CN114846397A

CN114846397A - Method for manufacturing patterned liquid crystal display element

Info

Publication number: CN114846397A
Application number: CN202080088920.7A
Authority: CN
Inventors: 三宅一世; 野田尚宏
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2019-12-18
Filing date: 2020-12-18
Publication date: 2022-08-02
Also published as: KR20220116219A; WO2021125327A1; JPWO2021125327A1; TW202130703A

Abstract

The invention provides a method for manufacturing a liquid crystal display element having 2 or 3 different alignment regions (in-plane (uniaxial) alignment region, out-of-plane alignment region, and tilt alignment region) in the same element, which is a simple and inexpensive method. The method for manufacturing the liquid crystal display element comprises the following steps: step (A): forming a radical generating film capable of generating radicals by irradiation with light on a substrate; and a step (B): a liquid crystal display element is produced by bringing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound into contact with the radical generating film, and irradiating the liquid crystal composition with light having a peak at 240 to 400nm, which is sufficient to cause the radical polymerizable compound to undergo a polymerization reaction, while maintaining the state, wherein the radical polymerizable compound has a function of vertically aligning the liquid crystal by polymerization, and further, the liquid crystal display element comprises at least one of the following requirements (Z1) and (Z2), and at least 2 of an in-plane alignment region, an out-of-plane alignment region, and an oblique alignment region are patterned. Requirement (Z1): the method further comprises a step (C) of irradiating the radical generating film obtained in the step (A) with light having a peak at 240 to 400nm to inactivate the radical generating ability of the radical generating film between the step (A) and the step (B). Requirement (Z2): the step (B) of irradiating the liquid crystal composition with light having a peak at 240 to 400nm is performed through a photomask.

Description

Method for manufacturing patterned liquid crystal display element

Technical Field

The present invention relates to a method for manufacturing a liquid crystal display element in which at least 2 regions out of an in-plane alignment region, an out-of-plane alignment region, and an oblique alignment region are patterned, by a method which is inexpensive and does not involve complicated steps.

Background

In recent years, liquid crystal display elements have been widely used in displays of mobile phones, computers, and televisions. Liquid crystal display elements have characteristics such as thin thickness, light weight, and low power consumption, and are expected to be applied to VR (Virtual Reality) and ultra-high definition displays in the future. Various display modes such as TN (Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), and the like have been proposed as display modes of a liquid crystal display, but a film (liquid crystal Alignment film) for inducing liquid crystals into a desired Alignment state is used In all modes.

In particular, in products having a touch panel such as a tablet PC, a smartphone, and a smart TV, an IPS mode in which display is not disturbed easily even when touched is preferable, and in recent years, a liquid crystal display element using FFS (Fringe Field Switching) and a technique using a non-contact technique using photo-alignment have been used in order to improve contrast and improve viewing angle characteristics.

However, FFS has the following problems: compared to IPS, the manufacturing cost of the substrate is high, and a display defect unique to FFS mode called Vcom shift occurs. Further, photo-alignment has an advantage that the size of a device to be manufactured can be increased or display characteristics can be greatly improved compared to a rubbing method, but a principle problem of photo-alignment (display failure due to a decomposed product in the case of a decomposed type, and afterimage due to insufficient alignment force in the case of an isomerized type) is cited. In order to solve these problems, various studies have been carried out by liquid crystal display element manufacturers or liquid crystal alignment film manufacturers.

On the other hand, in recent years, an IPS mode using zero plane anchoring (also referred to as weak anchoring) has been proposed, and it has been reported that by using this method, contrast is improved and a large low voltage driving is possible compared to a conventional IPS mode (see patent document 1).

Specifically, a liquid crystal alignment film having strong anchoring energy is used for one substrate, and a treatment is applied to the other substrate having an electrode for generating a lateral electric field to lose the alignment constraint of all liquid crystals, and the liquid crystal display element of the IPS mode is manufactured using the liquid crystal alignment film and the other substrate.

In recent years, a zero-plane state has been produced using a thick polymer brush or the like, and a technique of a zero-plane anchoring IPS mode (also referred to as a weak-anchoring IPS mode) has been proposed (see reference 2). By this technique, the contrast ratio is greatly improved or the driving voltage is greatly reduced.

On the other hand, there is a problem that the response speed, particularly the response speed at the time of voltage OFF, is remarkably lowered. This is because the driving voltage is low, and therefore, the influence of the response is made to be lower by a weaker electric field than in a normal driving method, and the recovery of the liquid crystal takes time because the anchoring force of the alignment film is extremely small.

As a method for solving this problem, a method of performing zero anchoring only on the pixel electrode has been proposed (for example, see patent document 3). From this, it is reported that improvement of luminance and response speed can be compatible.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 4053530

Patent document 2: japanese patent laid-open publication No. 2013-231757

Patent document 3: japanese patent laid-open publication No. 2017-211566

Disclosure of Invention

Problems to be solved by the invention

When an alignment film appropriately designed according to the application is used, the alignment state of various liquid crystals can be controlled. In particular, in-plane uniaxial orientation is obtained when an oriented film having an anchoring force in an in-plane uniaxial direction is used, and out-of-plane orientation is obtained when an oriented film having an anchoring force in an out-of-plane direction is used.

On the other hand, it is very difficult to fabricate a liquid crystal cell having both an in-plane uniaxial alignment region and an out-of-plane alignment region in the same cell. This is because it is necessary to form regions having greatly different anchoring forces in the same element, and in order to achieve this, it is necessary to change the anchoring force in any region after the liquid crystal element is formed, or to coat alignment films having different anchoring forces on the substrates constituting the element in advance. The former has not been reported so far, and the latter has been a great problem in industrialization because it is necessary to accurately apply the coating material to a very fine area and to prepare a technique for performing an alignment treatment.

If such technical problems can be solved, a liquid crystal element having an arbitrary alignment state in an arbitrary region can be formed, and application to an optical film, an optical property modulation element, or the like can be expected.

The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a method for manufacturing a liquid crystal display element, in which a chemical reaction is induced on a contact surface between an alignment film and a liquid crystal, and a chemical reaction is induced in an arbitrary region in an in-plane direction of the alignment film, thereby controlling the surface energy or anchoring energy of an interfacial reaction region to an arbitrary state, and a liquid crystal display element having 2 or 3 different alignment regions (in-plane (uniaxial) alignment region, out-of-plane alignment region, and oblique alignment region) in the same element is manufactured in a simple and inexpensive manner.

Means for solving the problems

As a result of intensive 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.

The present invention includes the following.

[1]

A method of manufacturing a liquid crystal display element, comprising:

step (A): forming a radical generating film capable of generating radicals by irradiation with light on a substrate; and

a step (B): a liquid crystal composition containing a liquid crystal and a radical polymerizable compound is brought into contact with the radical generating film, and while maintaining this state, the liquid crystal composition is irradiated with light having a peak at 240 to 400nm sufficient to cause the radical polymerizable compound to undergo a polymerization reaction,

the radical polymerizable compound has a function of vertically aligning the liquid crystal by polymerization,

further, a liquid crystal display element in which at least 2 regions out of the in-plane alignment region, the out-of-plane alignment region, and the tilt alignment region are patterned was manufactured, including at least one of the following requirements (Z1) and (Z2).

Requirement (Z1): the method further comprises a step (C) of irradiating the radical generating film obtained in the step (A) with light having a peak at 240 to 400nm to inactivate the radical generating ability of the radical generating film between the step (A) and the step (B).

Requirement (Z2): the step (B) of irradiating the liquid crystal composition with light having a peak at 240 to 400nm is performed through a photomask.

[2]

The method for manufacturing a liquid crystal display element according to item [1], wherein the radical generating film is a coating film subjected to uniaxial alignment treatment.

[3]

The method for manufacturing a liquid crystal display element according to [1] or [2], wherein the step (B) of irradiating the liquid crystal composition with light having a peak at 240 to 400nm is performed in the absence of an electric field.

[4]

The method for manufacturing a liquid crystal display element according to any one of [1] to [3], wherein the radical generating film has a polymer containing an organic group that initiates radical polymerization.

[5]

The method for producing a liquid crystal display element according to item [4], wherein the polymer having an organic group which initiates radical polymerization has a structural unit represented by the following formula (1) in a main chain,

[ chemical formula 1]

(in the formula (1), A represents an organic group which initiates radical polymerization).

[6]

The method for manufacturing a liquid crystal display element according to [4] or [5], wherein the polymer is at least one selected from a polyimide precursor obtained using a diamine component containing a diamine containing an organic group that initiates radical polymerization, a polyimide, a polyurea, and a polyamide.

[7]

The method for manufacturing a liquid crystal display element according to item [5], wherein the radical polymerization-initiating organic group is a group represented by formula (3).

[ chemical formula 2]

(in the formula (3), the dotted line represents a bond with a benzene ring, R ⁶ Represents a single bond, -CH ₂ -、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH ₂ O-、-N(CH ₃ )-、-CON(CH ₃ ) -or-N (CH) ₃ )CO-，

R ⁷ Represents a single bond, or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with a fluorine atom, or any of-CH's of the alkylene groups ₂ -or-CF ₂ -1 or more of-are each independently optionally substituted with a group selected from-CH ═ CH-, a 2-valent carbocyclic ring, and a 2-valent heterocyclic ring, and further optionally substituted with any of the groups listed below, i.e., -O-, -COO-, -OCO-, -NHCO-, -CONH-, or-NH-, under the condition that these groups are not adjacent to each other.

R ⁸ Is represented by a group selected from the formula [ X-1 ]]～[X-18]、[W]、[Y]、[Z]The organic group which initiates radical polymerization represented by the formula (1),

[ chemical formula 3]

Formula [ X-1]～[X-18]Wherein represents a group represented by ⁷ Bonding site of (2), S ₁ And S ₂ Each independently represents-O-, -NR-, or-S-, R 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, R ₁ And R ₂ Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms,

[ chemical formula 4]

Formula [ W ]]、[Y]、[Z]Wherein represents a group represented by ⁷ Bonding site of (2), S ³ Represents a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-、-N(CH ₃ )-、-CON(CH ₃ ) -, or-N (CH) ₃ ) CO-Ar tableAn aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene optionally having an organic group and/or a halogen atom as a substituent, R ⁹ And R ¹⁰ Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group or a phenethyl group, and in the case of an alkyl group or an alkoxy group, R represents ⁹ And R ¹⁰ Optionally forming a ring,

q represents any one of the following structures,

[ chemical formula 5]

In the formula, R ¹¹ represents-CH ₂ -, -NR-, -O-, or-S-, wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and represents a bonding site,

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).

[8]

The method for producing a liquid crystal display element according to item [6], wherein the diamine containing an organic group which initiates radical polymerization is a diamine represented by the following formula (2),

[ chemical formula 6]

(in the formula (2), A ¹ And A ² Each represents a hydrogen atom or a group represented by the following formula (3) wherein A ¹ And A ² At least one of them represents a group represented by the following formula (3),

e represents a single bond, -O-, -C (CH) ₃ ) ₂ -、-NH-、-CO-、-NHCO-、-COO-、-(CH ₂ ) _m -、-SO ₂ Or a 2-valent organic group composed of any combination thereof, m represents an integer of 1 to 8,

p represents an integer of 0 to 2, and when p is 2, a plurality of A ² And E independently have the above definitions, and when p is 0, A ¹ Is composed of a group represented by the following formula (3).

[ chemical formula 7]

[ chemical formula 8]

Formula [ X-1]～[X-18]Wherein represents a group represented by ⁷ Bonding site of (2), S ₁ 、S ₂ Each independently represents-O-, -NR-, or-S-, R 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, and R is ₁ 、R ₂ Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms,

[ chemical formula 9]

Formula [ W ]]、[Y]、[Z]In (1), represents andR ⁷ bonding site of (2), S ³ Represents a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-、-N(CH ₃ )-、-CON(CH ₃ ) -, or-N (CH) ₃ ) CO-, Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene optionally having an organic group and/or a halogen atom as a substituent, and R ⁹ And R ¹⁰ Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group or a phenethyl group, and in the case of an alkyl group or an alkoxy group, R represents ⁹ And R ¹⁰ Optionally forming a ring,

q represents any one of the following structures,

[ chemical formula 10]

[9]

The method for manufacturing a liquid crystal display element according to any one of [1] to [8], wherein at least one of the radical polymerizable compounds is a compound having one polymerizable unsaturated bond in one molecule and having compatibility with a liquid crystal.

[10]

The method for manufacturing a liquid crystal display element according to item [9], wherein the radical polymerizable compound has a polymerization reactive group selected from the following structures,

[ chemical formula 11]

(wherein R represents a site bonded to a portion other than the polymerizable unsaturated bond of the compound molecule; R ^b Represents an alkyl group having 3 to 20 carbon atoms, and E represents a bonding group selected from the group consisting of a single bond, -O-, -NRc-, -S-, an ester bond and an amide bond. R ^c Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, R ^b The alkyl group of (b) represents a linear, branched, or cyclic alkyl group).

[11]

The method for manufacturing a liquid crystal display element according to any one of [1] to [10], wherein the liquid crystal composition containing a liquid crystal and a radically polymerizable compound contains a radically polymerizable compound having a polymer obtained by polymerizing the radically polymerizable compound and having a Tg of 100 ℃ or lower.

[12]

The method of manufacturing a liquid crystal display element according to any one of [1] to [11], further comprising a step of manufacturing a liquid crystal cell by:

preparing a first substrate having a radical generating film, and a second substrate;

a radical generating film on the first substrate, the radical generating film being disposed so as to face the second substrate; and

a liquid crystal composition containing a liquid crystal and a radical polymerizable compound is filled between the first substrate and the second substrate.

[13]

The method of manufacturing a liquid crystal display element according to [12], wherein the second substrate has a radical generating film.

[14]

The method of manufacturing a liquid crystal display element according to [12], wherein the second substrate is a substrate covered with a liquid crystal alignment film having uniaxial alignment properties.

[15]

The method of manufacturing a liquid crystal display element according to item [14], wherein the liquid crystal alignment film having a uniaxial alignment property is a liquid crystal alignment film for horizontal alignment.

[16]

The method of manufacturing a liquid crystal display element according to any one of [12] to [15], wherein the first substrate having the radical generating film is a substrate having comb-teeth electrodes.

Effects of the invention

According to the present invention, it is possible to provide a method for manufacturing a liquid crystal display element, which can manufacture a liquid crystal display element having 2 or 3 different alignment regions (in-plane (uniaxial) alignment region, out-of-plane alignment region, and tilt alignment region) in the same element, in a simple and inexpensive manner.

Drawings

Fig. 1A is a photograph of the liquid crystal display element obtained in example 5.

