CN112292633A

CN112292633A - Method for manufacturing zero-plane anchoring film and liquid crystal display element

Info

Publication number: CN112292633A
Application number: CN201980041213.XA
Authority: CN
Inventors: 野田尚宏
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2018-06-18
Filing date: 2019-06-17
Publication date: 2021-01-29
Also published as: JP7367674B2; JPWO2019244821A1; TW202000870A; KR20210020127A; WO2019244821A1

Abstract

The invention provides an industrial manufacturing method of a zero-plane anchoring film, a good liquid crystal display element using the zero-plane anchoring film and a manufacturing method of the liquid crystal display element. A method of making a patterned zero-plane anchoring film, comprising: irradiating the radical generating film with radiation in a specific region to form a patterned radical generating film; and a step of bringing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound into contact with the patterned radical generating film, and imparting energy sufficient to cause the radical polymerizable compound to undergo a polymerization reaction to the liquid crystal composition while maintaining the state. And a method for manufacturing a functional film, comprising: a step of preparing a unit having a liquid crystal composition containing a liquid crystal and a radical polymerizable compound between a first substrate having a radical generating film and a second substrate having no radical generating film; and a step of imparting energy sufficient to polymerize the radical polymerizable compound to the unit.

Description

Method for manufacturing zero-plane anchoring film and liquid crystal display element

Technical Field

The present invention relates to a manufacturing method using a polymer stabilization technique that enables manufacturing of a zero-surface anchoring film (zero-anchoring film) by a method that is inexpensive and does not involve complicated steps, a liquid crystal display element that uses the manufacturing method and realizes further low-voltage driving, and a manufacturing method thereof.

Background

In recent years, liquid crystal display elements have been widely used in displays for mobile phones, computers, and televisions. Liquid crystal display elements have characteristics such as thinness, lightweight, and low power consumption, and are expected to be applied to VR, ultra-fine displays, and the like 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, and a film (liquid crystal alignment film) for inducing liquid crystals into a desired alignment state is used In all the 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 a problem that the manufacturing cost of the substrate is higher than that of IPS, and a display defect specific to an FFS mode called Vcom shift occurs. Further, photo-alignment has advantages that the size of a device to be manufactured can be increased and display characteristics can be greatly improved as compared with a rubbing method, but there is a problem in principle of photo-alignment (if the device is a decomposition type, display failure due to decomposition products exists, and if the device is an isomerization type, burn-in due to insufficient alignment force exists, and the like). In order to solve these problems, liquid crystal display element manufacturers and liquid crystal alignment film manufacturers have made various studies under the present circumstances.

On the other hand, in recent years, an IPS mode using a zero plane anchoring technique has been proposed, and it has been reported that by using this means, contrast can be improved and a large low voltage driving can be performed compared to a conventional IPS mode (see patent document 1).

Specifically, a liquid crystal alignment film having strong anchoring energy is used on one substrate, and a substrate provided with one electrode that generates a lateral electric field is subjected to a treatment that does not have any alignment regulating force of liquid crystal at all, and an IPS mode liquid crystal display element is manufactured using these steps.

In recent years, a technique of producing a zero-plane state using a thick polymer brush or the like and zero-plane anchoring IPS mode has been proposed (reference 2). By this technique, the contrast ratio is greatly improved and the drive voltage is greatly reduced.

On the other hand, there is a problem that the response speed, particularly the response speed when the voltage is OFF (OFF), is significantly reduced. The reason for this is that since the driving voltage is low, the influence of the response in a weak electric field as compared with a normal driving method and the anchoring force of the alignment film are extremely small, and therefore, it takes time to restore the liquid crystal. As a method for solving this problem, a means of forming a zero anchor only on the pixel electrode is proposed (patent document 3). Thus, it has been reported that the improvement of the luminance and the response speed can be compatible with each other.

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

It is considered that the delay of response speed during driving is suppressed by forming zero-plane anchors only on the electrodes of the IPS comb electrodes, and on the other hand, it is necessary to prepare a difficult technique of applying different materials to very fine regions in order to form the zero-plane anchors only on the electrodes, and it is considered that the practical industrialization is a major problem.

If the problems of the above-described technologies can be solved, there are also great cost advantages for panel manufacturers, and there are also advantages in that battery consumption is suppressed, image quality is improved, and the like.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for manufacturing a portion having an anchoring force with a zero-plane anchoring portion in a surface of a liquid crystal alignment film, a method for controlling an anchoring energy to an arbitrary state, and a lateral electric field liquid crystal display element which can simultaneously realize non-contact alignment, a reduction in driving voltage, and an increase in response speed at Off (Off) by a simple and inexpensive method at room temperature, and a method for manufacturing the same.

Means for solving the problems

The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that the above problems can be solved, and have completed the present invention having the following gist.

Namely, the present invention includes the following aspects.

[1] A method of making a patterned zero-plane anchoring film, comprising: irradiating the radical generating film with radiation in a specific region to form a patterned radical generating film; and a step of bringing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound into contact with the patterned radical generating film, and imparting energy sufficient to cause the radical polymerizable compound to undergo a polymerization reaction to the liquid crystal composition while maintaining the state.

[2] The method according to [1], wherein the radical generating film is a radical generating film subjected to a uniaxial orientation treatment.

[3] The method according to [1] or [2], wherein the step of imparting energy is performed in an electric field-free state.

[4] The method according to any one of [1] to [3], wherein the radical generating film is a film in which an organic group that induces radical polymerization is immobilized.

[5] The method according to any one of [1] to [3], wherein the radical generating film is obtained by applying a composition of a compound having a radical generating group and a polymer, curing the composition to form a film, and immobilizing the film in the film.

[6] The method according to any one of [1] to [3], wherein the radical generating film comprises a polymer containing an organic group which induces radical polymerization.

[7] The method according to [6], wherein the polymer having an organic group which induces radical polymerization is at least one polymer selected from the group consisting of a polyimide precursor obtained using a diamine component, a polyimide, a polyurea and a polyamide, and the diamine component contains a diamine having an organic group which induces radical polymerization.

[8] The method according to any one of [4], [6] and [7], wherein the organic group that induces radical polymerization is an organic group represented by any one of the following structures [ X-1] to [ X-18], [ W ], [ Y ] and [ Z ],

[ Compound 1]

(formula [ X-1]]～[X-18]Wherein S represents a site bonded to a portion other than the polymerizable unsaturated bond of the compound molecule₁、S₂Independently represents-O-, -NR-, -S-, R represents hydrogen atom, halogen atom, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, R represents₁、R₂Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms)

[ Compound 2]

(formula [ W)]、[Y]、[Z]Wherein 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, and R represents a site bonded to a portion other than the polymerizable unsaturated bond of the compound molecule⁹And R¹⁰Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R⁹And R¹⁰In the case of an alkyl group, the terminal groups may be bonded to each other to form a ring structure or may not be bonded to each other to form a ring structure; (ii) a Q represents the following structure;

[ Compound 3]

(in the formula, R¹¹represents-CH₂-, -NR-, -O-or-S-, wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and represents a site bonded to a portion other than Q in a compound molecule)

R₁₂Represents 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).

[9] The method according to claim 7, wherein the diamine having an organic group which induces radical polymerization is a diamine having a structure represented by the following general formula (6) or the following general formula (7),

[ Compound 4]

(in the formula (6), R⁶Represents a single bond, -CH₂-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂O-、-N(CH₃)-、-CON(CH₃) -or-N (CH)₃)CO-，

R⁷Represents a single bond, or a carbon atom number 1-20 subunit which is unsubstituted or substituted by a fluorine atomAlkyl, any-CH of the alkylene₂-or-CF₂-1 or more of-are each independently substituted or unsubstituted with a group selected from-CH ═ CH-, a divalent carbocyclic ring and a divalent heterocyclic ring, and are substituted or unsubstituted with any of the groups listed below, i.e., -O-, -COO-, -OCO-, -NHCO-, -CONH-, or-NH-not adjacent to each other;

R⁸represents a radical polymerization reactive group selected from the following formulae;

[ Compound 5]

(formula [ X-1]]～[X-18]Wherein S represents a site bonded to a portion other than a radical polymerization reactive group of a compound molecule₁、S₂Independently represents-O-, -NR-, -S-, R represents hydrogen atom, halogen atom, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, R represents¹、R²Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms))

[ Compound 6]

(in the formula (7), T¹And T²Each independently is a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH₂O-、-N(CH₃)-、-CON(CH₃) -or-N (CH)₃)CO-，

S⁰Represents a single bond, or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with a fluorine atom, or any-CH of the alkylene group₂-or-CF₂-1 or more of which are each independently substituted or unsubstituted by a group selected from-CH ═ CH-, a divalent carbocyclic ring and a divalent heterocyclic ring, and are substituted or unsubstituted by 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,

j is an organic group represented by any one of the following formulae,

[ Compound 7]

(formula [ W)]、[Y]、[Z]In the formula, represents and T₂A bonding site, Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene, with or without an organic group and/or a halogen atom as a substituent, and R⁹And R¹⁰Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q represents any of the following structures;

[ Compound 8]

(in the formula, R¹¹represents-CH₂-, -NR-, -O-or-S-, wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and represents a site bonded to a portion of a compound molecule other than Q)

R₁₂Represents 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)).

