaluation result>
Tables 4-1 and 4-2 show the characteristics evaluation results of the liquid crystal cells that have been oriented by the rubbing method.

In the weak anchoring liquid crystal cell using the additives (Add-1) to (Add-11) of the present invention, the orientation state and the black brightness are good, and the occurrence of the pretilt angle on the weak anchoring side is not confirmed and is 0. It was less than 1 °. It can be seen that Vmax is also significantly reduced as compared with the strong anchoring liquid crystal cell of Comparative Example 1, and the transmittance is greatly improved as compared with Comparative Examples 1 to 4. On the other hand, in Comparative Examples 2 to 3, the liquid crystal display element using Addd-C1 or Addd-C2 as an additive has many rubbing streaks and poor black brightness. Further, in Comparative Examples 2 to 4, it was confirmed that the Vmax was lower than that of the strong anchoring liquid crystal cell of Comparative Example 1, but the transmittance was lower. It was found that this was due to the generation of the pre-tilt angle due to the weak anchoring, and it was found that a very large pre-tilt angle of about 72 ° was generated in Comparative Example 2 and 83 ° in Comparative Example 3. On the other hand, regarding the response speed, the liquid crystal cells of Examples 1 to 11 using the additives of Synthesis Examples 1 to 11 have a slightly slower response speed than the strong anchoring liquid crystal cells of Comparative Example 1, but they are still within the allowable range. It can be seen that the response speed is fast and the response speed is significantly improved as compared with Comparative Examples 2 to 4. In the above Examples and Comparative Examples, when MLC-3019 (Δn: 0.104, Δε: 9.9) manufactured by Merck Group was used for the liquid crystal instead of LC-A, it was used in Comparative Examples 2 to 4. Good weak anchoring IPS characteristics can be obtained even when Add-C1 to Add-C3 are used, but good weak anchoring is obtained when used for a liquid crystal display having a large Δn or a liquid crystal display having a small Δε such as LC-A. The characteristics of IPS cannot be obtained. This means that, for example, when a liquid crystal display element is manufactured by narrowing the cell gap (for example, making it 3.5 μm or less), the additives used in Comparative Examples 2 to 4 cannot be used. .. With the additive of the present invention, good weak anchoring IPS characteristics can be obtained even when such a liquid crystal display having a high Δn and a small Δε can be used, and the response speed can be improved by narrowing the cell gap. Further, the VHR was also higher than that of Comparative Examples 2 to 4 especially at high temperature, and it was found that the reliability can be improved by using the additive of the present invention.

<LCD cell contents (optical orientation)>
Table 5 shows the contents of Examples and Comparative Examples of the liquid crystal cells subjected to the alignment treatment by the optical alignment method.

<Characteristic evaluation result>
Table 6 shows the characteristics evaluation results of the liquid crystal cells that have been oriented by the optical alignment method.

Even in the weak anchoring IPS prepared by the photoalignment method, when the additives (Add-1) to (Add-11) of the present invention are used, the weak anchoring IPS prepared by the rubbing method is used. It was confirmed that similar good characteristics could be obtained. On the other hand, when (Add-C1), (Add-C2), or (Add-C3) used in Comparative Examples 2 to 4 is used, a domain is generated as in Comparative Examples 6 to 8, and the drive cannot be performed. .. In the case of photo-orientation, unlike the rubbing method, the anisotropy of the pre-tilt angle does not appear, so if a relatively large pre-tilt angle occurs due to some influence, the direction of the pre-tilt angle is not specified and it becomes a domain. It is presumed that the domain cannot be driven because the domain area is expanded by the electric field when it is tried to be driven. It has been found that the additive of the present invention is very useful because no domain is generated even when photo-orientation is used and good weak anchoring IPS characteristics can be obtained. As for VHR, it was found that VHR was good at high temperature as well as rubbing, and it was found that the use of this polymerizable compound as an additive for weak anchoring IPS was effective in improving reliability.

According to the present invention, it is possible to provide a lateral electric field liquid crystal display element capable of realizing high backlight transmittance and fast response speed without generating a pretilt angle or a domain even when a liquid crystal having a high Δn and a low Δε is used. In addition, 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

A liquid crystal display element comprising a step of polymerizing the radically polymerizable compound in a state where the liquid crystal and the liquid crystal composition containing the radically polymerizable compound represented by the following formula (A) are in contact with the radical generating film. Production method.

(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), but at least one of the three Xs represents the formula (B).)