Fig. 1B is a diagram schematically showing a photograph of the liquid crystal display element of fig. 1A.

Fig. 2A is a photograph of the liquid crystal display element obtained in comparative example 4.

Fig. 2B is a diagram schematically showing a photograph of the liquid crystal display element of fig. 2A.

Fig. 3A is a photograph of the liquid crystal display element obtained in example 1.

Fig. 3B is a diagram schematically showing a photograph of the liquid crystal display element of fig. 3A.

Fig. 4A is a photograph of the liquid crystal display element obtained in example 23.

Fig. 4B is a diagram schematically showing a photograph of the liquid crystal display element of fig. 4A.

Fig. 5A is a photograph of the liquid crystal display element obtained in example 24.

Fig. 5B is a diagram schematically showing a photograph of the liquid crystal display element of fig. 5A.

Fig. 6 is a photograph of the liquid crystal display element obtained in example 25 and example 26.

Fig. 7 is a photograph of the liquid crystal display element obtained in example 27.

Fig. 8 is a photograph of the liquid crystal display element obtained in example 30.

Fig. 9A is a photograph of the liquid crystal display element obtained in example 32.

Fig. 9B is a diagram schematically showing a photograph of the liquid crystal display element of fig. 9A.

Fig. 10 is a schematic cross-sectional view showing an example of a liquid crystal display element according to the present invention.

Fig. 11 is a schematic cross-sectional view showing another example of the liquid crystal display element according to the present invention.

Detailed Description

The following describes in detail a method for manufacturing a liquid crystal display element according to the present invention, but the following description of the structural elements is an example of one embodiment of the present invention and is not limited to these.

(method of manufacturing liquid Crystal display element)

The method for manufacturing a liquid crystal display element of the present invention includes the following step (a) and the following step (B).

Step (A): forming a radical generating film capable of generating radicals by irradiation with light on a substrate;

a step (B): a liquid crystal composition containing a liquid crystal and a radical polymerizable compound is brought into contact with the radical generating film, and while maintaining this state, the liquid crystal composition is irradiated with light having a peak at 240 to 400nm sufficient to cause the radical polymerizable compound to undergo a polymerization reaction.

The radical polymerizable compound in the step (B) is a compound having a function of vertically aligning the liquid crystal by polymerization;

further, the method for manufacturing a liquid crystal display element of the present invention includes at least one of the following requirements (Z1) and (Z2).

Requirement (Z1): the method further comprises a step (C) of irradiating the radical generating film obtained in the step (A) with light having a peak at 240-400 nm to inactivate the radical generating ability of the radical generating film between the steps (A) and (B).

The present invention, which includes the above-described steps (a) and (B), and further satisfies at least one of the requirements (Z1) and (Z2), can produce a liquid crystal display element in which at least 2 regions out of an in-plane alignment region, an out-of-plane alignment region, and an oblique alignment region are patterned.

< Membrane Generation of free radicals >

In the present invention, a radical generating film is formed on a substrate.

Here, the radical generating film refers to a film that generates radicals.

The radical generating film is formed, for example, from a radical generating film forming composition.

< composition for forming free radical-generating film >

The composition for forming a free-radical-generating film contains a polymer and a group capable of generating a free radical. In this case, the radical generating film-forming composition may be a composition containing a polymer to which a radical generating group is bonded, or a composition containing a compound having a radical generating group and a polymer serving as a base resin.

By applying such a radical generating film-forming composition to a substrate and curing the applied film, a radical generating film in which a radical generating group is immobilized in the film can be obtained. The group capable of generating a radical is preferably an organic group which initiates radical polymerization.

When the radical generating film is composed of a polymer containing an organic group which initiates radical polymerization, examples of the polymer containing an organic group which induces radical polymerization include a polymer having a structural unit represented by the following formula (1) in the main chain.

[ chemical formula 12]

In formula (1), A represents an organic group that initiates radical polymerization.

In the case of using a polymer containing an organic group that initiates radical polymerization, in order to obtain a polymer having a group capable of generating a radical, it is preferable to produce the polymer as a monomer component, a monomer having a photoreactive side chain containing at least one selected from the group consisting of a methacryloyl group, an acryloyl group, a vinyl group, an allyl group, a coumarinyl group, a styryl group, and a cinnamoyl group, or a monomer having a site that generates a radical on the side chain that is decomposed by light irradiation. On the other hand, there is a risk that an unstable compound is finally formed in consideration of a problem that a monomer generating a radical spontaneously undergoes polymerization by itself.

Therefore, in terms of ease of synthesis, a polymer derived from a diamine having a radical generation site is preferable, and polyimide precursors such as polyamic acid and polyamic acid ester, polyimide, polyurea, and polyamide are more preferable.

Examples of the organic group that initiates radical polymerization include groups represented by the following formula (3).

[ chemical formula 13]

R ⁷ Represents a single bond, or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with a fluorine atom, or any of-CH's of the alkylene groups ₂ -or-CF ₂ -1 or more of which are each independently optionally substituted by a group selected from-CH ═ CH-, a 2-valent carbocyclic ring and a 2-valent heterocyclic ring, and further optionally substituted by any of the groups enumerated below, i.e., -O-, -COO-, -OCO-, -NHCO-, -CONH-or-NH-, under the condition that these groups are not adjacent to each other,

[ chemical formula 14]

Formula [ X-1]～[X-18]Wherein represents a group represented by ⁷ Bonding site of (2), S ₁ And S ₂ Each independently represents-O-, -NR-, or-S-, wherein R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon atomAlkoxy of number 1 to 10, R ₁ And R ₂ Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms,

[ chemical formula 15]

Formula [ W ]]、[Y]、[Z]Wherein represents a group represented by ⁷ Bonding site of (2), S ³ Represents a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-、-N(CH ₃ )-、-CON(CH ₃ ) -, or-N (CH) ₃ ) CO-, Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene optionally having an organic group and/or a halogen atom as a substituent, and R ⁹ And R ¹⁰ Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group or a phenethyl group, and in the case of an alkyl group or an alkoxy group, R represents ⁹ And R ¹⁰ Optionally forming a ring,

q represents any one of the following structures,

[ chemical formula 16]

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 organic group represented by the formula selected from the group consisting of [ W ], [ Y ] and [ Z ] is preferably the following organic group. In particular, (b) and (c) are more preferable from the viewpoint of reliability of the obtained liquid crystal display element.

[ chemical formula 17]

Preferred examples of the polymer having an organic group which initiates radical polymerization include diamines having an organic group which initiates radical polymerization.

The diamine having a radical generating site is specifically a diamine having a side chain capable of generating a radical and polymerizing, and examples thereof include diamines represented by the following formula (2). The present invention is not limited to this.

[ chemical formula 18]

In the formula (2), A ¹ And A ² Each represents a hydrogen atom or a group represented by the above formula (3) wherein A ¹ And A ² At least one of them represents a group represented by the above formula (3),

e represents a single bond, -O-, -C (CH) ₃ ) ₂ -、-NH-、-CO-、-NHCO-、-COO-、-(CH ₂ ) _m -、-SO ₂ Or a 2-valent organic group composed of any combination thereof, and m represents an integer of 1 to 8.

Examples of "any combination of these" include: -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-、-COO-(CH ₂ ) _m -OCO-, etc., but not limited thereto.

2 amino groups (-NH) in the case where p is 0 in the above formula (2) ₂ ) The bonding position of (2) is not limited. Specifically, there may be mentioned the 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position, 3,5 position on the benzene ring relative to the bonding group of the side chain. Wherein the polymer is synthesized fromFrom the viewpoint of reactivity in the case of amic acid, the position is preferably 2,4, 2,5, or 3, 5. In view of the easiness of synthesizing the diamine, the position of 2,4 or the position of 3,5 is more preferable.

Specific examples of the diamine having a photoreactive group containing at least one selected from the group consisting of a methacryloyl group, an acryloyl group, a vinyl group, an allyl group, a coumarinyl group, a styryl group, and a cinnamoyl group include the following compounds, but are not limited thereto.

[ chemical formula 19]

[ chemical formula 20]

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

The organic group represented by the formula selected from the group consisting of [ W ], [ Y ] and [ Z ] is most preferably a structure represented by the following formula in view of ease of synthesis, high or low versatility, characteristics, and the like, but is not limited thereto.

[ chemical formula 21]

(wherein n is an integer of 2 to 8, E is a single bond, -O-, -C (CH) ₃ ) ₂ -、-NH-、-CO-、-NHCO-、-COO-、-(CH ₂ ) _m -、-SO ₂ -、-O-(CH ₂ ) _m -O-、-O-C(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-, m is an integer of 1 to 8).

[ chemical formula 22]

(wherein n is an integer of 2 to 8).

The diamine may be used alone or in combination of two or more depending on the characteristics such as liquid crystal alignment property when a radical generating film is formed, sensitivity in polymerization reaction, voltage holding property, and accumulated charge.

The diamine having a site where such radical polymerization occurs is preferably used in an amount of 5 to 50 mol%, more preferably 10 to 40 mol%, and particularly preferably 15 to 30 mol%, based on the whole diamine component used for the synthesis of the polymer contained in the radical generating film-forming composition.

In addition, in the case where the polymer used in the radical generating film of the present invention is obtained from a diamine, a diamine other than the above-mentioned diamine having a radical generating site may be used in combination as the diamine component. Specifically, there may be mentioned: p-phenylenediamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2, 5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2, 4-dimethyl-m-phenylenediamine, 2, 5-diaminotoluene, 2, 6-diaminotoluene, 2, 5-diaminophenol, 2, 4-diaminophenol, 3, 5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4, 6-diaminoresorcinol, 4 '-diaminobiphenyl, 3' -dimethyl-4, 4 '-diaminobiphenyl, 3' -dimethoxy-4, 4 '-diaminobiphenyl, 3' -dihydroxy-4, 4 '-diaminobiphenyl, 2, 4-dimethyl-m-phenylenediamine, 2, 4-diaminotoluene, 2, 5-diaminophenol, 3, 5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4, 6-diaminoresorcinol, 4' -diaminobiphenyl, 3 '-dimethoxy-4, 4' -diaminobiphenyl, 3 '-dihydroxy-4, 4' -diaminobiphenyl, 2, 5-dimethyl-p-phenylenediamine, 2, 4-m-phenylenediamine, 2, 4-diaminobiphenyl, 4-m-xylene, 2, 4-diaminobiphenyl, 4, and a, 3,3' -dicarboxy-4, 4' -diaminobiphenyl, 3' -difluoro-4, 4' -diaminobiphenyl, 3' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, 3' -diaminobiphenyl, 2' -diaminobiphenyl, 2,3' -diaminobiphenyl, 4' -diaminodiphenylmethane, 3' -diaminodiphenylmethane, 3,4' -diaminodiphenylmethane, 2' -diaminodiphenylmethane, 2,3' -diaminodiphenylmethane, 4' -diaminodiphenyl ether, 3' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 2,2 '-diaminodiphenyl ether, 2,3' -diaminodiphenyl ether, 4 '-sulfonyldiphenylamine, 3' -sulfonyldiphenylamine, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4 '-thiodiphenylamine, 3' -thiodiphenylamine, 4 '-diaminodiphenylamine, 3' -diaminodiphenylamine, 3,4 '-diaminodiphenylamine, 2' -diaminodiphenylamine, 2,3 '-diaminodiphenylamine, N-methyl (4,4' -diaminodiphenyl) amine, N-methyl (3,3 '-diaminodiphenyl) amine, N-methyl (3-methyl) amine, N-methyl (4-amino) amine, 4' -diaminodiphenyl) amine, 3 '-diaminodiphenyl) amine, N, 3' -diaminodiphenyl, N, S, n-methyl (3,4' -diaminodiphenyl) amine, N-methyl (2,2' -diaminodiphenyl) amine, N-methyl (2,3' -diaminodiphenyl) amine, 4' -diaminobenzophenone, 3' -diaminobenzophenone, 3,4' -diaminobenzophenone, 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-aminophenyl) ethane, 1, 2-bis (3-aminophenyl) ethane, N-methyl (2,2' -diaminodiphenyl) amine, N-methyl (2,3' -diaminodiphenyl) amine, 4' -diaminodiphenyl ketone, 3' -diaminodiphenyl ketone, 3,4' -diaminodiphenyl ketone, 2,3' -diaminonaphthalene, 2' -diaminonaphthalene, 2-diaminonaphthalene, 1, 2-bis (4-aminophenyl) ethane, 1, 2-bis (4-amino) ethane, 2-bis (4-amino) ethane, 1, 2-bis (3-amino) ethane, 2-bis (4-amino) ethane, 2-bis (4-phenyl) ethane, 2-bis (3-bis (4-amino) ethane, 2-bis (2-amino) ethane, 2-bis (2-amino) ethane, 2-bis (2-amino) ethane, 2-bis (4-bis (2-amino) ethane, 2-bis (2-amino) ethane, 2-amino) naphthalene), 2-bis (2-amino) ethane, 2-bis (2-amino) naphthalene), 2-bis (4-bis (2-bis) ethane, 2-bis (4-bis (2-bis (4-bis) ethane, 2-bis (2-, 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'- [1, 4-phenylenebis (methylene) ] diphenylamine, 4' - [1, 3-phenylenebis (methylene) ] diphenylamine, 3,4'- [1, 4-phenylenebis (methylene) ] diphenylamine, 3,4' - [1, 3-phenylenebis (methylene) ] diphenylamine, 3'- [1, 4-phenylenebis (methylene) ] diphenylamine, 3' - [1, 3-phenylenebis (methylene) ] diphenylamine, 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-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N '- (1, 4-phenylene) bis (4-aminobenzamide), N' - (1, 3-phenylene) bis (4-aminobenzamide), N '- (1, 4-phenylene) bis (3-aminobenzamide), N' - (1, 4-aminobenzamide), N '- (1, 3-phenylene) bis (3-aminobenzamide), N' -bis (4-aminophenyl) terephthalamide, N, N ' -bis (3-aminophenyl) terephthalamide, N ' -bis (4-aminophenyl) isophthalamide, N ' -bis (3-aminophenyl) isophthalamide, 9, 10-bis (4-aminophenyl) anthracene, 4' -bis (4-aminophenoxy) diphenylsulfone, 2' -bis [4- (4-aminophenoxy) phenyl ] propane, 2' -bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2' -bis (4-aminophenyl) hexafluoropropane, 2' -bis (3-amino-4-methylphenyl) hexafluoropropane, N ' -bis (4-aminophenyl) isophthalamide, N ' -bis (3-aminophenyl) isophthalamide, 9, 10-bis (4-aminophenyl) anthracene, 4' -bis (4-aminophenoxy) diphenylsulfone, 2' -bis [4- (4-aminophenoxy) phenyl ] propane, 2' -bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2,2 '-bis (4-aminophenyl) propane, 2' -bis (3-amino-4-methylphenyl) propane, trans-1, 4-bis (4-aminophenyl) cyclohexane, 3, 5-diaminobenzoic acid, 2, 5-diaminobenzoic 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, 2 '-bis (3-aminophenyl) propane, 2' -bis (3-aminophenyl) propane, trans-1, 4-aminophenyl) cyclohexane, 3, 5-diaminobenzoic acid, 2, 5-diaminobenzoic acid, bis (4-aminophenoxy) methane, 1, 2-bis (4-aminophenoxy) ethane, 1, 3-bis (4-aminophenoxy) pentane, 1, 3-bis (4-aminophenoxy) pentane, 1, 5-pentane, 1, 4-pentane, 3-bis (4-aminophenoxy) pentane, 1, 3-pentane, 3-bis (4-amino-4-pentane, 1, 3-4-n-pentane, 3-n-2, 3-hexane, 1, 3-hexane, 1, 3-hexane, 2, 3-hexane, or toluene, 3-hexane, or one, or one, or more, 1, 5-bis (3-aminophenoxy) pentane, 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, Aromatic diamines such as 1, 12-bis (4-aminophenoxy) dodecane and 1, 12-bis (3-aminophenoxy) dodecane; alicyclic diamines such as bis (4-aminocyclohexyl) methane and bis (4-amino-3-methylcyclohexyl) methane; aliphatic diamines such as 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9-diaminononane, 1, 10-diaminodecane, 1, 11-diaminoundecane, and 1, 12-diaminododecane; diamines having a urea structure such as 1, 3-bis [2- (p-aminophenyl) ethyl ] urea, 1, 3-bis [2- (p-aminophenyl) ethyl ] -1-tert-butoxycarbonylurea, and the like; diamines having a nitrogen-containing unsaturated heterocyclic structure, such as N-p-aminophenyl-4-p-aminophenyl (tert-butoxycarbonyl) aminomethylpiperidine; diamines having an N-Boc group (Boc represents a tert-butoxycarbonyl group) such as N-tert-butoxycarbonyl-N- (2- (4-aminophenyl) ethyl) -N- (4-aminobenzyl) amine, and the like.