[10] The method according to any one of [1] to [9], 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.

[11] The method according to [10], wherein the polymerization reactive group of the radical polymerizable compound is selected from the following structures,

[ Compound 9]

(wherein, represents polymerizable unsaturation with a compound moleculeA site to which a portion other than the bond is bonded; r^bRepresents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR^c-S-, a binding group in an ester bond and an amide bond; r^cRepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).

[12] The method according to any one of [1] to [11], wherein the liquid crystal composition containing a liquid crystal and a radical polymerizable compound comprises a radical polymerizable compound: the Tg of the polymer obtained by polymerizing the radical polymerizable compound is 100 ℃ or lower.

[13] A method for manufacturing a liquid crystal cell, using any one of the methods according to [1] to [12], the method comprising:

a step of preparing a first substrate having a radical generating film and a second substrate having or not having a radical generating film;

a step of forming a cell so that the radical generating film on the first substrate faces the second substrate; and

and a step of filling a liquid crystal composition containing a liquid crystal and a radical polymerizable compound between the first substrate and the second substrate.

[14] The method of manufacturing a liquid crystal cell according to [13], wherein the second substrate is a second substrate having no radical generating film.

[15] The method of manufacturing a liquid crystal cell according to [14], wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment properties.

[16] The method of manufacturing a liquid crystal cell according to [15], wherein the liquid crystal alignment film having a uniaxial alignment property is a liquid crystal alignment film for horizontal alignment.

[17] The method of manufacturing a liquid crystal cell according to any one of [13] to [16], wherein the first substrate having the radical generating film is a substrate having comb-teeth electrodes.

[18] A liquid crystal composition comprising a liquid crystal and a radical polymerizable compound,

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,

the polymerization reactive group is selected from the following structures,

[ Compound 10]

(wherein R represents a site bonded to a portion other than the polymerizable unsaturated bond of the compound molecule; R^bRepresents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR^c-S-, a binding group in an ester bond and an amide bond; r^cRepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).

[19] A method for manufacturing a liquid crystal display element, wherein a film in a zero plane anchoring state is produced by using the method according to any one of [1] to [17 ].

[20] A liquid crystal display element obtained by the method according to [19 ].

[21] The liquid crystal display element according to [20], wherein the first substrate or the second substrate has an electrode.

[22] The liquid crystal display element according to [20] or [21], wherein the liquid crystal display element is a low-voltage-driven transverse electric field liquid crystal display element.

Effects of the invention

According to the present invention, the zero-plane anchor film can be produced industrially with high yield. The method of the present invention can be used to easily produce a liquid crystal display element similar to the zero plane anchoring IPS mode liquid crystal display element described in patent documents 1 and 2, using an inexpensive raw material and a conventional production method. Further, the liquid crystal display element obtained by the manufacturing method of the present invention can provide a liquid crystal display element having the following excellent characteristics: compared with the prior art, the response speed of the liquid crystal is higher when the liquid crystal is turned Off (Off), the driving voltage is low, no bright spots exist, the Vcom shift can be inhibited in the IPS mode, and the resolution can be higher in the FFS mode.

Drawings

Fig. 1 is a diagram of a TN cell having a substrate that forms a film having a zero plane anchor region and a non-zero plane anchor region by having a UV irradiated region and a region that is not UV irradiated. In the cell, the transparent areas are not UV-illuminated and the non-transparent areas are areas with UV-illumination.

Detailed Description

The present invention is a method for producing a film in which a zero-plane anchor region and a strong anchor region are patterned, characterized in that a polymerizable compound is polymerized by UV or heat in a state in which a liquid crystal containing a specific polymerizable compound is brought into contact with a radical generating film through a step of forming the radical generating film having an anchoring force on a substrate and irradiating the radical generating film with radiation in a region where the anchoring force is to be maintained. More specifically, the present invention is a method of manufacturing a film patterned with zero-plane anchor regions and strong anchor regions, comprising: a step of preparing a unit having a liquid crystal composition containing a liquid crystal and a radical polymerizable compound between a first substrate having a radical generating film treated with radiation and a second substrate having or not having a radical generating film; and a step of imparting energy sufficient to cause the radical polymerizable compound to undergo a polymerization reaction to the unit. Preferably, the method for manufacturing a liquid crystal cell includes: a step of preparing a first substrate having a radical generating film subjected to radiation irradiation treatment and a second substrate having no radical generating film; a step of manufacturing a cell so that the radical generating film faces the second substrate; and a step of filling a liquid crystal composition containing a liquid crystal and a radical polymerizable compound between the first substrate and the second substrate. For example, in a method for manufacturing a low-voltage-driven IPS liquid crystal display device, the second substrate is a substrate (disc) having no radical generating film and a uniaxially-aligned liquid crystal alignment film, and the first substrate is a substrate having comb-teeth electrodes.

In the present invention, the "zero plane anchoring film" means a film which has no orientation regulating force of liquid crystal molecules in the in-plane direction at all, or is weaker than intermolecular force between liquid crystals even if any, and which cannot uniaxially orient liquid crystal molecules in any direction only by the film. The zero-plane anchor film is not limited to a solid film, and may include a liquid film covering a solid surface. In general, in a liquid crystal display element, liquid crystal is aligned by using a pair of films for regulating alignment of liquid crystal molecules, that is, liquid crystal alignment films, but the liquid crystal may be aligned when the zero plane anchor film and the liquid crystal alignment film are used in pair. This is because the alignment regulating force of the liquid crystal alignment film is also transmitted in the thickness direction of the liquid crystal layer by the intermolecular force between the liquid crystal molecules, and as a result, the liquid crystal molecules close to the zero plane anchor film are also aligned. Therefore, when a liquid crystal alignment film for horizontal alignment is used as the liquid crystal alignment film, a horizontal alignment state can be produced in the liquid crystal cell as a whole. The horizontal alignment is a state in which the long axes of the liquid crystal molecules are aligned substantially parallel to the liquid crystal alignment film surface, and a tilt alignment of about several degrees is included in the category of horizontal alignment.

[ composition for Forming free-radical-generating film ]

The radical generating film-forming composition for forming the radical generating film used in the present invention contains a polymer as a component and a group capable of generating radicals. In this case, the composition may be a composition containing a polymer in which groups capable of generating radicals are bonded, or a composition of a compound having groups capable of generating radicals and a polymer as a base resin. By applying such a composition and curing the composition to form a film, a radical generating film in which a radical generating group is fixed in the film can be obtained. The group capable of generating a radical is preferably an organic group which induces radical polymerization.

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

[ Compound 11]

[ Compound 12]

(formula [ W)]、[Y]、[Z]Wherein 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, and R represents a site bonded to a portion other than the polymerizable unsaturated bond of the compound molecule⁹And R¹⁰Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R⁹And R¹⁰In the case of an alkyl group, the terminal groups may be bonded to each other to form a ring structure or may not be bonded to each other to form a ring structure; q represents any one of the following structures,

[ Compound 13]

(in the formula, R¹¹represents-CH₂-, -NR-, -O-or-S-, wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and represents a site bonded to a portion other than Q in the compound molecule. )

The polymer is preferably at least 1 polymer selected from polyimide precursors, polyimides, polyureas, polyamides, polyacrylates, polymethacrylates, polyorganosiloxanes, and the like.

In order to obtain the radical generating film used in the present invention, in the case of using the above-mentioned polymer having an organic group which induces radical polymerization, it is preferable to perform production using the following monomers as monomer components to obtain a polymer having a group capable of generating radicals: a monomer having a photoreactive side chain containing at least one selected from the group consisting of a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarinyl group, a styryl group, and a cinnamoyl group, or a monomer having a site generating a radical on a side chain thereof, which is decomposed by ultraviolet irradiation. On the other hand, considering the problem that the monomer generating a radical spontaneously polymerizes itself to finally form an unstable compound, a polymer derived from a diamine having a radical generating site is preferable in terms of ease of synthesis, and polyimide precursors such as polyamic acid and polyamic acid ester, polyimide, polyurea, and polyamide are more preferable.