(In the 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.)
The method for manufacturing a liquid crystal display element according to claim 1, wherein in the formula (B), the aromatic hydrocarbon group which may have the substituent is a phenyl group.
The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein M in the formula (A) is 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, and 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 method for manufacturing a liquid crystal display element according to any one of claims 1 to 3, wherein the radical generation film is a radical generation film subjected to uniaxial orientation processing.
The method for manufacturing a liquid crystal display element according to any one of claims 1 to 4, wherein the step of performing the polymerization reaction is performed under no electric field conditions.
The method for manufacturing a liquid crystal display element according to any one of claims 1 to 5, wherein the radical generating film is a film formed by immobilizing an organic group that induces radical polymerization.
The radical-generating film is coated with a composition containing a compound having an organic group that generates radicals and a polymer, and cured to form a film, whereby the organic group that generates radicals is formed in the film. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 5, which is obtained by immobilization.
The method for manufacturing a liquid crystal display element according to any one of claims 1 to 5, wherein the radical generating film is made of a polymer containing an organic group that induces radical polymerization.
The polymer containing an organic group that induces radical polymerization is at least one selected from a polyimide precursor, a polyimide, a polyurea, and a polyamide obtained by using a diamine component containing a diamine containing an organic group that induces radical polymerization. The method for manufacturing a liquid crystal display element according to claim 8, which is a polymer.
The ninth aspect of the present invention, wherein the organic group that induces radical polymerization is an organic group represented by the following formulas [X-1] to [X-18], [W], [Y], or [Z]. A method for manufacturing a liquid crystal display element.

(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.)

(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 indicated.) 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 diamine according to claim 9 or 10, wherein the diamine containing an organic group that induces radical polymerization is a diamine having a structure represented by the following formula (6), the following formula (7), or the following formula (7'). Manufacturing method of liquid crystal display element.

(In formula (6), R 6 is a single bond, -CH 2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH 2 O-, -N. Represents (CH 3 )-, -CON (CH 3 )-, or -N (CH 3 ) CO-.
R 7 represents an alkylene group having 1 to 20 carbon atoms which is single-bonded or substituted 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. May be replaced with a group selected from -CH = CH-, a divalent carbocycle, and a divalent heterocycle, and any of the following groups, i.e., -O-, -COO-. , -OCO-, -NHCO-, -CONH-, or -NH- may be replaced by these groups provided they are not adjacent to each other;
R 8 represents a radical polymerization reactive group represented by a formula selected from the following formulas [X-1] to [X-18].

(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.)))

(In equations (7) and (7'), T 1 and T 2 are independently single-bonded, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, respectively. -NH-, -CH 2 O-, -N (CH 3 )-, -CON (CH 3 )-, or -N (CH 3 ) CO-.
S 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 independently. It may be replaced with a group selected from -CH = CH-, a divalent carbocycle, and a divalent heterocyclic ring, and further, any of the following groups, that is, -O-, -COO-,. -OCO-, -NHCO-, -CONH-, or -NH- may be replaced by these groups provided that they are not adjacent to each other.
E is a single bond, -O-, -C (CH 3 ) 2- , -NH-, -CO-, -NHCO-, -COO-,-(CH 2 ) m- , -SO 2- , -O. -(CH 2 ) m -O-, -OC (CH 3 ) 2- , -CO- (CH 2 ) m- , -NH- (CH 2 ) m- , -SO 2- (CH 2 ) m -, -CONH- (CH 2 ) m- , -CONH- (CH 2 ) m -NHCO-, or -COO- (CH 2 ) m -OCO-, where m is an integer from 1 to 8.
J is an organic group represented by a formula selected from the following formulas [W], [Y] and [Z].

(In the formulas [W], [Y], and [Z], * represents a bond with T 2 , Ar represents an organic group and / or a halogen atom as a substituent, phenylene, naphthylene, and Indicates an aromatic hydrocarbon group selected from the group consisting of biphenylylene, R 9 and R 10 independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q is described below. Represents either structure.

(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 indicated.) 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. )) In equation (7'), q is independently 0 or 1, at least one q is 1, and p represents an integer of 1 to 2. )
The step of preparing the first substrate having the radical generation film and the second substrate having the radical generation film may be prepared.
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.
A step of filling the liquid crystal composition between the first substrate and the second substrate, and a step of causing the polymerization reaction.
The method for manufacturing a liquid crystal display element according to any one of claims 1 to 11.
The method for manufacturing a liquid crystal display element according to claim 12, 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 12, 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 14, 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 12 to 15, wherein either the first substrate or the second substrate is a substrate having a comb tooth electrode.
A liquid crystal composition comprising a liquid crystal display and a radically polymerizable compound 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), but at least one of the three Xs represents the formula (B).)

(In the 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.)
The liquid crystal composition according to claim 17, wherein the aromatic hydrocarbon group which may have the substituent in the formula (B) is a phenyl group.
The liquid crystal composition according to claim 17 or 18, wherein M in the formula (A) is 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, and 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.)
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 in a state where the liquid crystal composition containing the liquid crystal and the radically polymerizable compound represented by the following formula (A) is in contact with the radically polymerized film of the first substrate having the radically generated film. A liquid crystal display element characterized by having a polymerization reaction.

(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), but at least one of the three Xs represents the formula (B).)

(In the 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.)
The liquid crystal display element according to claim 20, wherein either the first substrate or the second substrate is a substrate having a comb tooth electrode.
The liquid crystal display element according to claim 20 or 21, which is a low voltage drive horizontal electric field liquid crystal display element.
A radically polymerizable compound represented by any of the following formulas (F-1) to (F-6).