The other diamines may be used alone or in combination of two or more thereof depending on the liquid crystal alignment properties when the film is formed into a radical generating film, the sensitivity in the polymerization reaction, the voltage holding property, the accumulated charge, and the like.

In the synthesis of the polymer being a polyamic acid, the tetracarboxylic dianhydride to be reacted with the diamine component is not particularly limited. Specifically, there may be mentioned: pyromellitic acid, 2,3,6, 7-naphthalene tetracarboxylic acid, 1,2,5, 6-naphthalene tetracarboxylic acid, 1,4,5, 8-naphthalene tetracarboxylic acid, 2,3,6, 7-anthracene tetracarboxylic acid, 1,2,5, 6-anthracene tetracarboxylic acid, 3,3',4, 4-biphenyl tetracarboxylic 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) methane, 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, 1, 4-dicarboxyphenyl) dimethyl silane, 2,3, 7-naphthalene tetracarboxylic acid, 1,2,5, 6-anthracene tetracarboxylic acid, 3,4' -biphenyl tetracarboxylic acid, 2,4, 4 '-biphenyl tetracarboxylic acid, 2, 4' -biphenyl tetracarboxylic acid, 3,3, 4-bis (3, 4-dicarboxyphenyl) methane, 3, 4-bis (3, 4-dicarboxyphenyl) propane, 4-bis (3, 4-dicarboxyphenyl) methane, 4-bis (3, 4-dicarboxyphenyl) propane, 3,3, 4-bis (3, 4-dicarboxyphenyl) methane, 3, 4-bis (3, 4-dicarboxyphenyl) propane, 3,3, 4-bis (3, 4-dicarboxyphenyl) sulfone, 4-bis (3,3, 4-bis (3, 6, bis (3, 4-dicarboxyphenyl) diphenylsilane, 2,3,4, 5-pyridinetetracarboxylic acid, 2, 6-bis (3, 4-dicarboxyphenyl) pyridine, 3',4,4' -diphenylsulfonetetracarboxylic acid, 3,4,9, 10-perylenetetracarboxylic acid, 1, 3-diphenyl-1, 2,3, 4-cyclobutanetetracarboxylic acid, oxydiphthalic tetracarboxylic acid, 1,2,3, 4-cyclobutanetetracarboxylic acid, 1,2,3, 4-cyclopentanetetracarboxylic acid, 1,2,4, 5-cyclohexanetetracarboxylic 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, 2,3,4, 5-tetrahydrofuranetetracarboxylic acid, 3, 4-dicarboxy-1-cyclohexylsuccinic acid, 2,3, 5-tricarboxycyclopentylacetic acid, 3, 4-dicarboxy-1, 2,3, 4-tetrahydro-1-naphthalenecarboxylic acid, bicyclo [3.3.0] octane-2, 4,6, 8-tetracarboxylic acid, bicyclo [4.3.0] nonane-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, dianhydrides of tetracarboxylic acids such as 4-butanetetracarboxylic acid, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic acid, 5- (2, 5-dioxotetrahydrofuran-yl) -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, and 1,2,4, 5-cyclohexanetetracarboxylic acid.

Of course, the tetracarboxylic dianhydride may be used alone or in combination of two or more depending on the characteristics such as liquid crystal alignment property, sensitivity in polymerization reaction, voltage holding property, and accumulated charge when a radical generating film is formed.

In the synthesis of the polymer as a polyamic acid ester, the structure of the tetracarboxylic acid dialkyl ester to be reacted with the diamine component is not particularly limited, and specific examples thereof are given below.

Specific examples of the aliphatic tetracarboxylic acid diester include: dialkyl 1,2,3, 4-cyclobutanetetracarboxylic acid, dialkyl 1, 2-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic acid, dialkyl 1, 3-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic acid, dialkyl 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutanetetracarboxylic acid, dialkyl 1,2,3, 4-cyclopentanetetracarboxylic acid, dialkyl 2,3,4, 5-tetrahydrofurantetracarboxylic acid, dialkyl 1,2,4, 5-cyclohexanetetracarboxylic acid, dialkyl 3, 4-dicarboxy-1-cyclohexylsuccinate, dialkyl 3, 4-dicarboxy-1, 2,3, 4-tetrahydro-1-naphthalenetetracarboxylic acid, 1, dialkyl 2,3, 4-butanetetracarboxylic acid, dialkyl bicyclo [3.3.0] octane-2, 4,6, 8-tetracarboxylic acid, dialkyl 3,3', dialkyl 4,4' -bicyclohexane-tetracarboxylic acid, dialkyl 2,3, 5-tricarboxycyclopentylacetate, cis-3, 7-dibutylcyclooctan-1, 5-diene-1, 2,5, 6-tetracarboxylic acid, dialkyl tricyclo [4.2.1.0<2,5> ] nonane-3, 4,7, 8-tetracarboxylic acid 3,4:7, 8-dialkyl ester, hexacyclic [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-dialkyl ester, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1, dialkyl 2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylate, and the like.

Examples of the aromatic tetracarboxylic acid dialkyl ester include: dialkyl pyromellitate,

dialkyl

3,3',4,4' -biphenyltetracarboxylic acid,

dialkyl

2,2',3,3' -biphenyltetracarboxylic acid,

dialkyl

2,3,3', 4-biphenyltetracarboxylic acid,

dialkyl

3,3',4,4' -benzophenonetetracarboxylic acid,

dialkyl

2,3,3',4' -benzophenonetetracarboxylic acid, dialkyl bis (3, 4-dicarboxyphenyl) ether, dialkyl bis (3, 4-dicarboxyphenyl) sulfone,

dialkyl

1,2,5, 6-naphthalenetetracarboxylic acid,

dialkyl

2,3,6, 7-naphthalenetetracarboxylic acid, and the like.

In the synthesis of the polymer in the case of polyurea, the diisocyanate to be reacted with the diamine component is not particularly limited, and can be used in accordance with availability and the like. Specific structures of the diisocyanates are shown below.

[ chemical formula 23]

In the formula R ₂ And R ₃ Represents an aliphatic hydrocarbon having 1 to 10 carbon atoms.

The aliphatic diisocyanates represented by K-1 to K-5 have poor reactivity but have the advantage of improving solvent solubility, and the aromatic diisocyanates represented by K-6 to K-7 have the effect of improving heat resistance while being rich in reactivity but have the disadvantage of reducing solvent solubility. In terms of versatility and characteristics, K-1, K-7, K-8, K-9 and K-10 are particularly preferable, K-12 is preferable from the viewpoint of electrical characteristics, and K-13 is preferable from the viewpoint of liquid crystal alignment properties. The diisocyanate may be used in combination with one or more kinds thereof, and is preferably used in various applications depending on the desired properties.

In addition, a part of diisocyanate may be replaced with the tetracarboxylic dianhydride described above, and the diisocyanate may be used in the form of a copolymer of polyamic acid and polyurea, or may be used in the form of a copolymer of polyimide and polyurea by chemical imidization.

The structure of the dicarboxylic acid to be reacted in the synthesis when the polymer is a polyamide is not particularly limited, and specific examples thereof are as follows. Specific examples of the aliphatic dicarboxylic acid include dicarboxylic acids such as malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, hexadiene diacid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2-dimethylglutaric acid, 3-diethylsuccinic acid, azelaic acid, sebacic acid, and suberic acid.

Examples of the alicyclic dicarboxylic acid include: 1, 1-Cyclopropanedicarboxylic acid, 1, 2-cyclopropanedicarboxylic acid, 1-cyclobutanedicarboxylic acid, 1, 2-cyclobutanedicarboxylic acid, 1, 3-cyclobutanedicarboxylic acid, 3, 4-diphenyl-1, 2-cyclobutanedicarboxylic acid, 2, 4-diphenyl-1, 3-cyclobutanedicarboxylic acid, 1-cyclobutane-1, 2-dicarboxylic acid, 1-cyclobutane-3, 4-dicarboxylic acid, 1-cyclopentanedicarboxylic acid, 1, 2-cyclopentanedicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid, 1-cyclohexanedicarboxylic acid, 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1,4- (2-norbornene) dicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 5-norbornene-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] octane dicarboxylic acid, 1, 3-adamantanedicarboxylic acid, 4, 8-dioxo-1, 3-adamantanedicarboxylic acid, 2, 6-spiro [3.3] heptane dicarboxylic acid, 1, 3-adamantane diacetic acid, camphoric acid, and the like.

Examples of the aromatic dicarboxylic acid include: phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2, 5-dimethylterephthalic acid, tetramethylterephthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 1, 4-anthracenedicarboxylic acid, 1, 4-anthraquinonedicarboxylic acid, 2, 5-biphenyldicarboxylic acid, 4' -biphenyldicarboxylic acid, 1, 5-biphenylenedicarboxylic acid, 4' -terphthalic acid, 4' -diphenylmethanedicarboxylic acid, 4' -diphenylethanedicarboxylic acid, 4' -diphenylpropanedicarboxylic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2, 5-dimethylterephthalic acid, 2, 4-naphthalenedicarboxylic acid, 1, 4' -naphthalenedicarboxylic acid, 4' -naphthalenedicarboxylic acid, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 4-naphthalenedicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 4-naphthalenedicarboxylic acid, 4, and mixtures thereof, 4,4' -diphenylhexafluoropropanedicarboxylic acid, 4' -diphenyletherdicarboxylic acid, 4' -bibenzyldicarboxylic acid, 4' -diphenylethenedicarboxylic acid, 4' -diphenylacetylenedicarboxylic acid, 4' -carbonyldibenzoic acid, 4' -sulfonyldibenzoic acid, 4' -dithiodibenzoic acid, p-phenylenediacetic acid, 3' -p-phenylenedipropionic acid, 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3' - [4,4' - (methylenedi-p-phenylene) ] dipropionic acid, 4' - [4,4' - (oxydiphenylene) ] dibutanoic acid, (isopropylidenediphenylenedioxy) dibutanoic acid, Dicarboxylic acids such as 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, 1,2, 5-thiadiazole-3, 4-dicarboxylic acid, 1,2, 5-oxadiazole-3, 4-dicarboxylic acid, 2, 3-pyridinedicarboxylic acid, 2, 4-pyridinedicarboxylic acid, 2, 5-pyridinedicarboxylic acid, 2, 6-pyridinedicarboxylic acid, 3, 4-pyridinedicarboxylic acid, 3, 5-pyridinedicarboxylic acid, and the like.

The various dicarboxylic acids mentioned above may be in the structure of acid dihalides or anhydrides. These dicarboxylic acids are particularly preferably dicarboxylic acids capable of giving polyamides having a linear structure, from the viewpoint of maintaining the orientation of liquid crystal molecules. Among them, terephthalic acid, isophthalic acid, 1, 4-cyclohexanedicarboxylic acid, 4 '-diphenyldicarboxylic acid, 4' -diphenylmethanedicarboxylic acid, 4 '-diphenylethanedicarboxylic acid, 4' -diphenylpropanedicarboxylic acid, 4 '-diphenylhexafluoropropanedicarboxylic acid, 2-bis (phenyl) propanedicarboxylic acid, 4' -terphthalic acid, 2, 6-naphthalenedicarboxylic acid, 2, 5-pyridinedicarboxylic acid, acid dihalides thereof, and the like are preferably used. These compounds may sometimes be present as isomers, and may be mixtures containing these. In addition, two or more compounds may be used in combination. The dicarboxylic acids used in the present invention are not limited to the above-mentioned exemplary compounds.

In the case of obtaining a polyamic acid, polyamic acid ester, polyurea, and polyamide by the reaction of a diamine (also referred to as "diamine component") as a raw material and a component selected from a tetracarboxylic dianhydride (also referred to as "tetracarboxylic dianhydride component"), a tetracarboxylic diester, a diisocyanate, and a dicarboxylic acid as a raw material, a known synthesis means can be used. In general, the method is a method of reacting a diamine component and one or more components selected from a tetracarboxylic dianhydride component, a tetracarboxylic diester, a diisocyanate, and a dicarboxylic acid in an organic solvent.

The reaction of the diamine component with the tetracarboxylic dianhydride component is advantageous in the following respects: the method is easy to carry out in an organic solvent, and does not produce byproducts.