Specifically, the diamine containing a radical generating site is, for example, a diamine having a side chain capable of generating a radical and performing polymerization, and examples thereof include a diamine represented by the following general formula (6), but the diamine is not limited thereto.

[ Compound 14]

R⁷Represents a single bond, or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with a fluorine atom, or any-CH of the alkylene group₂-or-CF₂1 or more of-are each independently substituted or not substituted by a group selected from-CH- ═ CH-, a divalent carbocyclic ring and a divalent heterocyclic ring, and under the condition that any of the groups enumerated below, i.e., -O-, -COO-, -OCO-, -NHCO-, -CONH-or-NH-are not adjacent to each otherWith or without substitution by these groups;

R⁸represents a radical polymerization reactive group selected from the following formulae.

[ Compound 15]

(formula [ X-1]]～[X-18]Wherein S represents a site bonded to a portion other than a radical polymerization reactive group of a compound molecule₁、S₂Each independently represents-O-, -NR-, -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms₁₂Represents 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, R₁、R₂Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms)

Two amino groups (-NH) in the formula (6)₂) The bonding position of (2) is not limited. Specifically, examples of the bonding group to the side chain include a 2,3 position, a 2,4 position, a 2,5 position, a 2,6 position, a 3,4 position, and a 3,5 position on the benzene ring. Among them, from the viewpoint of reactivity in synthesizing a polyamic acid, a position of 2,4, a position of 2,5, or a position of 3,5 is preferable. In view of easiness in synthesizing the diamine, the 2,4 position or the 3,5 position is more preferable.

Specific examples of the diamine having a photoreactive group containing at least 1 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.

[ Compound 16]

(in the formula, J¹Is a bonding group selected from a single bond, -O-, -COO-, -NHCO-, or-NH-, J²Represents a single bond or is unsubstituted or substituted by fluorine atomsAlkylene group having 1 to 20 carbon atoms

The diamine having a side chain of a site where radicals are generated by decomposition by ultraviolet irradiation includes a diamine represented by the following general formula (7), but is not limited thereto.

[ Compound 17]

(in the formula (7), T₁And T₂Each independently is a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH₂O-、-N(CH₃)-、-CON(CH₃) -or-N (CH)₃)CO-，

S⁰Represents a single bond, or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with a fluorine atom, or any-CH of the alkylene group₂-or-CF₂-1 or more of which are each independently substituted or unsubstituted by a group selected from-CH ═ CH-, divalent carbocyclic and divalent heterocyclic rings, and are substituted or unsubstituted by 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,

j is an organic group represented by any one of the following formulae,

[ Compound 18]

(formula [ W)]、[Y]、[Z]In the formula, represents and T₂Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene, with or without an organic group and/or a halogen atom as a substituent, and R⁹And R¹⁰Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q represents any of the following structures;

[ Compound 19]

Two amino groups (-NH) in the above formula (7)₂) The bonding position of (2) is not limited. Specifically, examples of the bonding group to the side chain include a 2,3 position, a 2,4 position, a 2,5 position, a 2,6 position, a 3,4 position, and a 3,5 position on the benzene ring. Among them, from the viewpoint of reactivity in synthesizing a polyamic acid, a position of 2,4, a position of 2,5, or a position of 3,5 is preferable. In view of easiness in synthesizing the diamine, the 2,4 position or the 3,5 position is more preferable.

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

[ Compound 20]

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

The diamine may be used in a mixture of 1 or 2 or more depending on the characteristics such as liquid crystal alignment property, polymerization reaction sensitivity, voltage holding property, and accumulated charge when the diamine is formed into a radical generating film.

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% of the total diamine components used for the synthesis of the polymer contained in the radical generating film-forming composition.

In addition, in the case where the polymer used for the radical generating film of the present invention is obtained from a diamine, other diamines than the diamine having the radical generating site described above may be used in combination as the diamine component as long as the effect of the present invention is not impaired. Specific examples thereof include 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, 5-dimethyl-p-phenylenediamine, 2, 4-diaminotoluene, 2, 5-diaminophenol, 2, 4-diaminobenzyl alcohol, 4,6-, 3,3' -dicarboxy-4, 4' -diaminobiphenyl, 3' -difluoro-4, 4' -biphenyl, 3' -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' -diaminodiphenyl ether, 2,3' -diaminodiphenyl ether, and mixtures thereof, 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-substituted diphenylamines, N-substituted diphenylamines, 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, 1, 4-diaminonaphthalene, 2 '-diaminobenzophenone, 2,3' -diaminobenzophenone, 1, 5-diaminonaphthalene, 1, 6-diaminonaphthalene, 1, 7-diaminonaphthalene, 1, 8-diaminonaphthalene, 2, 5-diaminonaphthalene, 2, 6-diaminonaphthalene, 2, 7-diaminonaphthalene, 2, 8-diaminonaphthalene, 1, 2-bis (4-aminophenyl) ethane, 1, 2-bis (3-aminophenyl) ethane, 1, 3-bis (4-aminophenyl) propane, 1, 3-bis (3-aminophenyl) propane, 1, 4-bis (4-aminophenyl) butane, 1, 4-bis (3-aminophenyl) butane, bis (3, 5-diethyl-4-aminophenyl) methane, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenyl) benzene, 1, 3-bis (4-aminophenyl) benzene, 1, 4-bis (4-aminobenzyl) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4' - [1, 4-phenylenebis (methylene) ] diphenylamine, 4,4' - [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-aminobenzamide), N '- (1, 4-phenylene) bis (3-aminobenzamide), N' - (1, 3-phenylene) bis (3-aminobenzamide), N, N ' -bis (4-aminophenyl) terephthalamide, 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, 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, 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 such as N-tert-butoxycarbonyl-N- (2- (4-aminophenyl) ethyl) -N- (4-aminobenzyl) amine, and the like.

The other diamines may be used in combination of 1 or 2 or more depending on the properties such as liquid crystal alignment property, polymerization reaction sensitivity, voltage holding property, and accumulated charge when the film is formed as a radical generating film.

In the synthesis of the polymer being a polyamic acid, the tetracarboxylic dianhydride to be reacted with the diamine component is not particularly limited. Specific examples thereof include 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, 1,3, 3-hexafluoro-2, 2-bis (3, 4-dicarboxyphenyl) propane, Bis (3, 4-dicarboxyphenyl) dimethylsilane, bis (3, 4-dicarboxyphenyl) diphenylsilane, 2,3,4, 5-pyridinetetracarboxylic acid, 2, 6-bis (3, 4-dicarboxyphenyl) pyridine, 3',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, 1,2,3, 4-cyclopentanetetracarboxylic acid, 1,2, 4-cyclohexanedicarboxylic acid, 1,3, 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, 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-dioxotetrahydrofuryl) -3-methyl-3-cyclohexane-1, 2-dicarboxylic acid, tetracyclo [6,2,1,1,0<2,7> ] dodecane-4, 5,9, 10-tetracarboxylic acid, 3,5, 6-tricarboxynorbornane-2: 3,5: 6-dicarboxylic acid, 1,2,4, a dianhydride of a tetracarboxylic acid such as 5-cyclohexanetetracarboxylic acid.

Of course, the tetracarboxylic dianhydride may be used in combination of 1 type or 2 or more types depending on the characteristics such as liquid crystal alignment property, sensitivity of 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-tetrahydrofurante, 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, Dialkyl 1,2,3, 4-butanetetracarboxylic acid ester, dialkyl bicyclo [3,3,0] octane-2, 4,6, 8-tetracarboxylic acid ester, dialkyl 3,3',4,4' -dicyclohexyltetracarboxylic acid ester, dialkyl 2,3, 5-tricarboxycyclopentylacetate, cis-3, 7-dibutylcyclooctan-1, 5-diene-1, 2,5, 6-tetracarboxylic acid ester, dialkyl tricyclo [4.2.1.0<2,5> ] nonane-3, 4,7, 8-tetracarboxylic acid 3,4:7, 8-dialkyl ester, hexacyclo [6.6.0.1<2,7> ] 0<3,6>.1<9,14>.0<10,13> ] hexadecane-4, 5,11, 12-tetracarboxylic acid 4,5:11, 12-dialkyl ester, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid dialkyl ester, and the like.