The organic solvent used in the above reaction is not particularly limited as long as it dissolves the polymer produced. Further, even if the organic solvent is an organic solvent that does not dissolve the polymer, the organic solvent may be used in combination with the above-mentioned solvent within a range that the polymer to be produced does not precipitate. Further, the organic solvent is preferably dehydrated and dried because water in the organic solvent may inhibit the polymerization reaction and hydrolyze the polymer formed.

Examples of the organic solvent include: n, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylphosphoric triamide, gamma-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentyl ketone, methylnonyl ketone, methylethylketone, methylisoamylketone, methylisopropyl ketone, methylcellosolve, ethylcellosolve, methylcellosolve acetate, butylcellosolve acetate, and the like, Ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-t-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, methyl ether, propylene glycol, ethylene glycol mono-isopropyl ether, propylene glycol mono-methyl ether, propylene glycol mono-butyl ether, propylene glycol mono-ethyl glycol mono-butyl ether, propylene glycol mono-ethyl ether, propylene glycol mono-butyl ether, propylene glycol mono-ethyl ether, propylene glycol mono-butyl ether, butylene ether, propylene glycol mono-butyl ether, butylene ether, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, and the like. These organic solvents may be used alone or in combination.

When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, the following method may be mentioned: a method of adding the tetracarboxylic dianhydride component directly or by dispersing or dissolving the diamine component in an organic solvent by stirring a solution obtained by dispersing or dissolving the diamine component in the organic solvent; a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride component in an organic solvent; a method of alternately adding the tetracarboxylic dianhydride component and the diamine component, and any of these methods can be used. In the case where the diamine component or the tetracarboxylic dianhydride component is composed of a plurality of compounds, these components may be reacted in a state of being mixed in advance, or they may be reacted in sequence, or low molecular weight materials obtained by the respective reactions may be further subjected to a mixing reaction to produce a high molecular weight material.

The temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted can be selected from any temperature, for example, from-20 to 100 ℃, preferably from-5 to 80 ℃. The reaction can be carried out at any concentration, and 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, based on the reaction solution.

The ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component in the polymerization reaction can be arbitrarily selected depending on the molecular weight of the polyamic acid to be obtained. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced. The preferable range is 0.8 to 1.2.

The method for synthesizing the polymer used in the present invention is not limited to the above method, and when synthesizing polyamic acid, the reaction is carried out by a known method using a tetracarboxylic acid derivative such as a tetracarboxylic acid or a tetracarboxylic acid dihalide having a corresponding structure in place of the tetracarboxylic acid dianhydride, as in the case of the general method for synthesizing polyamic acid. In the case of synthesizing polyurea, a diamine may be reacted with a diisocyanate. In the production of the polyamic acid ester or the polyamide, the diamine and a component selected from the group consisting of a tetracarboxylic acid diester and a dicarboxylic acid may be derivatized to an acid halide in the presence of a known condensing agent or by a known method, and then reacted with the diamine.

Examples of the method for imidizing the polyamic acid to obtain a polyimide include thermal imidization in which a solution of the polyamic acid is directly heated, and imidization in which a catalyst is added to a solution of the polyamic acid. In addition, the imidization ratio of the polyamic acid to the polyimide is preferably 30% or more, and more preferably 30 to 99% from the viewpoint of being able to improve the voltage holding ratio. On the other hand, from the viewpoint of suppressing whitening characteristics, that is, precipitation of a polymer in a varnish, it is preferably 70% or less. In view of both properties, it is more preferably 40 to 80%.

The temperature at which the polyamic acid is thermally imidized in a solution is usually 100 to 400 ℃, preferably 120 to 250 ℃, and is preferably carried out while removing water generated by the imidization reaction from the system.

The catalytic imidization of the polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyamic acid, and stirring the mixture at a temperature of usually-20 to 250 ℃ and preferably 0 to 180 ℃. The amount of the basic catalyst is usually 0.5 to 30 times, preferably 2 to 20 times, the amount of the acid anhydride is usually 1 to 50 times, preferably 3 to 30 times, the amount of the acid amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine, and among these, pyridine is preferable because it has a suitable basicity for allowing the reaction to proceed. The acid anhydride includes acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like, and among these, acetic anhydride is preferable because purification after completion of the reaction is easy. The imidization rate based on the catalyst imidization can be controlled by adjusting the amount of the catalyst and the reaction temperature, the reaction time, and the like.

When the polymer to be produced is recovered from the reaction solution of the polymer, the reaction solution may be precipitated by adding a poor solvent. Examples of the poor solvent used for the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated by being put into the poor solvent can be recovered by filtration, and then dried at normal temperature or under reduced pressure or by heating. Further, if the operation of re-dissolving the polymer obtained by precipitation and recovery in an organic solvent and re-precipitating and recovering is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent in this case include alcohols, ketones, hydrocarbons and the like, and if 3 or more kinds of poor solvents selected from them are used, purification efficiency is further improved, and therefore, it is preferable.

In addition, in the case where the above-mentioned radical generating film is composed of a polymer containing an organic group which initiates radical polymerization, the radical generating film-forming composition used in the present invention may contain other polymers than the polymer containing an organic group which initiates radical polymerization. In this case, the content of the other polymer in the total polymer components is preferably 5 to 95% by mass, and more preferably 30 to 70% by mass.

The radical generating film forming composition preferably has a molecular weight of the polymer of 5,000 to 1,000,000, more preferably 10,000 to 150,000, in terms of a weight average molecular weight measured by GPC (Gel Permeation Chromatography) method, in consideration of strength of the radical generating film obtained by coating the radical generating film, workability at the time of forming the coating film, uniformity of the coating film, and the like.

The polymer used in the present invention for obtaining the radical generating film by applying a composition of a compound having a radical generating group and a polymer and curing the composition to form a film to immobilize the composition in the film can be at least 1 polymer selected from the group consisting of polyimide precursors obtained by the above-mentioned production methods and polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, and the like, which is obtained by using a diamine having a site generating radical polymerization as a diamine component in an amount of 0 mol% based on the whole diamine component used for the synthesis of the polymer contained in the radical generating film forming composition. Examples of the compound having a radical-generating group to be added at this time include the following compounds.

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

Further, even when the radical generating film is composed of a polymer containing an organic group which initiates radical polymerization, a compound having the radical generating group may be contained for the purpose of promoting radical polymerization when light irradiation is performed.

The radical generating film-forming composition may contain an organic solvent which dissolves or disperses the polymer component and other components than the radical generator used as necessary. Such an organic solvent is not particularly limited, and examples thereof include the organic solvents exemplified in the synthesis of the polyamic acid. Among them, from the viewpoint of solubility, N-methyl-2-pyrrolidone, γ -butyrolactone, N-ethyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropane amide, and the like are preferable. Particularly, N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is preferable, and a mixed solvent of two or more kinds may be used.

Further, it is preferable to use a solvent for improving the uniformity or smoothness of the coating film in combination with an organic solvent having high solubility of the components contained in the radical generating film forming composition.

Examples of the solvent for improving the uniformity or smoothness of the coating film include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol acetate, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol t-butyl ether, dipropylene glycol monomethyl ether, 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, ethylene glycol monomethyl ether, ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol mono-butyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-butyl ether, propylene glycol mono-ethyl ether, propylene glycol mono-butyl ether, propylene glycol mono-ethyl ether, propylene glycol, Dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, isopropyl ether, isobutyl ether, diisobutyl ether, isobutyl ether, butyl acetate, butyl butyrate, butyl ether, butyl acetate, ethyl 3-ethoxypropionate, methylethyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl acetate, ethyl 3-2-ethyl acetate, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, 2-ethyl-1-hexanol, and the like. These solvents may be mixed in plural. When these solvents are used, the amount of the solvent 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 liquid crystal aligning agent.

The radical generating film-forming composition may contain other components than those described above. Examples thereof include a compound that improves the film thickness uniformity and surface smoothness when the radical generating film forming composition is applied, a compound that improves the adhesion between the radical generating film forming composition and the substrate, and a compound that further improves the film strength of the radical generating film forming composition.

Examples of the compound for improving the uniformity of the film thickness or the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. More specifically, the examples include Eftop EF301, EF303, EF352 (manufactured by Mitsubishi Material electronics), MEGAFAC F171, F173, R-30 (manufactured by DIC), FLUORAD FC430, FC431 (manufactured by 3M), Asahiguard AG710, SURLON S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC). When these surfactants are used, the proportion thereof is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the total amount of the polymers contained in the radical generating film forming composition.

Specific examples of the compound for improving the adhesion between the radical generating film forming composition and the substrate include a functional silane-containing compound, an epoxy-containing compound, and the like. Examples thereof include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1, 4, 7-triazacyclodecane, 10-triethoxysilyl-1, 4, 7-triazacyclodecane, 9-trimethoxysilyl-3, 6-diazisononyl acetate, 9-triethoxysilyl-3, 6-diazisononyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxirane) -3-aminopropyltrimethoxysilane, N-bis (oxirane) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, dimethyl-ethyl-3-aminopropyltriethoxysilane, dimethyl-ethyl-3-aminopropyl-trimethoxysilane, dimethyl-3-amino-propyl-trimethoxysilane, dimethyl-3-ethyl-3-propyl-triethoxysilane, ethylene glycol diglycidyl ether, dimethyl-3-ethyl-propyl-trimethoxysilane, dimethyl-ethyl-3-ethyl-propyl-triethoxysilane, dimethyl-3-ethyl-3-propyl-trimethoxysilane, dimethyl-ethyl-3-ethyl-methyl-ethyl-3-propyl-trimethoxysilane, ethyl-, Polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, 6-tetraglycidyl-2, 4-hexanediol, N, N, N ', N ' -tetraglycidyl-m-phenylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, n-diglycidyl) aminopropyltrimethoxysilane, and the like.

In addition, in order to further improve the film strength of the radical generating film, a phenol compound such as 2,2' -bis (4-hydroxy-3, 5-dihydroxymethylphenyl) propane or tetrakis (methoxymethyl) bisphenol may be added. When the above compound is used, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the polymers contained in the radical generating film-forming composition.

In addition to the above, a dielectric or conductive substance for the purpose of changing electrical characteristics such as dielectric constant or conductivity of the radical generating film may be added to the radical generating film forming composition within a range not to impair the effects of the present invention.

< method for producing film for generating free radical >

The radical generating film according to the present invention is obtained by using the radical generating film forming composition. For example, a cured film obtained by applying the radical generating film-forming composition used in the present invention to a substrate and then drying/sintering the composition may be used as it is as a radical generating film. The cured film may be subjected to rubbing, irradiation with polarized light, light of a specific wavelength, or the like, treatment with an ion beam, or the like, or irradiation with UV as an alignment film for PSA to a liquid crystal display element filled with liquid crystal.

The irradiation light used in the production of the radical generating film is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include light having a peak at 240 to 400 nm. Preferably, the peak value is 250 to 365nm, and more preferably 250 to 360 nm. More specifically, for example, light having a peak at around 254nm or 313nm may be used.

Further, light having a specific wavelength or a wavelength equal to or higher than the specific wavelength may be cut by a known cut filter as necessary.

The substrate to which the radical generating film-forming composition is applied is not particularly limited as long as it is a substrate having high transparency, and is not limited to an electrode.

For example, a substrate having a transparent electrode for driving liquid crystal formed on a substrate can be given as a preferable embodiment.

Specific examples thereof include substrates having transparent electrodes formed on plastic plates such as glass plates, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose, and cellulose acetate butyrate.

Electrode patterns such as standard IPS comb-tooth electrodes and PSA fishbone electrodes, and projection patterns such as MVA can be used for the substrates that can be used in IPS liquid crystal display elements.

In addition, as a high-functional element such as a TFT-type element, an element in which an element such as a transistor is formed between an electrode for driving liquid crystal and a substrate is used.

In the case of a liquid crystal display element of a transmissive type, a substrate as described above is generally used, but in the case of a liquid crystal display element of a reflective type, an opaque substrate such as a silicon wafer may be used as long as it is a single-sided substrate. In this case, a material such as aluminum that reflects light can be used for the electrodes formed on the substrate.

Examples of the method of applying the radical generating film forming composition include spin coating, printing, ink jet, spray coating, roll coating, etc., but transfer printing is widely used industrially from the viewpoint of productivity, and is also preferably used in the present invention.

The step of drying after application of the radical generating film-forming composition is not necessarily essential, but when the time from application to firing is not uniform among the substrates or when the substrate is not fired immediately after application, the step of drying is preferably included. The drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transportation of the substrate or the like. For example, the following methods can be mentioned: drying the mixture for 0.5 to 30 minutes, preferably 1 to 5 minutes, on a heating plate at the temperature of 40 to 150 ℃, preferably 60 to 100 ℃.

The coating film formed by applying the radical generating film-forming composition by the above-described method, the so-called radical generating film, can be sintered to form a cured film. In this case, the sintering temperature may be generally any temperature of 100 to 350 ℃, and is preferably 140 to 300 ℃, more preferably 150 to 230 ℃, and still more preferably 160 to 220 ℃. The sintering time can be generally any time from 5 minutes to 240 minutes. Preferably 10 to 90 minutes, and more preferably 20 to 90 minutes. The heating can be generally performed by a known method, for example, a hot plate, a hot air circulation oven, an IR (infrared) oven, a belt oven, or the like.

The thickness of the radical generating film after curing can be selected as needed, but is preferably 5nm or more, more preferably 10nm or more, because reliability of the liquid crystal display element is easily obtained. Further, when the thickness of the cured film is preferably 300nm or less, more preferably 150nm or less, the power consumption of the liquid crystal display element does not become extremely large, and therefore, the thickness is preferable.

The first substrate having the radical generating film can be obtained as described above, but the radical generating film may be subjected to uniaxial orientation treatment. Examples of the method of performing the uniaxial orientation treatment include a photo-orientation method, an oblique vapor deposition method, rubbing, a uniaxial orientation treatment by a magnetic field, and the like.

In the case of performing the alignment treatment by performing the rubbing treatment in one direction, for example, the substrate is moved so that the rubbing cloth comes into contact with the film while rotating a rubbing roller around which the rubbing cloth is wound. In the case of the first substrate of the present invention on which the comb-teeth electrodes are formed, the direction is selected according to the electrical properties of the liquid crystal, but in the case of using a liquid crystal having positive dielectric anisotropy, the rubbing direction is preferably substantially the same direction as the direction in which the comb-teeth electrodes extend.

< liquid Crystal composition containing liquid Crystal and radically polymerizable Compound >

The liquid crystal display element of the present invention is produced using a liquid crystal composition containing a liquid crystal and a radical polymerizable compound.