Examples of the aromatic tetracarboxylic acid dialkyl ester include a dialkyl pyromellitate, a dialkyl 3,3',4,4' -biphenyltetracarboxylic acid ester, a dialkyl 2,2',3,3' -biphenyltetracarboxylic acid ester, a dialkyl 2,3,3', 4-biphenyltetracarboxylic acid ester, a dialkyl 3,3',4,4' -benzophenonetetracarboxylate, a dialkyl 2,3,3',4' -benzophenonetetracarboxylate, a dialkyl bis (3, 4-dicarboxyphenyl) ether ester, a dialkyl bis (3, 4-dicarboxyphenyl) sulfone ester, a dialkyl 1,2,5, 6-naphthalenetetracarboxylate, and a dialkyl 2,3,6, 7-naphthalenetetracarboxylate.

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 may be used in accordance with availability and the like. Specific structures of the diisocyanates are shown below.

[ Compound 21]

In the formula R₂、R₃Represents 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 view of versatility and characteristics, K-1, K-7, K-8, K-9 and K-10 are particularly preferable, K-12 is particularly preferable from the viewpoint of electrical characteristics, and K-13 is particularly preferable from the viewpoint of liquid crystal alignment properties. The diisocyanate may be used in combination with 1 or more kinds thereof, and is preferably used in various applications depending on the desired properties.

In addition, a part of the 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-cyclohexanedicarboxylic acid, 1, 2-cyclohexanedicarboxylic acid, 1,4- (2-norbornene) dicarboxylic acid, 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, etc.

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-biphenyldicarboxylic acid, 4' -terphenyldicarboxylic acid, 4' -diphenylmethanedicarboxylic acid, 4' -diphenylethanedicarboxylic acid, 4' -diphenylpropanedicarboxylic acid, 5-dimethylisophthalic acid, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 4,4' -diphenylhexafluoropropane dicarboxylic acid, 4' -diphenyl ether dicarboxylic acid, 4' -dibenzyldicarboxylic acid, 4' -stilbenedicarboxylic acid, 4' -diphenylacetylene dicarboxylic acid (4,4' -tolanedicarboxylic 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, 4' - (oxydiphenylene) ] dibutanoic acid, Dicarboxylic acids such as (isopropylidenedip-phenylenedioxy) dibutyrate and bis (p-carboxyphenyl) dimethylsilane.

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

The various dicarboxylic acids mentioned above may be acid dihalides or anhydrides of dicarboxylic acids. 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' -biphenyldicarboxylic acid, 4' -diphenylmethanedicarboxylic acid, 4' -diphenylethanedicarboxylic acid, 4' -diphenylpropanedicarboxylic acid, 4' -diphenylhexafluoropropanedicarboxylic acid, 2-bis (phenyl) propanedicarboxylic acid, 4-terphenyldicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 5-pyridinedicarboxylic acid, acid dihalides thereof, and the like are preferably used. These compounds sometimes exist as isomers, and may be mixtures containing them. In addition, 2 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 formed. 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. Since moisture in the organic solvent acts as a cause of inhibiting the polymerization reaction and hydrolyzing the polymer formed, it is preferable to use an organic solvent that has been dehydrated and dried.

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, hexamethylsulfoxide, gamma-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentyl ketone, methylnonyl ketone, methylethylketone, methylisoamylketone, methylisopropylketone, methylcellosolve, ethylcellosolve, methylcellosolve acetate, dimethylvalerolactone, dimethylcellosolve, ethylcellosolve, butyl cellosolve acetate, 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-tert-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, ethyl carbitol, ethylene glycol monoacetate, ethylene glycol monoacetyl ether, diethylene glycol monomethyl ether, propylene glycol monoethyl ether, Diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic 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 the 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 a tetracarboxylic dianhydride component and a diamine component. Any of these methods may 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 may 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 mole number of the tetracarboxylic dianhydride component to the total mole number 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 corresponding polyamic acid is obtained by reacting a tetracarboxylic acid derivative having a corresponding structure, such as tetracarboxylic acid or a tetracarboxylic acid dihalide, with a known method, 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 catalytic imidization in which a catalyst is added to a solution of the polyamic acid. 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 improving the voltage holding ratio. On the other hand, from the viewpoint of whitening properties, that is, from the viewpoint of suppressing precipitation of a polymer in a varnish, it is preferably 70% or less. In view of both characteristics, 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 basic group 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 catalytic 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 formation of the precipitate 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 may 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 the precipitation recovery in the 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 comprises a polymer containing an organic group which induces radical polymerization, the radical generating film forming composition used in the present invention may comprise other polymers than the polymer containing an organic group which induces radical polymerization. In this case, the content of the other polymer in the total polymer component is preferably 5 to 95% by mass, more preferably 30 to 70% by mass.

The molecular weight of the polymer contained in the radical generating film forming composition is preferably 5000 to 1000000, more preferably 10000 to 150000, in terms of a weight average molecular weight measured by a Gel Permeation Chromatography (GPC) method, in consideration of the strength of the radical generating film obtained by coating the radical generating film, workability in forming a coating film, uniformity of the coating film, and the like.

As the polymer used in the radical generating film of the present invention obtained by applying a composition of a compound having a radical generating group and a polymer and curing the composition to form a film to fix the composition in the film, at least 1 polymer selected from a polyimide precursor produced by the above production method, and a polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, and the like can be used, the polymer is obtained using a diamine component which is 0 mol% of the diamine component having a site where radical polymerization occurs in the total diamine component used for synthesis of the polymer contained in the radical generating film forming composition. The compound having a radical-generating group to be added at this time includes the following compounds.

The compound that generates radicals by heat is a compound that generates radicals by heating to a decomposition temperature or higher. Examples of the radical thermal polymerization initiator include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxy acetals (dibutyl peroxycyclohexane, etc.), peroxy alkyl esters (tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, tert-amyl 2-ethylcyclohexane peroxide, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 2' -bis (2-hydroxyethyl) azobisisobutyronitrile, etc.). Such radical thermal polymerization initiators may be used in 1 kind alone, or 2 or more kinds may be used in combination.

The compound that generates radicals by light is not particularly limited as long as it is a compound that initiates 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, benzoanthraquinone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, and mixtures thereof, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4-dimethylaminobenzoic acid ethyl ester, isoamyl 4-dimethylaminobenzoate, 4,4' -di (tert-butylperoxycarbonyl) benzophenone, 3,4,4' -tri (tert-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2- (4' -methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (3',4' -dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (2',4' -dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (2 '-methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4' -pentyloxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 4- [ 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, and mixtures thereof, 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-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-hexylperoxy carbonyl) benzophenone, 3' -bis (methoxycarbonyl) -4,4' -bis (tert-butylperoxycarbonyl) benzophenone, 3,4 '-bis (methoxycarbonyl) -4,3' -bis (tert-butylperoxycarbonyl) benzophenone, 4 '-bis (methoxycarbonyl) -3,3' -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 2 or more of them may be used in combination.

When the radical generating film contains a polymer containing an organic group which induces radical polymerization, the radical generating film may contain the compound having a radical generating group in order to accelerate radical polymerization when energy is applied.

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. N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is particularly preferable, and a mixed solvent of 2 or more kinds may be used.

Further, it is preferable to use a solvent for improving the uniformity and 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 and 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 monobutyl ether, ethylene glycol monob, 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, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl acetate, isopropyl propionate, isobutyl propionate, butyl acetate, butyl butyrate, butyl propionate, isobutyl propionate, ethyl propionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, 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 components other than those described above. Examples thereof include: a compound which improves the film thickness uniformity and surface smoothness when the radical generating film forming composition is applied, a compound which improves the adhesion between the radical generating film forming composition and the substrate, a compound which further improves the film strength of the radical generating film forming composition, and the like.

Examples of the compound for improving the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. More specifically, examples thereof include Eftop EF301, EF303, EF352 (manufactured by Tohkem Products), MEGAFAC F171, F173, R-30 (manufactured by Dainippon ink), FLUORAD FC430, FC431 (manufactured by Sumitomo 3M), Asahiguard AG710, SURLON S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi glass Co., Ltd.). When these surfactants are used, the amount thereof is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, based on 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, 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-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N' -tetraglycidyl-4, 4 '-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, poly (ethylene glycol) diglycidyl ether, poly (propylene glycol) diglycidyl ether, 1,3, N, N', N '-tetraglycidyl-2, 4-hexanediol, 4' -diaminodiphenylmethane, N, 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 these compounds are 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 composition for forming a free-radical-generating film.

In addition to the above, a dielectric or conductive material for changing the electrical characteristics such as the dielectric constant and the electrical 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.

[ free radical generating film ]

The radical generating film of the present invention is obtained by using the above-mentioned 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 and sintering the composition may be used as it is as a radical generating film. The cured film may be rubbed, irradiated with polarized light, light of a specific wavelength, or the like, treated with an ion beam, or the like, or irradiated with UV as an alignment film for PSA to a liquid crystal display element filled with liquid crystal.

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 preferably a substrate in which a transparent electrode for driving liquid crystal is formed on a substrate.

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

Electrode patterns such as standard IPS comb-teeth electrodes and PSA fishbone electrodes, or projection patterns such as MVA, may be used for the substrate that can be used in the IPS liquid crystal display device.

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

In the case of a transmissive liquid crystal display element, the substrate as described above is generally used, but in the case of a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used if it is a single-sided substrate. In this case, a material such as aluminum that reflects light may 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, and roll coating, and the transfer printing method is widely used industrially from the viewpoint of productivity, and is 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 firing is not performed 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 on a hot plate at the temperature of 40-150 ℃, preferably 60-100 ℃ for 0.5-30 minutes, preferably 1-5 minutes.

The coating film formed by applying the radical generating film forming composition by the above method 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 may be generally any time from 5 minutes to 240 minutes. Preferably 10 to 90 minutes, and more preferably 20 to 90 minutes. The heating may be generally carried out by a known method such as a hot plate, a hot air circulation oven, an IR oven, a belt oven, or the like.

The thickness of the cured film may be selected as needed, and is preferably 5nm or more, more preferably 10nm or more, because the reliability of the liquid crystal display device is easily obtained. In addition, 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.

When the alignment treatment is performed 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 in which the comb-teeth electrodes are formed, the direction can be 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 set to be substantially the same direction as the extending direction of the comb-teeth electrodes.

The process of creating the zero anchor portion and the strong anchor portion includes a method of irradiating radiation in an arbitrary pattern through a photomask or the like. The method is a step of irradiating the radical generating film with radiation in advance to eliminate the radical generating site and prevent the formation of a zero-anchoring state. Examples of the radiation used in this step include polarized light, light having a specific wavelength, and an ion beam. It is particularly preferable that the photo radical generating site is irradiated with light having a wavelength at which the absorbance of the corresponding portion is highest.

The second substrate of the present invention is the same as the first substrate described above except that the radical generating film is not provided. The substrate is preferably a substrate having a liquid crystal alignment film, which is known in the art.

< liquid Crystal cell >

The liquid crystal cell of the present invention is obtained by forming a radical generating film on a substrate by the above-described method, disposing the substrate having the radical generating film (first substrate) and a known substrate having a liquid crystal alignment film (second substrate) so that the radical generating film and the liquid crystal alignment film face each other, sandwiching a spacer, fixing the spacer with a sealant, injecting a liquid crystal composition containing a liquid crystal and a radical polymerizable compound, and sealing the mixture. In this case, the size of the spacer used 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 thus produced 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.

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

In the production of the liquid crystal display element of the present invention, 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 "a compound having a monofunctional polymerization reactive 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 is compatible with a liquid crystal.

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

[ Compound 22]

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

The compound having a monofunctional radical polymerization reactive group is an unsaturated bond capable of radical polymerization 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, vinyl fluoride, etc.), but is not limited thereto. These various radically polymerizable monomers may be used alone, or 2 or more kinds may be used in combination. These compounds are preferably compatible with liquid crystals.

Further, the radical polymerizable compound is also preferably a compound represented by the following formula (1).

[ Compound 23 ]

In the formula (1), R^aAnd R^bEach independently represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR^cA bonding group of- (O-X-O) -, - (S) -, - (Y-O) -, an ester bond, an amide bond, R^cRepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In addition, the radical polymerizable compound represented by the formula (1) is preferably a compound in which E is an ester bond (-C (═ O) -O-or-O-C (═ O) -) in the formula, and particularly preferably a compound having the following structure, from the viewpoint of ease of synthesis, compatibility with a liquid crystal, and polymerization reactivity, and is not particularly limited.

[ Compound 24 ]

In the formulas (1-1) and (1-2), Ra and Rb independently represent a linear alkyl group having 2-8 carbon atoms.

These various radically polymerizable monomers may be used alone, or 2 or more kinds may be used in combination. Further, it preferably has compatibility with liquid crystal.

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, more preferably 20% by mass or less, based on the total mass of the liquid crystal and the radical polymerizable compound.

The Tg of the polymer obtained by polymerizing the radically polymerizable compound is preferably 100 ℃ or lower.

Note that, the liquid crystal generally means: the substance in a state exhibiting both properties of a solid and a liquid includes a nematic liquid crystal and a smectic liquid crystal as typical liquid crystal phases, and the liquid crystal usable in the present invention is not particularly limited. If exemplified, 4-pentyl-4' -cyanobiphenyl.

Next, energy sufficient to cause the radical polymerizable compound to undergo a polymerization reaction is applied to the liquid crystal cell into which the mixture (liquid crystal composition) containing the liquid crystal and the radical polymerizable compound is introduced. This can be performed, for example, by applying heat or UV irradiation, and the radical polymerizable compound is polymerized at that time, thereby exhibiting desired characteristics. Among them, UV irradiation is preferable in that a pattern having orientation can be formed by using UV and a polymerization reaction can be generated in a short time.

In addition, heating may be performed when UV irradiation is performed. The heating temperature in the UV irradiation is preferably within a temperature range in which the introduced liquid crystal exhibits liquid crystallinity, and is usually 40 ℃ or higher, and is preferably lower than a temperature at which the liquid crystal becomes an isotropic phase.

Here, the UV irradiation wavelength at the time of UV irradiation is preferably selected to have a wavelength at which the yield of the reaction quantum of the polymerizable compound to be reacted is best, the irradiation amount of UV is usually 0.01 to 30J, preferably 10J or less, and when the irradiation amount of UV is small, the decrease in reliability including the destruction of the member constituting the liquid crystal display can be suppressed, and the tact time in manufacturing can be improved by reducing the UV irradiation time, which is preferable.

Further, the heating for polymerization by heating alone without UV irradiation is preferably performed at a temperature at which the polymerizable compound reacts, that is, in a temperature range lower than the decomposition temperature of the liquid crystal. Specifically, it is, for example, 100 ℃ to 150 ℃.

When sufficient energy is applied to cause the radical polymerizable compound to undergo a polymerization reaction, it is preferably in an electric field-free state without applying a voltage.

< liquid Crystal display element >

The liquid crystal cell obtained in this manner can be used to produce a liquid crystal display element.

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

Further, a backlight, a polarizing plate, a λ/4 plate, a transparent electrode, a polarizing film, a color filter layer, and the like may be provided in the liquid crystal cell as needed in a conventional manner to produce a transmissive liquid crystal display element.

Examples

The present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The polymerization of the polymer and the method for evaluating the shorthand notation and the characteristics of the compound used in the preparation of the film-forming composition are as follows.

[ Compound 25 ]

NMP: n-methyl-2-pyrrolidone,

GBL: gamma-butyl lactone,

BCS: butyl cellosolve

< measurement of viscosity >

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

< measurement of imidization Rate >

20mg of the polyimide powder was put into an NMR sample tube (NMR sample tube Standard (. phi.5) manufactured by Softykuba Seisakusho), 0.53ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture) was added thereto, and the mixture was dissolved completely by applying ultrasonic waves. The 500MHz proton NMR of the solution was measured by a measuring apparatus (JNW-ECA 500, manufactured by DATUM, Japan).

The imidization rate is determined using protons derived from 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 amide groups in the vicinity of 9.5 to 10.0 ppm.