The polymerizable compound used together with the liquid crystal is not particularly limited as long as it is a radical polymerizable compound, and is, for example, a compound having one or two or more polymerizable unsaturated bonds in one molecule. Preferably, the compound has one polymerizable unsaturated bond in one molecule (hereinafter, sometimes referred to as "compound having a monofunctional polymerizable group", or the like). The polymerizable unsaturated bond is preferably a radical polymerizable unsaturated bond, for example, a vinyl bond.

At least one of the radical polymerizable compounds is preferably a compound having one polymerizable unsaturated bond in one molecule, that is, a compound having a monofunctional radical polymerizable group, which has compatibility with a liquid crystal.

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

[ chemical formula 24]

(wherein R represents a site bonded to a portion other than the polymerizable unsaturated bond of the compound molecule; R ^b A linear alkyl group having 3 to 20 carbon atoms, E represents a single bond, -O-, -NR ^c -, -S-, a bonding group in an ester bond and an amide bond. R ^c Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, R ^b The alkyl group of (b) represents a linear, branched, or cyclic alkyl group).

In addition, in the liquid crystal composition containing a liquid crystal and a radical polymerizable compound, the following radical polymerizable compound is preferably contained: the Tg of the polymer obtained by polymerizing the above radically polymerizable compound is 100 ℃ or lower.

The compound having a monofunctional polymerizable reactive group is a compound having a radical polymerizable ability in the presence of an organic radical, and examples thereof include: methacrylate monomers such as t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, lauryl methacrylate, and n-octyl methacrylate; acrylate monomers such as t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, benzyl acrylate, lauryl acrylate, and n-octyl acrylate; styrene, vinyl monomers such as styrene derivatives (e.g., o-, m-, p-methoxystyrene, o-, m-, p-t-butoxystyrene, o-, m-, p-chloromethylstyrene, etc.), vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate, etc.), vinyl ketones (e.g., vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, etc.), N-vinyl compounds (e.g., N-vinylpyrrolidone, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, etc.), (meth) acrylic acid derivatives (e.g., acrylonitrile, methacrylonitrile, acrylamide, isopropylacrylamide, methacrylamide, etc.), vinyl halides (e.g., vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachlorobutadiene, fluoroethylene, etc.), but is not limited thereto. These various radically polymerizable monomers may be used alone or in combination of two or more. In addition, these are preferably compatible with liquid crystal.

The radical polymerizable compound is also preferably a compound represented by the following formula (a).

[ chemical formula 25]

(in the formula (A), R ^a And R ^b Each independently represents an alkyl group having 3 to 20 carbon atoms, E represents a single bond, -O-, -NR ^c A bonding group of- (O-X-O) -, - (S) -, - (Y-O) -, an ester bond, an amide bond, R ^c Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, R ^a Or R ^b The alkyl group of (b) represents a linear, branched, or cyclic alkyl group).

The radical polymerizable compound represented by formula (a) is preferably a compound in which E is an ester bond (-C (═ O) -O-or-O-C (═ O) -) in the formula, and more preferably a compound having the following structure, from the viewpoints of ease of synthesis, compatibility with a liquid crystal, and polymerization reactivity, and is not particularly limited.

[ chemical formula 26]

(in the formulae (A-1) and (A-2), R ^a And R ^b Each independently represents a linear alkyl group having 3 to 20 carbon atoms, R ^a And R ^b Each alkyl group of (a) independently represents a linear, branched, or cyclic alkyl group).

The radical polymerizable compound according to the present invention may have a vertically aligned group.

Examples of the vertical alignment group of the radical polymerizable compound used in the present invention include a group represented by the following formula [ S1 ].

[ chemical formula 27]

Formula [ S1]In, X ¹ And X ² Independently represent a single bond, - (CH) ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH) ₃ ) -, -NH-, -O-, -COO-, -OCO-, or- ((CH) ₂ ) _a1 -A ₁ ) _m1- (a 1 each independently represents an integer of 1 to 15, A ₁ Each independently represents an oxygen atom or-COO-, m ₁ Is 1 or 2. ). Among them, from the viewpoint of availability of raw materials and ease of synthesis, a single bond, - (CH) is preferred ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-or-COO-. More preferably a single bond, - (CH) ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O-or-COO-.

G ¹ And G ² Independently a 2-valent cyclic group selected from a 2-valent aromatic group having 6 to 12 carbon atoms or a 2-valent alicyclic group having 3 to 8 carbon atoms, any hydrogen atom in the cyclic group may be replaced by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms or a fluorine atom, m and n are independently integers of 0 to 3, the total is 0 to 4, R is 0 to 4 ¹ Is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, any hydrogen of these groups may be replaced by fluorine, wherein when the sum of m and n is 0, R is ¹ Groups having a steroid skeleton are also possible.

Examples of the 2-valent aromatic group having 6 to 12 carbon atoms include: phenylene, biphenylene, naphthylene, and the like. Examples of the alicyclic group having 2 valences and 3 to 8 carbon atoms include: cyclopropylene, cyclohexylene, and the like.

Preferable specific examples of the formula [ S1] include the following structures [ S1-x1] to [ S1-x7 ].

[ chemical formula 28]

Formula [ S1-x1]]～[S1-x7]In, R ¹ Is 1 c in carbon number20 alkyl group, X ^p Is represented by- (CH) ₂ ) _a - (a is an integer of 1 to 15), A ₁ Is oxygen atom or-COO- ("+" marked bonding site) and (CH) ₂ ) _a2 Bonding) A ₂ Is oxygen atom or-COO- (wherein, the bonding position marked with "-" is connected with (CH) ₂ ) _a2 Bonding) a ₁ 、a ₃ Each independently is an integer of 0 or 1, a ₂ Is an integer of 2 to 10, and Cy is 1, 4-cyclohexylene or 1, 4-phenylene.

Preferable examples of the group having a steroid skeleton include the following formula [ S3-x ].

[ chemical formula 29]

In the formula [ S3-x ], Col represents any one of the formulas [ Col1] to [ Col4], and G represents any one of the formulas [ G1] to [ G2 ]. Denotes the bonding site.

Examples of preferred embodiments of the radical polymerizable compound according to the present invention include a radical polymerizable compound having a vertical alignment group in which any of the radical polymerizable groups is bonded to the vertical alignment group [ S1 ].

These various radically polymerizable monomers may be used alone or in combination of two or more. In addition, these preferably have compatibility with liquid crystals.

The content of the radical polymerizable compound in the liquid crystal composition is preferably 3% by mass or more, more preferably 5% by mass or more, preferably 50% by mass or less, and more preferably 20% by mass or less, based on the total mass of the liquid crystal and the radical polymerizable compound.

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

< liquid crystal cell >

The liquid crystal display element according to the present invention can have, for example, the following cell structure.

After the radical generating film is formed on the substrate by the above method, the first substrate and the second substrate having the radical generating film are arranged so that the radical generating film on the first substrate faces the second substrate, and a liquid crystal composition containing a liquid crystal and a radical polymerizable compound is filled between the first substrate and the second substrate, thereby producing a liquid crystal cell.

The liquid crystal display element manufactured in the present invention can use the liquid crystal cell obtained in this way.

In a more detailed description of the method for producing the liquid crystal cell, the radical generating film on the first substrate is disposed so as to face the second substrate, the substrates are fixed with a sealant by sandwiching a spacer therebetween, and a liquid crystal composition containing a liquid crystal and a radical polymerizable compound is injected between the first and second substrates and sealed to obtain the liquid crystal cell.

The size of the spacer used in this case is usually 1 to 30 μm, preferably 2 to 10 μm.

The method for injecting the liquid crystal composition containing the liquid crystal and the radical polymerizable compound is not particularly limited, and examples thereof include: a vacuum method in which the inside of the liquid crystal cell is depressurized and then a mixture containing a liquid crystal and a polymerizable compound is injected, a dropping method in which a mixture containing a liquid crystal and a polymerizable compound is dropped and then sealed, and the like.

An alignment film for aligning the liquid crystal is preferably formed on the second substrate.

The alignment film may be a known liquid crystal alignment film, or may be any of the radical generating films according to the present invention, and may be appropriately selected according to the purpose.

The alignment film formed on the first substrate can be subjected to uniaxial alignment treatment.

As described later, for example, when the out-of-plane alignment region is formed on the liquid crystal display element, the radical generating film is preferably formed on the second substrate.

In addition, for example, when an in-plane alignment region or an oblique alignment region is formed on a liquid crystal display element, a liquid crystal alignment film for horizontal alignment subjected to uniaxial alignment treatment is preferably formed on the second substrate.

< formation of in-plane orientation, out-of-plane orientation, and obliquely oriented regions >

A liquid crystal cell obtained by using substrates on which a radical generating film is formed and disposing a mixture (liquid crystal composition) containing a liquid crystal and a radical polymerizable compound between the substrates is irradiated with light sufficient to cause a polymerization reaction of the radical polymerizable compound.

In this way, the present invention forms a radical generating film having an anchoring force on a substrate, and irradiates the radical generating film with light in a region where the anchoring force is to be maintained in a state where a liquid crystal containing a specific polymerizable compound is brought into contact with the radical generating film. The polymerizable compound is polymerized to vertically align the liquid crystal, and as a result, an out-of-plane alignment (vertical alignment) region is formed in the region irradiated with light.

The light to be irradiated here may have a peak at 240 to 400 nm. The light is preferably irradiated with light having a wavelength at which the absorbance of a portion corresponding to the photoradical generating site becomes high, more preferably light having a peak at 250 to 365nm, and still more preferably light having a peak at 250 to 360 nm.

More specifically, for example, light having a peak around 313nm can be used. If necessary, light having a specific wavelength or a wavelength equal to or higher than the specific wavelength may be cut off by a known cut-off filter.

The dose of light irradiation is usually 0.01 to 30J, and preferably 10J or less. It is preferable that the smaller the light irradiation amount, the more the reduction in reliability due to the destruction of the members constituting the liquid crystal display element is suppressed, and the tact (takt) in manufacturing is improved by reducing the light irradiation time.

Further, heating may be performed when light is irradiated. The heating temperature when light is irradiated is preferably within a temperature range in which introduced liquid crystal exhibits liquid crystallinity, and is usually 40 ℃ or higher, and it is preferable to heat at a temperature lower than a temperature at which the liquid crystal changes to an isotropic phase.

In addition, it is preferable that the irradiation with light during the polymerization reaction of the radical polymerizable compound is performed in an electric field-free state without applying a voltage.

On the other hand, when the liquid crystal cell is irradiated with light, a photomask is disposed outside the liquid crystal cell, and when the spacer photomask is irradiated with light, an unexposed portion (a region where no radical is generated) forms an in-plane alignment (horizontal alignment) region, and an exposed portion forms an out-of-plane alignment (vertical alignment) region as described above.

The pattern shape and pattern size of the photomask to be used are not particularly limited and can be appropriately selected according to the purpose. Examples of the pattern shape include a line pattern shape, a line/pitch (L/S) pattern shape, and a dot shape. As the pattern size, a pattern having a micron size can be formed, and for example, if a photomask having an L/S pattern shape with a pitch of 5 μm is used, an alignment pattern with a pitch of 5 μm can be formed.

In addition, the in-plane alignment (horizontal alignment) region can also be formed by irradiating the radical generating film with light before assembling the cell of the liquid crystal cell and deactivating the radical generating ability of the radical generating film. By irradiating the radical generating film with light in advance, the radical generating ability is eliminated, and the anchoring strength in the in-plane direction can be maintained at all times. That is, a liquid crystal cell is produced using a radical generating film in which the radical generating ability is inactivated, and the liquid crystal cell is irradiated with light, so that an in-plane alignment (horizontal alignment) region can be formed in a region in which the radical generating ability is inactivated.

The light used for deactivating the radical generating ability of the radical generating film includes light having a peak at 240 to 400 nm. The light preferably has a peak at 250 to 365nm, and more preferably has a peak at 250 to 360 nm. More specifically, for example, light having a peak around 313nm can be used. If necessary, light having a specific wavelength or a wavelength equal to or higher than the specific wavelength may be cut off by a known cut-off filter.

The dose of light irradiation is usually 0.01 to 30J, and preferably 10J or less.

In the unexposed area or the area where the radical generating ability is inactivated, the radical generating film is preferably subjected to uniaxial alignment treatment for good in-plane alignment of the liquid crystal.

In the unexposed area or the area where the radical generating ability is inactivated, the polymer contained in the radical generating film-forming composition in the radical generating film is preferably a polymer that does not contain a site having a function of vertical alignment in order to align the liquid crystal in a good plane.

As described above, when the out-of-plane alignment region is formed using the radical generating film, the cell is prepared using the first and second substrates on which the radical generating film is formed, a liquid crystal composition containing a predetermined radical polymerizable compound is injected, and then light is irradiated from the outside of the cell to polymerize the polymerizable compound, thereby vertically aligning the liquid crystal.

On the other hand, when the in-plane alignment region is formed using the radical generating film, the first and second substrates on which the radical generating film is formed may be irradiated with light in advance before cell assembly to deactivate the radical generating ability, and then cell assembly may be performed, whereby the interface reaction can be suppressed even when the manufactured liquid crystal cell is irradiated with light.

Alternatively, a photomask may be disposed outside the liquid crystal cell, and light may be irradiated through the photomask to the liquid crystal cell produced without deactivating the radical generating ability, so that radicals are not generated in the unexposed portion and no interface reaction is induced.

In a liquid crystal display element, a tilt alignment (tilt alignment) region can be formed by fabricating a liquid crystal cell such that an in-plane alignment region and an out-of-plane alignment region face each other.

For example, when radical generating films are used for both the first substrate and the second substrate, the above-described method of forming the out-of-plane alignment region and the method of forming the in-plane alignment region are appropriately combined, whereby an oblique alignment region can be produced.

More specifically, for example, an out-of-plane alignment region can be formed by using a radical generating film on one of the first substrate and the second substrate, and an in-plane alignment region can be formed by using a radical generating film whose radical generating ability has been inactivated on the other substrate, whereby an oblique alignment (tilt alignment) region can be formed.

In addition, a radical generating film may be used for one of the first substrate and the second substrate, and a liquid crystal alignment film having no radical generating ability may be used for the other substrate. When a liquid crystal alignment film having no radical generating ability is used as the other substrate, an in-plane alignment film or an out-of-plane alignment film may be used as the liquid crystal alignment film. By combining with the above-described method of producing the in-plane oriented region and the out-of-plane oriented region using the radical generating film, various patterns comprising various combinations of the in-plane oriented region, the tilt oriented region, and the out-of-plane oriented region can be formed.

The liquid crystal alignment film is preferably subjected to uniaxial alignment treatment.

In the method for manufacturing a liquid crystal display element of the present invention, the content of the radical polymerizable compound contained in the liquid crystal composition or the irradiation amount when the liquid crystal cell is irradiated with light can be adjusted so that the liquid crystal is aligned not in a homeotropic orientation and an obliquely aligned region is formed.

As described above, according to the method for manufacturing a liquid crystal display element of the present invention, it is possible to manufacture a liquid crystal display element in which at least 2 regions of an in-plane alignment region, an out-of-plane alignment region, and an oblique alignment region are patterned in a liquid crystal display element having a radical generation film.

< liquid crystal display element >

According to the manufacturing method of the present invention, a liquid crystal display element in which at least 2 regions out of an in-plane alignment region, an out-of-plane alignment region, and an oblique alignment region are patterned can be industrially manufactured with good productivity. Therefore, the liquid crystal display element produced by the production method of the present invention can be widely used in practical applications.

For example, it can be used as a reflective liquid crystal display element by providing a reflective electrode, a transparent electrode, a λ/4 plate, a polarizing film, a color filter layer, and the like in a liquid crystal cell as needed in a conventional manner.

In addition, a backlight, a polarizing plate, a λ/4 plate, a transparent electrode, a polarizing film, a color filter layer, and the like can be provided as necessary in the liquid crystal cell as a transmissive liquid crystal display element.

Fig. 10 is a schematic cross-sectional view showing an example of the liquid crystal display device of the present invention, and is an example of an IPS mode liquid crystal display device.

In the liquid crystal display element 101 illustrated in fig. 10, the liquid crystal composition 103 is sandwiched between the comb-teeth electrode substrate 102 provided with the radical generating film 102c and the counter substrate 104 provided with the liquid crystal alignment film 104 a. The comb-shaped electrode substrate 102 includes: the radical generating film includes a base 102a, a plurality of linear electrodes 102b formed on the base 102a and arranged in a comb-tooth shape, and a radical generating film 102c formed on the base 102a so as to cover the linear electrodes 102 b. The counter substrate 104 includes: a substrate 104b, and a liquid crystal alignment film 104a formed on the substrate 104 b.

In the liquid crystal display element 101, when a voltage is applied to the linear electrodes 102b, an electric field is generated between the linear electrodes 102b as indicated by the electric lines of force L.

Fig. 11 is a schematic cross-sectional view showing another example of the liquid crystal display device of the present invention, and is an example of an FFS mode liquid crystal display device.

In the liquid crystal display element 101 illustrated in fig. 11, the liquid crystal composition 103 is sandwiched between the comb-teeth electrode substrate 102 provided with the radical generating film 102h and the counter substrate 104 provided with the liquid crystal alignment film 104 a. The comb-shaped electrode substrate 102 includes: a base material 102d, a surface electrode 102e formed on the base material 102d, an insulating film 102f formed on the surface electrode 102e, a plurality of line electrodes 102g formed on the insulating film 102f and arranged in a comb-tooth shape, and a radical generating film 102h formed on the insulating film 102f so as to cover the line electrodes 102 g. The counter substrate 104 includes: a substrate 104b, and a liquid crystal alignment film 104a formed on the substrate 104 b.

In the liquid crystal display element 101, when a voltage is applied to the surface electrode 102e and the linear electrode 102g, an electric field is generated between the surface electrode 102e and the linear electrode 102g as indicated by the electric line of force L.

[ examples ]

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to these examples.

In the examples, the methods of abbreviation and property evaluation of compounds used in polymerization of the polymer and preparation of the radical generating film forming composition are as follows.

[ chemical formula 30]

[ chemical formula 31]

NMP: n-methyl-2-pyrrolidone,

BCS: butyl cellosolve

< measurement of viscosity >

The polyamic acid solution was measured for viscosity at 25 ℃ in a sample volume of 1.1mL using an E-type viscometer TVE-22H (manufactured by Toyobo industries Co., Ltd.) and a Cone Rotor (Cone Rotor) TE-1(1 ℃ 34', R24).

< measurement of molecular weight >

The molecular weight was measured by an ordinary temperature GPC (gel permeation chromatography) apparatus, and the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated as values converted to polyethylene glycol and polyethylene oxide.

GPC apparatus: GPC-101 (manufactured by Showa Denko K.K.), column: GPC KD-803 and GPC KD-805 (manufactured by SHOWA DENKO K.K.): 50 ℃ and eluent: n, N-dimethylformamide (as additive, lithium bromide monohydrate (LiBr. H) ₂ O) 30mmol/L, phosphoric acid anhydrous crystals (O-phosphoric acid) 30mmol/L, Tetrahydrofuran (THF) 10mL/L), flow rate: 1.0 mL/min

Standard sample for standard curve preparation: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh) and polyethylene glycol (molecular weight; about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratories, Inc.).

< measurement of imidization Rate >

20mg of polyimide powder was put into an NMR sample tube (manufactured by Standby SoftCorp. NMR sample tube Standard)

) To this solution, 0.53mL of deuterated dimethyl sulfoxide (DMSO-d) was added ₆ 0.05 mass% TMS (tetramethylsilane) blend) was added, and ultrasonic waves were applied to completely dissolve the TMS (tetramethylsilane) blend. The 500MHz proton NMR of the solution was measured by a measuring apparatus (JNW-ECA 500, manufactured by DATUM, Japan).

The imidization ratio is determined using protons having a structure that does not change before and after imidization as reference protons, and is obtained by the following equation using the peak integrated value of the protons and the peak integrated value of the protons derived from NH present in an amide group at about 9.5 to 10.0 ppm.

Imidization ratio (%) - (1-. alpha.x/y). times.100

Wherein x is a peak integrated value of NH protons derived from amide groups, y is a peak integrated value of a reference proton, and α is a number ratio of the reference proton to NH protons of 1 amide group in the case of a polyamic acid (imidization ratio of 0%).

< Synthesis of Compound DA-4 >

[ chemical formula 32]

(first step)

Tetrahydrofuran (120g), 2-hydroxy-4 '- (2-hydroxyethoxy) -2-methylpropiophenone (28.4g, 126mmol), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (28.0g, 181mmol) and N, N-dimethylaminopyridine (0.735g, 6.02mmol) were added to 4,4' -dinitro- [1,1 '-biphenyl ] -2,2' -dicarboxylic acid (20.0g, 60.2mmol) and stirred at room temperature overnight. After the reaction was completed, liquid-separation extraction was performed twice with water/chloroform, and the obtained organic phase was concentrated to obtain a syrup-like tea oil. This was purified by column chromatography in a mixed solvent of ethyl acetate/hexane 3/1 (volume ratio). The obtained fraction was concentrated to give a yellow transparent oil, and the oil was allowed to stand to precipitate white crystals. The precipitated crystals were washed with a slurry of a mixed solvent of ethyl acetate/hexane 3/1 (vol.%), filtered, and dried to obtain compound DA-4-1 (yield: 29.8g, 40.0mmol, yield 67%).

¹ H-NMR(500MHz)in DMSO-d ₆ ：8.57(d，J＝2.5Hz，2H)，8.37(dd，J＝8.5Hz，2.5Hz，2H)，8.18(d，J＝9.0Hz，4H)，7.55(d，J＝8.5Hz，2H)，6.85(d，J＝9.0Hz，4H)，5.631(s，2H)，4.39-4.35(m，4H)，4.02-3.99(m，2H)，3.96-3.94(m，2H)，1.40(s，12H).

(second step)

Tetrahydrofuran (240g) was added to the compound DA-4-1(29.8g, 40.0mmol) obtained in the first step, nitrogen substitution was performed, then 3% platinum carbon (hydrous product) (2.38g) was added thereto, nitrogen substitution was further performed, a hydrogen tedlar bag (tedlar bag) was attached, and stirring was performed at room temperature for about 17 hours. After completion of the reaction, platinum carbon was removed by a membrane filter, and then the reaction mixture was concentrated and dried to obtain compound (DA-4) (yield: 27.4g, 40.0mmol, yield quant).

¹ H-NMR(500MHz)in DMSO-d ₆ ：8.20(dd，J＝7.1Hz，1.9Hz，4H)，6.99(d，J＝2.5Hz，2H)，6.92(dd，J＝7.3Hz，1.9Hz，4H)，6.80(d，J＝8.2Hz，2H)，6.67(dd，J＝8.2Hz，2.5Hz，2H)，5.64(s，2H)，5.24(s，4H)，4.22(t，J＝4.5Hz，4H)，4.00(br，4H)，1.39(s，12H).

(polymerization of Polymer and preparation of radical-generating film-Forming composition)

< Synthesis example 1> polymerization of TC-1(50) TC-2(50)/DA-1(70) DA-2(30)

In a 100mL 4-neck flask equipped with a nitrogen introduction tube, an air cooling tube and a mechanical stirrer, 3.78g (35.0mmol) of DA-1 and 4.96g (15.0mmol) of DA-2 were weighed out, and 35.0g of NMP was added thereto and stirred under a nitrogen atmosphere to completely dissolve them. After confirming the dissolution, 6.26g (25.0mmol) of TC-2 and 25.0g of NMP were added, and the mixture was stirred under nitrogen at 60 ℃ for 3 hours. Thereafter, 4.12g (21.0mmol) of TC-1 and 16.5g of NMP were added thereto, and the mixture was stirred at room temperature for 12 hours. The polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity became 1000 mPas, to obtain a polymerization solution having a polyamic acid concentration of 20 mass%.

In a 200mL Erlenmeyer flask equipped with a magnetic stirrer, 50.0g of the polyamic acid solution obtained above was weighed, 92.9g of NMP was added to prepare a solution having a solid content concentration of 7% by mass, 10.6g (103mmol) of acetic anhydride and 3.28g (41.4mmol) of pyridine were added while stirring, and after stirring at room temperature for 30 minutes, the mixture was heated and stirred at 60 ℃ for 3 hours. Thereafter, the solution was returned to room temperature, and the solution was poured into 500mL of methanol with stirring to precipitate a solid. This operation was repeated twice, and then air-dried and dried in a vacuum oven set to 60 ℃, thereby obtaining a polyimide powder (PI-1) having Mn of 11,453, Mw of 27,655, and imidization rate of 67.0%.

< Synthesis example 2 >

Synthesis of TC-1(50) TC-2(50)/DA-1(50) DA-2(50) polyimides

Polyimide powder (PI-2) was obtained in the same manner as in synthesis example 1, except that the amount of the monomer used was changed as shown in table 1. The polyimide powder had Mn of 21,959, Mw of 67,088 and imidization rate of 62.2%.

< Synthesis example 3>

Synthesis of TC-1(50) TC-2(50)/DA-2(100) polyimide

Polyimide powder (PI-3) was obtained in the same manner as in synthesis example 1, except that the amount of the monomer used was changed as shown in table 1. The polyimide powder had Mn of 21,959, Mw of 67,088 and imidization rate of 72.0%.

Synthesis example 4 polymerization of TC-3(100)/DA-3(50) DA-4(50) Polyamic acid

In a 100mL 4-neck flask equipped with a nitrogen inlet, an air-cooling tube and a mechanical stirrer, 2.44g (10.00mmol) of DA-3 and 6.85g (10.00mmol) of DA-4 were weighed, and 52.6g of NMP was added thereto and stirred under a nitrogen atmosphere to completely dissolve them. After confirming the dissolution, 4.21g (18.80mmol) of TC-3 and 23.9g of NMP were added, and the mixture was stirred at 40 ℃ for 12 hours under a nitrogen atmosphere. The polymerization viscosity was confirmed, and TC-3 was further added so that the polymerization viscosity became 400 mPas, to obtain a polymerization solution (PAA-1) having a polyamic acid concentration of 15 mass%. The polyamic acid had Mn of 16,331 and Mw of 42,999.

< Synthesis example 5> Synthesis of AC-1(40) AC-2(60) polymethacrylate

In a 100mL 4-neck flask equipped with a nitrogen inlet, an air-cooling tube and a mechanical stirrer, 5.00g (15.0mmol) of AC-1, 6.91g (22.6mmol) of AC-2 and 0.185g (1.13mmol) of AIBN were measured, and 67.5g of NMP was added thereto and stirred under a nitrogen atmosphere to completely dissolve the AIBN. The solution was degassed under vacuum and then heated and stirred at 60 ℃ for 12 hours under a nitrogen atmosphere. After that, the solution was returned to room temperature, and the mixture was poured into 300mL of methanol with stirring to precipitate a solid. After repeating this operation twice, the obtained product was air-dried and dried in a vacuum oven set to 60 ℃, thereby obtaining a polymethacrylate powder (PMA-1) having Mn of 37,197 and Mw of 116,919.

< free radical generating film-forming composition: preparation of AL-1

In a 15mL vial (visual) equipped with a magnetic stirrer, 0.90g of the polyimide powder (PI-1) obtained in Synthesis example 1 was weighed, 5.10g of NMP was added thereto, and the mixture was stirred at 50 ℃ to obtain a polymer solution having a solid content of 15 mass%. To this was added 6.00g of NMP, and 3.00g of BCS, and further stirred for 3 hours, thereby obtaining a radical generating film forming composition according to the present invention: AL-1 (solid content: 6.0 mass%, NMP: 74 mass%, BCS: 20 mass%).

< free radical generating film-forming composition: preparation of AL-2

Using the polyimide powder (PI-2) obtained in Synthesis example 2, a radical generating film forming composition according to the present invention was obtained in the same manner as for the preparation of AL-1: AL-2 (solid content: 6.0 mass%, NMP: 74 mass%, BCS: 20 mass%).

< free radical generating film-forming composition: preparation of AL-3

Using the polyimide powder (PI-3) obtained in Synthesis example 3, a radical generating film forming composition according to the present invention was obtained in the same manner as for the preparation of AL-1: AL-3 (solid content: 6.0 mass%, NMP: 74 mass%, BCS: 20 mass%).

< free radical generating film-forming composition: preparation of AL-4

In a 15mL vial (visual) equipped with a magnetic stirrer, 6.00g of the polyamic acid (PAA-1) obtained in Synthesis example 4 was measured, and 6.00g of NMP and 3.00g of BCS were added and stirred for 3 hours, thereby obtaining a radical generating film forming composition according to the present invention: AL-4 (solid content: 6.0 mass%, NMP: 74 mass%, BCS: 20 mass%).

< free radical generating film-forming composition: preparation of AL-5

In a 15mL vial (visual) equipped with a magnetic stirrer, 0.27g of the polymethacrylate powder (PMA-1) obtained in Synthesis example 5 and 0.63g of the polyimide powder (PI-3) obtained in Synthesis example 3 were weighed, and 5.10g of NMP was added thereto and stirred at 60 ℃ to obtain a polymer solution having a solid content of 15 mass%. To this was added 6.00g of NMP, and 3.00g of BCS, and further stirred for 3 hours, thereby obtaining a radical generating film forming composition according to the present invention: AL-5 (solid content: 6.0 mass%, NMP: 74 mass%, BCS: 20 mass%).