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

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

< preparation of Polymer polymerization and radical generating film Forming composition >

Synthesis example 1

Polymerization of TC-1, TC-2(50)/DA-1(50), DA-2(50) polyimides

In a 100ml 4-necked flask equipped with a nitrogen inlet tube, an air-cooling tube and a mechanical stirrer, 1.62g (15.00mmol) of DA-1 and 3.96g (15.00mmol) of DA-2 were weighed, and 48.2g of NMP48.2g was added thereto and stirred under a nitrogen atmosphere to completely dissolve the mixture. After confirming the dissolution, 3.75g (15.00mmol) of TC-2 was added, and the mixture was reacted at 60 ℃ for 3 hours under a nitrogen atmosphere. The temperature was again returned to room temperature, and 2.71g (13.80mmol) of TC-1 was added to the mixture, followed by reaction at 40 ℃ under nitrogen for 12 hours. The polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity reached 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, 60g of the polyamic acid solution obtained above was weighed, 111.4g of NMP was added to prepare a 7 mass% solution, 9.10g (88.52mmol) of acetic anhydride and 3.76g (47.53mmol) of pyridine were added while stirring, and after stirring at room temperature for 30 minutes, the mixture was stirred at 55 ℃ for 3 hours to effect a reaction. After completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500ml of methanol with stirring to precipitate a solid. The solid was recovered by filtration, and further the solid was put into 300ml of methanol and washed with stirring for 30 minutes, which was performed 2 times in total, and the solid was recovered by filtration, air-dried, and then dried in a vacuum oven at 60 ℃, to obtain polyimide (PI-1) having a number average molecular weight of 11300, a weight average molecular weight of 32900, and an imidization rate of 53%.

Synthesis example 2

Polymerization of TC-1, TC-2(50)/DA-1(50), DA-3(50) polyimides

In a 100ml 4-neck flask equipped with a nitrogen introduction tube, an air cooling tube and a mechanical stirrer, 1.62g (15.00mmol) of DA-1 and 4.96g (15.00mmol of DA-3) were weighed, 51.90g of NMP was added, and the mixture was stirred under a nitrogen atmosphere to completely dissolve the DA-1 and the NMP, after confirming the dissolution, 3.75g (15.00mmol) of TC-2 was added, the mixture was reacted at 60 ℃ under a nitrogen atmosphere for 3 hours, the mixture was returned to room temperature again, 2.64g (13.5mmol) of TC-1 was added, the mixture was reacted at 40 ℃ under a nitrogen atmosphere for 12 hours, and the polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity reached 1000 mPas, whereby a polymerization solution having a polyamic acid concentration of 20 mass% was obtained.

In a 200ml Erlenmeyer flask equipped with a magnetic stirrer, 60g of the polyamic acid solution obtained above was weighed, 111.4g of NMP was added to prepare a 7 mass% solution, 8.38g (81.4mmol) of acetic anhydride and 3.62g (45.8mmol) of pyridine were added with stirring, and after stirring at room temperature for 30 minutes, the reaction was carried out by stirring at 55 ℃ for 3 hours. After completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500ml of methanol with stirring to precipitate a solid. The solid was recovered by filtration, and the solid was further put into 300ml of methanol and washed with stirring for 30 minutes, which was performed 2 times in total, and the solid was recovered by filtration, air-dried, and then dried in a vacuum oven at 60 ℃, to obtain polyimide (PI-2) having a number average molecular weight Mn of 13100, a weight average molecular weight Mw of 34000, and an imidization rate of 55%.

Synthesis example 3

Polymerization of TC-1, TC-2(50)/DA-1(50), DA-4(50) polyimides

In a 100ml 4-necked flask equipped with a nitrogen inlet tube, an air-cooling tube and a mechanical stirrer, 1.62g (15.00mmol) of DA-1 and 5.65g (15.00mmol) of DA-4 were weighed out, and 55.4g of NMP was added thereto and stirred under a nitrogen atmosphere to completely dissolve them. After confirming the dissolution, 3.75g (15.00mmol) of TC-2 was added, and the mixture was reacted at 60 ℃ for 3 hours under a nitrogen atmosphere. The temperature was again returned to room temperature, and 2.82g (14.40mmol) of TC-1 was added to the reaction solution, followed by reaction at 40 ℃ under nitrogen for 12 hours. The polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity reached 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, 60g of the polyamic acid solution obtained above was weighed, 111.4g of NMP was added to prepare a 7 mass% solution, 8.36g (81.2mmol) of acetic anhydride and 3.65g (46.1mmol) of pyridine were added while stirring, and after stirring at room temperature for 30 minutes, the mixture was stirred at 55 ℃ for 3 hours to effect reaction. After completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500ml of methanol with stirring to precipitate a solid. The solid was recovered by filtration, and further the solid was put into 300ml of methanol and washed with stirring for 30 minutes, which was performed 2 times in total, and the solid was recovered by filtration, air-dried, and then dried in a vacuum oven at 60 ℃, to obtain polyimide (PI-3) having a number average molecular weight Mn of 12900, a weight average molecular weight Mw of 31000, and an imidization rate of 51%.

Free radical generating film forming composition: preparation of AL1

In a50 ml Erlenmeyer flask equipped with a magnetic stirrer, 2.0g of the polyimide powder (PI-1) obtained in Synthesis example 1 was weighed, 18.0g of NMP was added, and the mixture was stirred at 50 ℃ to completely dissolve the powder. Further, 6.7g of NMP and 6.7g of BCS were added and further stirred for 3 hours, thereby obtaining a radical generating film forming composition of the present invention: AL1 (solid content: 6.0 mass%, NMP: 66 mass%, BCS: 30 mass%).

Free radical generating film forming composition: preparation of AL2

In a50 ml Erlenmeyer flask equipped with a magnetic stirrer, 2.0g of the polyimide powder (PI-2) obtained in Synthesis example 2 was weighed, 18.0g of NMP was added, and the mixture was stirred at 50 ℃ to completely dissolve the powder. Further, 6.7g of NMP and 6.7g of BCS were added and further stirred for 3 hours, thereby obtaining a radical generating film forming composition of the present invention: AL2 (solid content: 6.0 mass%, NMP: 66 mass%, BCS: 30 mass%).

Non-free radical generating film-forming composition: preparation of AL3

In a50 ml Erlenmeyer flask equipped with a magnetic stirrer, 2.0g of the polyimide powder (PI-3) obtained in Synthesis example 3 was weighed, 18.0g of NMP was added, and the mixture was stirred at 50 ℃ to completely dissolve the powder. Further, 6.7g of nmp and 6.7g of bcs were added, and the mixture was further stirred for 3 hours, thereby obtaining a comparative non-radical generating film-forming composition: AL3 (solid content: 6.0 mass%, NMP: 66 mass%, BCS: 30 mass%).

[ TABLE 1]

TABLE 1 composition of polyimides

[ TABLE 2]

TABLE 2 composition of film-forming composition

[ TABLE 3]

TABLE 3 compositions using liquid crystals

Using liquid crystals	Liquid crystal display device	Additive agent
			LC-1	MLC-3018U	Is free of
LC-2	MLC-3018U	HMA 10wt％
			LC-3	MLC-3018U	IDHex 7wt％
LC-4	MLC-3018U	C2C6 5wt％
			LC-5	MLC-3019	Is free of
LC-6	MLC-3019	HMA 10wt％
			LC-7	MLC-3019	IDHex 7wt％
LC-8	MLC-3019	C2C6 5wt％

< production of polymerizable Compound >

Polymerizable Compound Synthesis example 1

Synthesis of ethyl 2- (heptanoyloxymethyl) acrylate

[ Compound 26 ]

Step 1: synthesis of 2-hydroxy ethyl methacrylate

In a500 ml four-necked flask equipped with a nitrogen inlet tube, 10mg of 4-methoxyphenol and DABCO (1, 4-diazabicyclo [2.2.2] were weighed]Octane) 21.88g (195.1mmol), 50ml of pure water was added, 11.52g (390.1mmol) of paraformaldehyde was added under nitrogen atmosphere at 10 ℃ or lower with stirring, and the mixture was stirred for 1 hour. While confirming the change from the slurry state to the solution state, acetonitrile 300ml was added, and 19.53g (195.1mmol) of ethyl acrylate was added dropwise, followed by reaction at 50 ℃ for 5 hours. After the reaction was completed, the reaction solution was transferred to a separatory funnel, and 50ml of n-hexane was added. The layer was confirmed to be divided into 3 layers, and the lower 2 layers were collected and the operation was performed 3 times. Further, hydrochloric acid was added to adjust the pH to 4 to 5, and ethyl acetate was used for extraction. To the extracted solution was added anhydrous magnesium sulfate, and after drying by stirring, the mixture was filtered and concentrated to obtain 22.9g (175.6mmol, yield 90%) of a colorless transparent oily liquid. Structure by nuclear magnetic resonance spectroscopy (¹H-NMR spectrum) was confirmed as the target. The measurement data are shown below.