< free radical generating film-forming composition: preparation of AL-6

In a 15mL vial (visual) equipped with a magnetic stirrer, 0.45g of the polymethacrylate powder (PMA-1) obtained in Synthesis example 5 and 0.45g of the polyimide powder (PI-3) obtained in Synthesis example 3 were weighed, and 5.10g of NMP was added thereto and stirred at 60 ℃ to obtain a polymer solution having a solid content of 15 mass%. To this was added 6.00g of NMP, and 3.00g of BCS, and further stirred for 3 hours, thereby obtaining a radical generating film forming composition according to the present invention: AL-6 (solid content: 6.0 mass%, NMP: 74 mass%, BCS: 20 mass%).

< non-radical generating film-forming composition: preparation of AL-7

Using the polymethacrylate powder (PMA-1) obtained in Synthesis example 5, a non-radical generating film-forming composition according to the comparative example of the present invention was obtained in the same manner as for the preparation of AL-1: AL-7 (solid content: 6.0 mass%, NMP: 74 mass%, BCS: 20 mass%).

The compositions of the polyamic acid and the polyimide are shown in table 1 below.

[ Table 1]

The composition of the polymethacrylate is shown in table 2 below.

[ Table 2]

The compositions of the radical generating film forming composition and the non-radical generating film forming composition are shown in the following table 3.

[ Table 3]

The composition of the liquid seed crystal is shown in table 4 below.

[ Table 4]

(polymerizable Compound)

The polymerizable compounds (additives) described in table 4 were obtained in the following manner.

< Synthesis example 1 of polymerizable Compound

Synthesis of didecyl itaconate (IC-12)

[ chemical formula 33]

30.0g (231mmol) of itaconic acid and 81.6g (438mmol) of 1-dodecanol were weighed into a 4-neck flask equipped with a water-splitting distillation receiving tube (Dean-Stark tube), and completely dissolved in cyclohexane (700 mL). After confirming the dissolution, 1.13g (11.5mmol) of concentrated sulfuric acid and 0.51g (2.31mmol) of dibutylhydroxytoluene (BHT) were added, and the mixture was heated and stirred at 120 ℃ for 24 hours under a nitrogen atmosphere. Using nuclear magnetic resonance spectroscopy ( ¹ H-NMR spectrum), 100mL of n-hexane was added to the reaction solution, and the mixture was washed 3 times with 100g of a 10% sodium carbonate aqueous solution and 3 times with 100mL of pure water, and dried over anhydrous magnesium sulfate. After filtration, concentration and vacuum drying, 78.0g of a white solid was obtained (167 mmol: yield 76.3%). Structural utilization ¹ The H-NMR spectrum confirmed that the compound was the objective compound. The measurement data are shown below.

¹ H-NMR(400MHz,CDCl ₃ )δ：6.30(1H)、5.65(1H)、4.20-4.00(4H)、3.32(2H)、1.64-1.58(4H)、1.40-1.25(36H)、0.96-0.83(6H)

< Synthesis example 2 of polymerizable Compound

Synthesis of dihexylacrylamide (AAA-C6C6)

[ chemical formula 34]

In a 4-neck flask, 33.3g (180mmol) of dihexylamine and 27.3g (270mmol) of triethylamine were measured, and 500mL of THF was added and dissolved completely at room temperature. After confirming the dissolution, the reaction vessel was cooled with ice and held at 0 ℃ in the system, and 17.9g (198mmol) of acryloyl chloride was slowly added dropwise. Using nuclear magnetic resonance spectroscopy ( ¹ H-NMR spectrum), 100mL of ethyl acetate was added to the reaction solution, and the mixture was washed 3 times with 100g of a 10% aqueous solution of sodium carbonate and 3 times with 100mL of pure water, and dried over anhydrous magnesium sulfate. After filtration, concentration and vacuum drying, 33.6g of a transparent oily liquid was obtained(140 mmol: yield 78.1%). Structural utilization ¹ The H-NMR spectrum confirmed that the compound was the objective compound. The measurement data are shown below.

¹ H-NMR(400MHz,DMSO-d6)δ：6.62(1H)、6.04(1H)、5.58(1H)、3.20-4.00(4H)、3.35-3.25(4H)、1.64-1.58(4H)、1.30-1.25(12H)、0.96-0.83(6H)

< Synthesis example 3 of polymerizable Compound

Synthesis of 4-pentylcyclohexyl methacrylate (MACH-C5)

[ chemical formula 35]

In a 4-neck flask, 25.0g (147mmol) of 4-pentylcyclohexanol and 22.3g (220mmol) of triethylamine were weighed out, and 400mL of THF was added and dissolved completely at room temperature. After confirming the dissolution, the temperature was maintained at 0 ℃ in the system in an ice bath, and 18.4g (176mmol) of methacryloyl chloride was slowly added dropwise. Using nuclear magnetic resonance spectroscopy ( ¹ H-NMR spectrum), 100mL of hexane was added to the reaction solution, and the mixture was washed 3 times with 100g of a 10% aqueous sodium carbonate solution and 3 times with 100mL of pure water, and dried over anhydrous magnesium sulfate. After filtration, concentration and vacuum drying, 20.3g of a transparent oily liquid (86.2 mmol: 58.0% yield) was obtained. Structural utilization ¹ The H-NMR spectrum confirmed that the product was the intended product. The measurement data are shown below.

¹ H-NMR(400MHz,DMSO-d6)δ：6.15-5.95(1H)、5.65-5.60(1H)、4.95-4.90(0.60H)、4.65-4.57(0.40H)、1.89-1.86(3H)、1.79-1.74(2H)、1.56-1.50(2H)、1.36-1.15(11H)、0.87-0.84(3H)

< purchase of polymerizable Compound >

The polymerizable compound DMA was purchased from Tokyo chemical industry Co., Ltd. (TCI) as it was.

(production of liquid Crystal display element)

Liquid crystal cells were prepared using the AL-1 to AL-7 obtained above and SE-6414 and NRB-U438 (manufactured by Nissan chemical Co., Ltd.) as liquid crystal aligning agents for horizontal alignment, and liquid crystal display elements having the structures shown in Table 5 below were prepared.

The structure of the liquid crystal cell is shown in table 5 below.

[ Table 5]

< first/second substrate >

The first and second substrates were alkali-free glass substrates having a size of 30mm × 40mm and a thickness of 1.1 mm. An ITO (Indium-Tin-Oxide) electrode having a thickness of 10 μm was formed on the substrate. The first substrate and the second substrate are the same substrate, and names are separated for convenience.

< surface treatment Process of AL-1, AL-2, AL-3, SE-6414 >

AL-1, AL-2, AL-3, and SE-6414 were filtered through a filter having a pore size of 1.0 μm, applied to the electrode-formed surface of the first and second substrates by a spin coating method, and dried on a hot plate at 80 ℃ for two minutes. Then, the film was sintered for 30 minutes in a thermal cycle furnace having an internal temperature of 230 ℃ to obtain a coating film having a film thickness of 100 nm.

The first and second substrates with the coating films obtained above were subjected to rubbing treatment. After bonding, the first substrate is subjected to rubbing treatment in the rubbing direction from the longitudinal direction, and the second substrate is subjected to rubbing treatment in the rubbing direction from the lateral direction so that the rubbing directions are antiparallel to each other. The friction cloth is rayon cloth made by Jichuan chemical industry: YA-20R, 120mm roller diameter.

The rubbing treatment for AL-1, AL-2 and AL-3 was carried out under the conditions of a rotation speed of 500rpm, a moving speed of 30mm/sec and a pressing amount of 0.3 mm.

The rubbing treatment in SE-6414 was carried out under the conditions of a rotation speed of 1000rpm, a moving speed of 20mm/sec and a pressing amount of 0.4 mm.

After the rubbing treatment, ultrasonic washing was performed in pure water for 1 minute, and drying was performed at 80 ℃ for 15 minutes.

< surface treatment Process of AL-4, AL-5, AL-6, AL-7, NRB-U438

AL-5, AL-6, and AL-7 were filtered through a filter having a pore size of 1.0 μm, applied to the electrode-formed surface of the first and second substrates by spin coating, and dried on a hot plate at 70 ℃ for 90 seconds.

Then, the linearly polarized light having a wavelength of 313nm was irradiated at 0.005J/cm using a high-pressure mercury lamp (313 nm band-pass filter manufactured by CERMA PRECISION Co., Ltd.) ² Exposed to light and sintered on a hot plate at 150 ℃ for 30 minutes.

AL-4 and NRB-U438 were filtered through a filter having a pore size of 1.0 μm, applied to the electrode-formed surfaces of the first and second substrates by a spin coating method, dried on a hot plate at 80 ℃ for two minutes, and fired in a thermal cycle furnace having an internal temperature of 230 ℃ for 30 minutes. Then, the linearly polarized light having a wavelength of 254nm was irradiated at 0.3J/cm using a low-pressure mercury lamp (a short-wavelength cut-off filter having a wavelength of 240nm or less manufactured by Ushio Motor Co., Ltd.) ² And exposing and sintering for 30 minutes in a thermal cycle heating furnace with the internal temperature of 230 ℃.

< one exposure >

After the surface treatment process, the two substrates (first and second substrates) with the liquid crystal alignment films were subjected to irradiation with light having a wavelength of 313nm at a wavelength of 10J/cm using a high-pressure mercury lamp (short-wavelength cut-off filter of 300nm or less manufactured by CERMA PRECISION Co., Ltd.) ² And (6) exposing. When selective irradiation with light is desired, a photomask (100, 50, 30, 5 μm L/S with chrome wiring manufactured by Mitani Micronics) is placed on the substrate, and pattern exposure is performed. This operation is described as one exposure.

Further, the primary exposure was performed for the purpose of intentionally inactivating radicals that generate radicals contained in the alignment film, and was only suitable for examples 23, 24, 27, 28, 29, 30, and 32.

< production of liquid Crystal cell >

Using the finished surface treatment method, the two substrates (first and second substrates) with liquid crystal alignment films after the completion of the primary exposure method further performed in examples 23, 24, 27, 28, 29, 30, and 32 were sealed with the liquid crystal injection port left, and an empty cell having a cell gap of about 4 μm was produced. The step of performing the rubbing process in the surface treatment step is to form the dummy cells so that the rubbing directions of the first substrate and the second substrate are antiparallel to each other.

In this empty cell, a liquid crystal (as shown in table 4, in the case of positive liquid crystal MLC-3019 for IPS manufactured by Merck or negative liquid crystal MLC-7026 for IPS manufactured by Merck, a liquid crystal to which each additive is added in a predetermined amount with respect to the liquid crystal) was vacuum-injected at room temperature, and then the injection port was sealed to prepare a liquid crystal cell. 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 ℃ for 10 minutes.

< second exposure >

The obtained liquid crystal cell was irradiated with light having a wavelength of 313nm using a high-pressure mercury lamp (a short-wavelength cut-off filter having a wavelength of 300nm or less manufactured by CERMA PRECISION). The irradiation dose is shown in table 5. When selective irradiation with light is desired, a photomask (L/S of 100, 50, 30, 5 μm, manufactured by Mitani Micronics) is placed on the liquid crystal cell, and pattern exposure is performed. This operation is then described as a second exposure. The secondary exposure is intended to react a radical-generating group contained in the alignment film with a polymerizable compound (additive) in the liquid crystal.

(results of visual evaluation of liquid Crystal alignment Properties after Secondary Exposure)

The alignment state of the liquid crystal cell after the secondary exposure was confirmed using a polarizing plate arranged in crossed nicols (crossed nicols). The angle formed by the uniaxial alignment direction of the liquid crystal and the polarization direction was set to 45 degrees. In this case, light is transmitted when the liquid crystal is uniaxially aligned, and light is not transmitted when the liquid crystal is out-of-plane aligned.

As an example, since the unit 7 (example 5) can perform out-of-plane alignment control, the exposed region becomes a dark field (fig. 1A and 1B).

Fig. 1A shows a photograph of a liquid crystal display element, and fig. 1B schematically shows a photograph of the liquid crystal display element of fig. 1A (hereinafter, in fig. 2 to 5 and fig. 9, similarly, a photograph of the liquid crystal display element is shown in fig. a, and a schematic diagram of the photograph is shown in fig. B).

In fig. 1 (fig. 1A and 1B are also collectively referred to as fig. 1), an exposed portion of a reference numeral 1 is indicated as a dark field (black), and a non-exposed portion of a reference numeral 2 is indicated as a bright field (white).

Since the unit 27 (comparative example 4) cannot perform out-of-plane alignment control, the exposed portion becomes a bright field (fig. 2A and 2B).

In fig. 2 (fig. 2A and 2B are also collectively referred to as fig. 2), both the exposed portion and the unexposed portion are shown as a bright field (white).

Since the cell 1 (example 1) is in tilt (tilt) orientation (partially out-of-plane orientation), the coloring of the exposed portion is reduced (partially dark field), and the cell is shown as a gray intermediate color (fig. 3A and 3B).

In fig. 3 (fig. 3A and 3B are collectively referred to as fig. 3), a portion B where the exposed portion of the symbol 1 is a dark field (black) is mixed with a portion a of a light and dark intermediate color (gray). The unexposed part of the symbol 2 is indicated as a bright field (white).

Liquid crystal display elements in examples and comparative examples shown in tables 6 to 8 below were evaluated by the same method as shown in fig. 1 to 3.

In tables 6 to 8, the regions where the secondary exposed regions are indicated as dark field (black) and out-of-plane orientation control is possible are indicated as good, the regions where the secondary exposed regions are indicated as bright field (white) and out-of-plane orientation control is not possible are indicated as x, and the regions where the secondary exposed regions are indicated as intermediate color (gray) and have uniaxial orientation and nonuniform orientation with an oblique angle are indicated as Δ.

The results of visual evaluation of the liquid crystal alignment properties after the secondary exposure are shown in table 6 below.

[ Table 6]

In order to induce out-of-plane alignment from an in-plane uniaxial alignment state, it is necessary to (i) contain a group capable of generating a radical in an alignment film, (ii) contain a polymerizable compound (additive) in a liquid crystal, and (iii) irradiate light. In order to form a good out-of-plane orientation state, it is effective to consider the content of a radical-generating group, the content of a polymerizable compound, the amount of light irradiation, and the like.

The results of visual evaluation of the liquid crystal alignment properties after the secondary exposure are shown in table 7 below.

[ Table 7]

	Cell number of liquid crystal cell	Orientation state
			Example 12	17	〇
Example 13	17	〇
			Example 14	18	〇
Example 15	20	〇
			Example 16	8	△
Example 17	19	〇

The polymerizable compound (additive) required for the out-of-plane orientation control is not limited to DMA. The out-of-plane orientation can be controlled by any additive having an appropriate structure. The liquid crystal type is not limited to MLC-7026, which is a liquid crystal having a negative dielectric constant, and can be controlled to be in-plane alignment even in MLC-3019, which is a liquid crystal having a positive dielectric constant.

The results of visual evaluation of the liquid crystal alignment properties after the secondary exposure are shown in table 8 below.

[ Table 8]

	Cell number of liquid crystal cell	Orientation state
			Example 18	21	〇
Example 19	22	〇
			Example 20	23	〇
Example 21	24	〇
			Example 22	25	〇
Comparative example 5	26	×
			Comparative example 6	28	×

Even when a photo-alignment film subjected to photo-alignment treatment is used, out-of-plane alignment control can be performed without depending on the type of polymer constituting the alignment film and the exposure wavelength required for photo-alignment. In addition, as shown in the liquid crystal cells 22 and 23 used in examples 19 and 20, etc., when an alignment film material having no radical-generating group is used, out-of-plane alignment control can be performed by mixing with a polymer material having a radical-generating group. In this case, the out-of-plane orientation can be controlled by introducing an appropriate amount of a radical-generating group. Further, as in examples 21 and 22, the out-of-plane alignment control may be performed only when the first substrate is coated with the photo-alignment film having the radical generating ability. Depending on the type of photo-alignment film used, for example, when the alignment restriction force of the liquid crystal is small, the alignment restriction force of the liquid crystal is reduced by light irradiation.

(results of visual evaluation of liquid Crystal alignment Property in one Exposure)

The alignment state of the liquid crystal cell after the second exposure was confirmed using a polarizing plate disposed in crossed nicols. In addition, the angle formed by the uniaxial alignment direction of the liquid crystal cell and the polarization direction was set to 45 degrees. The results are shown in Table 9 below.

[ Table 9]

As a single exposure, when the entire surface of the first substrate is exposed, a tilt (tilt) orientation is formed (fig. 4A and 4B).

In fig. 4 (fig. 4A and 4B are also collectively referred to as fig. 4), a portion indicated by reference numeral 3 is a region where only the first substrate is exposed by the first exposure and the entire surface is exposed by the second exposure. The portion indicated by the symbol 3 indicates a gray intermediate color, and forms a tilt (tilt) orientation. The portion denoted by symbol 4 is a non-exposure region where only the first substrate is exposed by one exposure, and not exposed by the second exposure. The portion indicated by symbol 4 is indicated by a bright field (white), and forms an in-plane orientation.

The first substrate and the second substrate are subjected to full-surface exposure by one exposure to form in-plane alignment (fig. 5A and 5B).

In fig. 5 (fig. 5A and 5B are also collectively referred to as fig. 5), a portion denoted by reference numeral 5 is a region where the first and second substrates are exposed by one exposure and the entire surface is exposed by the second exposure. The portion indicated by reference numeral 6 is a non-exposure region where the first and second substrates are exposed by one exposure and not exposed by the second exposure. The portions indicated by the

reference numerals

5 and 6 are both in bright field (white), and in-plane orientation is formed. This can confirm that: by irradiating the substrate before cell fabrication with light, the radical-generating group contained in the alignment film is deactivated, and no reaction with the polymerizable compound (additive) is induced during secondary exposure, so that out-of-plane alignment is not formed.

(evaluation of orientation patterning)

The alignment state of the pattern-exposed liquid crystal display element was confirmed using a polarizing plate arranged in crossed nicols. In addition, the angle formed by the uniaxial alignment direction of the liquid crystal cell and the polarization direction was set to 45 degrees. The evaluation of the alignment pattern was made by visual observation from the viewpoint of alignment control by light irradiation, alignment uniformity, and sharpness of the alignment control surface (interface between uniaxial in-plane alignment and out-of-plane alignment). The results are shown in Table 10 below.

[ Table 10]

	Cell number of liquid crystal cell	State of patterning
			Example 25	7	Even and bright (fig. 6 left)
Example 26	21	Even and bright (fig. 6 right)

The change in orientation from in-plane (uniaxial) orientation to out-of-plane orientation by light irradiation can be uniformly controlled, and the interface of different orientations is sharp (fig. 6). As shown in fig. 6, it was confirmed that the alignment regions were clearly patterned in the bright field (white) in-plane alignment region and the dark field (black) out-of-plane alignment region.

In addition, this does not depend on the kind of polymer constituting the alignment film or the alignment treatment method. Since the alignment patterns can be made using materials of significantly different kinds, alignment patterning is possible in all of the examples in tables 6 to 8 in which out-of-plane alignment control is assumed to be possible.

(evaluation of fine alignment Pattern)

The alignment state of the pattern-exposed liquid crystal display element was confirmed using a polarizing plate disposed in crossed nicols. In addition, the angle formed by the uniaxial alignment direction of the liquid crystal cell and the polarization direction was set to 45 degrees. The evaluation of the alignment pattern was made by visually observing and determining whether or not alignment control, alignment uniformity, and sharpness of the alignment control surface (interface between in-plane uniaxial alignment and out-of-plane alignment) could be performed by light irradiation. The results are shown in Table 11 below.

[ Table 11]

A liquid crystal display element produced by using a substrate subjected to pattern exposure as a primary exposure can produce a uniform and clear fine alignment pattern regardless of the L/S width of a photomask.

For example, a photograph of the liquid crystal display element obtained in example 27 is shown in fig. 7. At this time, since only the first substrate is pattern-exposed as one exposure, the intermediate color (gray) portion indicated by reference numeral 7 in fig. 7 is in a tilt (tilt) alignment state. The dark field (black) portion indicated by symbol 8 in fig. 7 forms an out-of-plane orientation state.

FIG. 8 shows the results of example 30 obtained by changing the L/S width of the photomask of example 27. In fig. 8, the difference between the intermediate color (gray) portion and the dark field (black) portion is as described in fig. 7.

When the neutral color (gray) portion is to be uniaxially aligned in the plane, the second substrate may be subjected to pattern exposure in the same manner as the first substrate, and the exposed portions may be bonded to each other to produce a liquid crystal cell, followed by secondary exposure.

As a liquid crystal display element subjected to pattern exposure by the second exposure without performing the first exposure, as shown in example 31, it was confirmed that the alignment patterning could be performed under the condition that the L/S width of the photomask was 100 μm. The liquid crystal display element of example 31 was also clearly patterned in the bright field (white) in-plane alignment region and the dark field (black) out-of-plane alignment region.

Further, as shown in example 32, it was confirmed that three alignment states of in-plane uniaxial alignment, out-of-plane alignment, and oblique alignment can be produced in one liquid crystal display element by performing pattern exposure on both the first and second substrates, and then performing secondary exposure after producing a liquid crystal cell by vertically bonding the pattern directions.

Results of the liquid crystal display element obtained in example 32 are shown (fig. 9A and 9B). Fig. 9A shows a photograph of the liquid crystal display element, and a schematically illustrated diagram of the photograph of the liquid crystal display element of fig. 9A is shown in fig. 9B.

As shown in fig. 9 (fig. 9A and 9B are also collectively referred to as fig. 9), the dark field (black) portion indicated by reference numeral 9 is in an out-of-plane alignment state. The bright field (white) portion indicated by reference numeral 10 is oriented in plane. The intermediate color (gray) portion indicated by reference numeral 11 (a portion indicated by a diagonal line pattern in fig. 9B) is in a tilt (tilt) oriented state.

Industrial applicability

According to the present invention, a liquid crystal display element in which at least 2 regions out of an in-plane alignment region, an out-of-plane alignment region, and an oblique alignment region are patterned can be industrially produced with good productivity.

Description of the symbols

101 liquid crystal display element

102 comb electrode substrate

102a base material

102b wire electrode

102c free radical generating film

102d base material

102e face electrode

102f insulating film

102g wire electrode

102h radical generating membranes

103 liquid crystal composition

104 opposite substrate

104a liquid crystal alignment film

104b, a substrate.

Claims

1. A method of manufacturing a liquid crystal display element, comprising:

step (A): forming a radical generating film capable of generating radicals by irradiation of light on a substrate; and

a step (B): bringing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound into contact with the radical generating film, and while maintaining this state, irradiating the liquid crystal composition with light having a peak at 240 to 400nm sufficient to cause the radical polymerizable compound to undergo a polymerization reaction,

further, the manufacturing method includes at least one of the following requirements (Z1) and (Z2), and manufactures a liquid crystal display element in which at least 2 regions of an in-plane alignment region, an out-of-plane alignment region, and an oblique alignment region are patterned:

requirement (Z1): a step (C) of irradiating the radical generating film obtained in the step (A) with light having a peak at 240 to 400nm to inactivate the radical generating ability of the radical generating film;

element (Z2): the step (B) of irradiating the liquid crystal composition with light having a peak at 240 to 400nm is performed through a photomask.

2. The method for manufacturing a liquid crystal display element according to claim 1, wherein the radical generation film is a coating film subjected to uniaxial alignment treatment.

3. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein the step of irradiating the liquid crystal composition with light having a peak at 240 to 400nm in the step (B) is performed in the absence of an electric field.

4. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 3, wherein the radical generating film has a polymer containing an organic group that initiates radical polymerization.

5. The method of manufacturing a liquid crystal display element according to claim 4, wherein the polymer containing an organic group that initiates radical polymerization has a structural unit represented by the following formula (1) in a main chain,

6. The method for manufacturing a liquid crystal display element according to claim 4 or 5, wherein the polymer is at least one selected from a polyimide precursor obtained using a diamine component containing a diamine containing an organic group that initiates radical polymerization, a polyimide, a polyurea, and a polyamide.

7. The method for manufacturing a liquid crystal display element according to claim 5, wherein the radical polymerization initiating organic group is a group represented by the following formula (3),

in the formula (3), the dotted line represents a bond to a benzene ring, R ⁶ Represents a single bond, -CH ₂ -、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH ₂ O-、-N(CH ₃ )-、-CON(CH ₃ ) -or-N (CH) ₃ )CO-，

R ⁷ Represents a single bond, or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with a fluorine atom, or any of-CH's of the alkylene groups ₂ -or-CF ₂ 1 or more of-are independently replaced or not replaced by a group selected from-CH- ═ CH-, a 2-valent carbocyclic ring and a 2-valent heterocyclic ring, and further, are replaced or not replaced by any of the groups mentioned below, i.e., -O-, -COO-, -OCO-, -NHCO-, -CONH-or-NH-under the condition that these groups are not adjacent to each otherInstead of this, the user can,

formula [ X-1]～[X-18]Wherein represents a group represented by ⁷ Bonding site of (2), S ₁ And S ₂ Each independently represents-O-, -NR-, or-S-, wherein R 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, and R is ₁ And R ₂ Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms,

formula [ W ]]、[Y]、[Z]Wherein represents a group represented by ⁷ The bonding site of (3); s ³ Represents a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-、-N(CH ₃ )-、-CON(CH ₃ ) -, or-N (CH) ₃ ) CO-; ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene, which may or may not have an organic group and/or a halogen atom as a substituent; r ⁹ And R ¹⁰ Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group or a phenethyl group, and in the case of an alkyl group or an alkoxy group, R represents ⁹ And R ¹⁰ Form a ring or not form a ring;

q represents any one of the following structures,

in the formula, R ¹¹ represents-CH ₂ -, -NR-, -O-, or-S-, wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and x represents a bond,

8. The method for manufacturing a liquid crystal display element according to claim 6, wherein the diamine containing an organic group that initiates radical polymerization is a diamine represented by the following formula (2),

in the formula (2), A ¹ And A ² Each represents a hydrogen atom or a group represented by the following formula (3) wherein A ¹ And A ² At least one of them represents a group represented by the following formula (3),

p represents an integer of 0 to 2; when p is 2, a plurality of A ² And E each independently have the foregoing definitions; in addition, when p is 0, A ¹ Comprising a group represented by the following formula (3),

R ⁷ Represents a single bond, or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with a fluorine atom, or any of-CH's of the alkylene groups ₂ -or-CF ₂ -1 or more of-are each independently replaced by or not replaced by a group selected from-CH ═ CH-, 2-valent carbocyclic ring and 2-valent heterocyclic ringFurther, any of the groups mentioned below, i.e., -O-, -COO-, -OCO-, -NHCO-, -CONH-or-NH-may or may not be substituted by these groups,

R ⁸ is represented by a group selected from the formula [ X-1 ]]～[X-18]、[W]、[Y]And [ Z]An organic group which initiates radical polymerization represented by the formula (1),

q represents any one of the following structures,

in the formula (I), the compound is shown in the specification,R ¹¹ represents-CH ₂ -, -NR-, -O-, or-S-, wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and represents a bond,

9. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 8, wherein at least one of the radical polymerizable compounds is a compound having one polymerizable unsaturated bond in one molecule, which is compatible with a liquid crystal.

10. The method for manufacturing a liquid crystal display element according to claim 9, wherein the radical polymerizable compound has a polymerization reactive group selected from the following structures,

wherein represents a site bonded to a portion other than the polymerizable unsaturated bond of the compound molecule; r ^b Represents an alkyl group having 3 to 20 carbon atoms; e represents a single bond, -O-, -NR ^c A linking group of- (O-X-O) -, -S-, an ester bond and an amide bond, wherein R is ^c Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; r ^b The alkyl group of (b) represents a linear, branched or cyclic alkyl group.

11. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 10, wherein the radical polymerizable compound contained in the liquid crystal composition containing a liquid crystal and a radical polymerizable compound satisfies the following conditions: the polymer obtained by polymerizing the radical polymerizable compound has a Tg of 100 ℃ or lower.

12. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 11, further comprising a step of manufacturing a liquid crystal cell by:

preparing a first substrate having a radical generating film and a second substrate;

a radical generating film on the first substrate and arranged to face the second substrate; and

13. The method for manufacturing a liquid crystal display element according to claim 12, wherein the second substrate has a radical generating film.

14. The method for manufacturing a liquid crystal display element according to claim 12, wherein the second substrate is a substrate covered with a liquid crystal alignment film having uniaxial alignment properties.

15. The method for manufacturing a liquid crystal display element according to claim 14, wherein the liquid crystal alignment film having a uniaxial alignment property is a liquid crystal alignment film for horizontal alignment.

16. The method for manufacturing a liquid crystal display element according to any one of claims 12 to 15, wherein the first substrate having the radical generating film is a substrate having comb-teeth electrodes.