¹H NMR(400MHz,CDCl₃)δ:6.81(1H)、5.80(1H)、4.31(2H)、4.17(1H)、1.98(1H)、0.93(3H)

And a 2 nd step: synthesis of ethyl 2- (heptanoyloxymethyl) acrylate

In a500 ml 4-necked flask equipped with a nitrogen introduction tube, 19.9g (152.9mmol) of 2-hydroxymethylacrylic acid obtained by the above-mentioned method was weighed, THF300ml and triethylamine 23.2g (229.3mmol) were added, and while keeping at 10 ℃ or lower under a nitrogen atmosphere, heptanoyl chloride 25.0g (168.2mmol) was added dropwise to the mixture, followed by reaction for 6 hours. After completion of the reaction, precipitated triethylamine hydrochloride was removed by filtration, the reaction solution was concentrated, redissolved in ethyl acetate 300ml, washed 3 times with 10% potassium carbonate aqueous solution 100ml, washed 3 times with pure water 50ml, dried over anhydrous magnesium sulfate, filtered and concentrated to obtain a thin yellow viscous body. Further, the extract was purified by flash column chromatography (elution solvent: ethyl acetate: n-hexane: 20:80), and the solvent was removed and dried in vacuo to obtain 32.2g (133.0mmol: yield 87%) of a colorless transparent oily liquid. Structure by nuclear magnetic resonance spectroscopy (¹H-NMR spectrum) was confirmed as the target. The measurement data are shown below.

¹H NMR(400MHz,CDCl₃)δ:6.37(1H)、5.80(1H)、3.80(2H)、4.23-4.21(2H)、2.39-2.37(2H)、1.64-1.58(2H)、1.30-1.27(9H)、0.86(3H)

Polymerizable Compound Synthesis example 3

Synthesis of dihexyl itaconate

[ Compound 27 ]

In a 4-necked flask equipped with a Dean-Stark tube, 23.8g (182.9mmol) of itaconic acid and 35.5g (347.5mmol) of 1-hexanol were weighed out, and 500ml of cyclohexane, 0.9g (9.1mmol) of concentrated sulfuric acid and 0.04g (1.82mmol) of dibutylhydroxytoluene (BHT) were added to conduct dehydration condensation reaction at 110 ℃ for 24 hours under a nitrogen atmosphere. After completion of the reaction, 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 100ml of pure waterWashed 3 times and dried over anhydrous magnesium sulfate. After filtration and concentration, vacuum drying was performed to obtain 48.6g (162.8mmol: yield 89%) of a colorless transparent oily liquid. Structure by nuclear magnetic resonance spectroscopy (¹H-NMR spectrum) was confirmed as the target. The measurement data are shown below.

¹H NMR(400MHz,CDCl₃)δ:6.30(1H)、5.65(1H)、4.20-4.00(4H)、3.32(2H)、1.64-1.58(4H)、1.40-1.25(12H)、0.96-0.83(6H)

< production of liquid Crystal display element >

Liquid crystal display elements were produced using the liquid crystal aligning agents SE-6414 (manufactured by Nissan chemical industries, Ltd.) for horizontal alignment and AL1 to AL3 obtained as described above, and having the compositions shown in Table 3.

(first substrate)

The first substrate (hereinafter also referred to as an IPS substrate) is an alkali-free glass substrate having a size of 30mm × 35mm and a thickness of 0.7 mm. An ITO (Indium-Tin-Oxide) electrode having a comb-tooth pattern with an electrode width of 10 μm and an electrode-to-electrode interval of 10 μm was formed on a substrate to form a pixel. The size of each pixel is 10mm in length and 5mm in width.

AL1 to AL3 or SE-6414 were filtered through a 1.0 μm filter, applied to the electrode-formed surface of the IPS substrate by spin coating, and dried on a hot plate at 80 ℃ for 1 minute. Then, AL1 to AL3 were sintered at 220 ℃ for 20 minutes, and SE-6414 was sintered at 220 ℃ for 20 minutes, to form coating films each having a film thickness of 100 nm.

The substrate with the coating film was shielded from light by a metal plate, and half of the substrate was irradiated with ultraviolet light at an exposure of 5000mJ using a high-pressure mercury lamp through a band-pass filter having a wavelength of 313 nm. Hereinafter, this operation is referred to as 1 UV treatment.

After the exposure treatment, rubbing was performed so that the rubbing direction was inclined by 5 ° from the longitudinal direction of the comb-teeth electrode. Rayon cloth manufactured by the Jichuan chemical industry is used for friction: YA-20R was conducted under conditions of a roll diameter of 120mm, a rotation speed of 300rpm, a moving speed of 50mm/sec and an extrusion amount of 0.4 mm. After the rubbing treatment, ultrasonic irradiation was performed for 1 minute in pure water, and the resultant was dried at 80 ℃ for 10 minutes.

(second substrate)

The second substrate (also referred to as a back-surface ITO substrate) was an alkali-free glass substrate having a size of 30mm × 35mm and a thickness of 0.7mm, and an ITO film was formed on the back surface (the surface facing the outside of the cell). Further, columnar spacers having a height of 4 μm were formed on the front surface (the surface facing the inside of the cell).

SE-6414 was filtered through a 1.0 μm filter on the glass surface of the back ITO substrate, and then coated by a spin coating method, and dried on a hot plate at 80 ℃ for 1 minute. Then, AL1 and AL2 were sintered at 220 ℃ for 20 minutes, and SE-6414 was sintered at 220 ℃ for 20 minutes, to form coating films each having a film thickness of 100nm, and then subjected to rubbing treatment. The friction treatment used rayon cloth manufactured by the kagawa chemical industry: YA-20R, roll diameter 120mm, rotation speed 1000rpm, movement speed 50mm/sec, extrusion amount 0.4mm under the condition of friction. After the rubbing treatment, ultrasonic irradiation was performed for 1 minute in pure water, and the resultant was dried at 80 ℃ for 10 minutes.

(preparation of liquid Crystal cell)

The above 2 kinds of substrates (first substrate and second substrate) with the liquid crystal alignment film were used, and the periphery was sealed with the liquid crystal injection port left, to fabricate an empty cell with a cell gap of about 4 μm. At this time, a case where the rubbing directions of the first substrate and the second substrate were antiparallel and a case where the rubbing directions crossed at 85 ° were prepared.

In this empty cell, a liquid crystal (obtained by adding each additive under optimum conditions in a positive liquid crystal MLC-3019 for IPS manufactured by Merck and a liquid crystal MLC3018U for TN manufactured by Merck) was vacuum-injected at normal 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 and a TN mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was heat-treated at 120 ℃ for 10 minutes.

As the 2 UV treatments, irradiation was carried out using a high-pressure mercury lamp through a band-pass filter having a wavelength of 313 nm. The liquid crystal cell was irradiated with ultraviolet rays so that the exposure amount reached 5000 mJ. The details of the unit produced below are shown in table 4 below.

[ TABLE 4]

Unit numbering	Free radical generating membrane	Liquid crystal display device	Orientation mode
				1	AL-1	LC-1	TN
2	AL-2	LC-1	TN
				3	AL-3	LC-1	TN
4	AL-1	LC-2	TN
				5	AL-2	LC-2	TN
6	AL-3	LC-2	TN
				7	AL-1	LC-3	TN
8	AL-2	LC-3	TN
				9	AL-3	LC-3	TN
10	AL-1	LC-4	TN
				11	AL-2	LC-4	TN
12	AL-3	LC-4	TN
				13	AL-1	LC-5	Level of
14	AL-2	LC-5	Level of
				15	AL-3	LC-5	Level of
16	AL-1	LC-6	Level of
				17	AL-2	LC-6	Level of
18	AL-3	LC-6	Level of
				19	AL-1	LC-7	Level of
20	AL-2	LC-7	Level of
				21	AL-3	LC-7	Level of
22	AL-1	LC-8	Level of
				23	AL-2	LC-8	Level of
24	AL-3	LC-8	Level of

SE-6414 is used on the side opposite to the back ITO

< visual evaluation of liquid Crystal alignment >

The alignment of the TN-mode liquid crystal cell was confirmed using a polarizing plate fixed to a crossed nicol. In the case where the UV treatment is not performed, since the alignment regulating force of the one-side alignment film is lost (that is, a zero-anchoring state is formed), the liquid crystal cannot be twisted sufficiently by the regulating force of the chiral dopant in the liquid crystal, and thus the liquid crystal is changed to a horizontal alignment state. On the other hand, the UV-treated area loses polymerization reactivity, and thus the anchoring force is maintained. Thus, a twisted orientation is generated. Thereby, 2 alignment states are generated within the pixel. As shown in fig. 1, the film was marked with "white" when the film was irradiated with UV and "horizontal" when the film was not irradiated with UV, and "x" when no change was observed in each region.

[ TABLE 5]

TABLE 5 evaluation of alignment Pattern Forming characteristics

Examples	Unit numbering	Pattern formability
			Example 1	4	○
Example 2	5	○
			Example 3	7	○
Example 4	8	○
			Example 5	10	○
Example 6	11	○
			Comparative example 1	1	×
Comparative example 2	2	×
			Comparative example 3	3	×
Comparative example 4	6	×
			Comparative example 5	9	×
Comparative example 6	12	×

In the case of using a liquid crystal without an additive material for the liquid crystal, and in the case of using a material that does not generate radicals by light, the alignment patterning, i.e., the alignment regulating force, is not changed even if the UV treatment is performed 1 time. From this, it is understood that the combination of the photo radical generating film of the present invention and the additive is important.

< evaluation of electro-optical Properties >

The change in threshold voltage and the measurement of mode efficiency were carried out by measuring the V-T curve using the cells 13 to 24 (horizontal alignment cells). The white LED backlight and the luminance meter are fixed so that the optical axes are the same, and during this period, the liquid crystal cell (liquid crystal display element) having the polarizing plate attached thereto is fixed so that the luminance becomes minimum, and the V-T curve is measured by applying a voltage up to 8V at 1V intervals and measuring the luminance in the voltage. The value of the driving threshold voltage is estimated from the obtained V-T curve. The mode efficiency was measured by calculating the ratio of the luminance at Vmax of the liquid crystal cell to the luminance of the LED transmitted light at the parallel nicols of the polarizer.

The anchoring determination is based on the magnitude of the threshold voltage, which is estimated by the Fredericks transfer method.

[ TABLE 6]

TABLE 6

Since the cells 13 to 24 are horizontally oriented cells, even if the cell has a zero anchor orientation, the cell does not change visually. On the other hand, in the 1 UV-exposed portion and the unexposed portion, the threshold voltage and luminance change of the V-T curve were observed. From this examination, it was also found that by performing 1 exposure, regions having different anchoring forces within the pixel were created.

Industrial applicability

According to the present invention, the zero-plane regions having different anchors can be produced from inexpensive raw materials in an industrial yield. The liquid crystal display element obtained by the method of the present invention is useful as a liquid crystal display element of a vertical alignment type such as a PSA type liquid crystal display and an SC-PVA type liquid crystal display.

Claims

1. A method of making a patterned zero-side anchoring film, comprising:

irradiating the radical generating film with radiation in a specific region to form a patterned radical generating film; and

and a step of bringing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound into contact with the patterned radical generating film, and imparting energy sufficient to cause a polymerization reaction of the radical polymerizable compound to the liquid crystal composition while maintaining the state.

2. The method of claim 1, wherein,

the radical generating film is a radical generating film subjected to uniaxial orientation treatment.

3. The method of claim 1 or 2,

the step of imparting energy is performed in a field-free state.

4. The method according to any one of claims 1 to 3,

the radical generating film is a film in which an organic group that induces radical polymerization is immobilized.

5. The method according to any one of claims 1 to 3,

the radical generating film is obtained by coating a composition of a compound having a radical generating group and a polymer, curing it and forming a film, thereby immobilizing in the film.

6. The method according to any one of claims 1 to 3,

the radical generating film comprises a polymer containing organic groups that induce radical polymerization.

7. The method of claim 6,

the polymer having an organic group which induces radical polymerization is at least one polymer selected from the group consisting of a polyimide precursor obtained by using a diamine component containing a diamine having an organic group which induces radical polymerization, a polyimide, a polyurea, and a polyamide.

8. The method of any one of claims 4,6, and 7,

the organic group that induces radical polymerization is an organic group represented by any one of the following structures [ X-1] to [ X-18], [ W ], [ Y ] and [ Z ],

formula [ X-1]～[X-18]Wherein represents a compound bonded to a portion other than the polymerizable unsaturated bond of the compound moleculeSite, S₁、S₂Independently represents-O-, -NR-, -S-, R represents hydrogen atom, halogen atom, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, R represents₁、R₂Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;

formula [ W ]]、[Y]、[Z]Wherein 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, and R represents a site bonded to a portion other than the polymerizable unsaturated bond of the compound molecule⁹And R¹⁰Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R⁹And R¹⁰In the case of an alkyl group, the terminal groups may be bonded to each other to form a ring structure or may not be bonded to each other to form a ring structure; q represents the following structure;

in the formula, R¹¹represents-CH₂-, -NR-, -O-or-S-, wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and represents a site bonded to a portion other than Q of the compound molecule;

R₁₂represents 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.

9. The method according to claim 7, wherein the diamine having an organic group which induces radical polymerization is a diamine having a structure represented by the following general formula (6) or the following general formula (7),

in the formula (6), R⁶Represents a single bond, -CH₂-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂O-、-N(CH₃)-、-CON(CH₃) -or-N (CH)₃)CO-，

R⁷Represents 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 groups₂-or-CF₂-1 or more of-are each independently substituted or unsubstituted with a group selected from-CH ═ CH-, a divalent carbocyclic ring and a divalent heterocyclic ring, and with or unsubstituted with any of the groups listed below, i.e., -O-, -COO-, -OCO-, -NHCO-, -CONH-, or-NH-not adjacent to each other;

R⁸represents a radical polymerization reactive group selected from the following formulas,

formula [ X-1]～[X-18]Wherein S represents a site bonded to a portion other than a radical polymerization reactive group of a compound molecule¹、S²Independently represents-O-, -NR-, -S-, R represents hydrogen atom, halogen atom, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, R represents₁、R₂Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;

in the formula (7), T₁And T₂Each independently is a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH₂O-、-N(CH₃)-、-CON(CH₃) -or-N (CH)₃)CO-，

S⁰Represents a single bond, or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with a fluorine atomany-CH of alkylene₂-or-CF₂-1 or more of which are each independently substituted or unsubstituted by a group selected from-CH ═ CH-, divalent carbocyclic and divalent heterocyclic rings, and are substituted or unsubstituted by 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,

j is an organic group represented by any one of the following formulae,

formula [ W ]]、[Y]、[Z]In the formula, represents and T₂A bonding site, Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene, with or without an organic group and/or a halogen atom as a substituent, and R⁹And R¹⁰Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q represents any of the following structures;

10. The method according to any one of claims 1 to 9,

at least one of the radical polymerizable compounds is a compound having compatibility with a liquid crystal and having one polymerizable unsaturated bond in one molecule.

11. The method of claim 10, wherein,

the polymerization reactive group of the radical polymerizable compound is selected from the following structures,

wherein the formula represents a site bonded to a portion other than the polymerizable unsaturated bond of the compound molecule; r^bRepresents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR^c-S-, a binding group in an ester bond and an amide bond; r^cRepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

12. The method according to any one of claims 1 to 11,

the liquid crystal composition containing the liquid crystal and the radical polymerizable compound comprises the following radical polymerizable compounds: the Tg of a polymer obtained by polymerizing the radically polymerizable compound is 100 ℃ or lower.

13. A method of manufacturing a liquid crystal cell,

use of the method according to any one of claims 1 to 12,

the method for manufacturing the liquid crystal unit comprises the following steps:

14. The method of manufacturing a liquid crystal cell according to claim 13,

the second substrate is a second substrate having no radical generating film.

15. The method of manufacturing a liquid crystal cell according to claim 14,

the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment properties.

16. The method of manufacturing a liquid crystal cell according to claim 15,

the liquid crystal alignment film having uniaxial alignment is a liquid crystal alignment film for horizontal alignment.

17. The method for producing a liquid crystal cell according to any one of claims 13 to 16,

the first substrate having the radical generating film is a substrate having comb-teeth electrodes.

18. A liquid crystal composition comprising a liquid crystal and a radical polymerizable compound,

the polymerization reactive group is selected from the following structures,

19. A method for manufacturing a liquid crystal display element, characterized by using a film in a manufactured zero-plane anchoring state obtained by the method according to any one of claims 1 to 17.

20. A liquid crystal display element is characterized in that,

the liquid crystal display element is obtained by the method according to claim 19.

21. The liquid crystal display element according to claim 20,

the first substrate or the second substrate has an electrode.

22. The liquid crystal display element according to claim 20 or 21,

the liquid crystal display element is a low-voltage driving transverse electric field liquid crystal display element.