KR20210020127A - Method for manufacturing zero plane anchoring film and liquid crystal display device - Google Patents

Abstract

The present invention provides an industrial manufacturing method of a zero plane anchoring film, and a good liquid crystal display element and a method of manufacturing a liquid crystal display element using the same.
A step of forming a patterned radical generating film by irradiating radiation to a specific region on the radical generating film, and bringing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound into contact with the patterned radical generating film and maintaining the state , A method for producing a patterned zero surface anchoring film, comprising the step of imparting sufficient energy to the liquid crystal composition for polymerization reaction of the radically polymerizable compound, and a liquid crystal composition containing a liquid crystal and a radically polymerizable compound, A function comprising a step of preparing a cell having a cell between a first substrate having a generating film and a second substrate not having a radical generating film, and providing the cell with sufficient energy to polymerize the radically polymerizable compound. It is done by the method of creating a film.

Description

Method for manufacturing zero plane anchoring film and liquid crystal display device

The present invention is an inexpensive and inexpensive method that does not include a complicated process, a manufacturing method to which a polymer stabilization technology capable of manufacturing a zero surface anchoring film is applied, and a liquid crystal display for realizing a further low voltage driving using the manufacturing method. It relates to a device and a method of manufacturing the same.

Recently, liquid crystal display elements are widely used in displays of mobile phones, computers, and TVs. The liquid crystal display device has characteristics such as thinness, light weight, and low power consumption, and in the future, further application to contents such as VR and ultra-high-definition displays is expected. Various display modes, such as TN (Twisted Nematic), IPS (In-Plane Switching), and VA (Vertical Alignment), are proposed as a display method of a liquid crystal display.In all modes, a film that guides the liquid crystal to a desired alignment state (liquid crystal alignment film) ) Is being used.

In particular, for products equipped with touch panels such as tablet PCs, smartphones, and smart TVs, the IPS mode, which makes the display difficult to be disturbed by touching, is preferred, and in recent years, FFS (Frindge Field Switching) has improved contrast and viewing angle characteristics. ), or a technology using a non-contact technology using optical alignment has been used.

However, FFS has a problem in that the manufacturing cost of the substrate is higher than that of IPS, and display defects peculiar to the FFS mode called Vcom shift occur. In addition, with regard to photo-alignment, compared to the rubbing method, there is an advantage in that the size of the device that can be manufactured can be increased and the display characteristics can be greatly improved. In the case of the derived display defect and the isomerization type, burn-in due to insufficient orientation force, etc.) can be mentioned. In order to solve such a problem, a liquid crystal display element maker and a liquid crystal aligning film maker are devising various inventions.

On the other hand, in recent years, an IPS mode using zero plane anchoring has been proposed, and it has been reported that by using this method, contrast improvement and significantly lower voltage driving are possible compared to the conventional IPS mode (see Patent Document 1).

Specifically, a liquid crystal alignment film having a strong anchoring energy is used for the substrate on one side, and a treatment such as not having the alignment regulating force of the liquid crystal at all is performed on the substrate side with the electrode on the side generating the transverse electric field on the other side, This is a method of making IPS mode liquid crystal display elements using them.

In recent years, a zero surface state is created using a thick polymer brush or the like, and a technology proposal for a zero surface anchoring IPS mode has been made (Patent Document 2). With this technology, the contrast ratio is greatly improved and the driving voltage is greatly reduced.

On the other hand, there is a problem that the response speed, in particular, the response speed at the time of voltage OFF is significantly lowered. This is because the driving voltage is lowered, the effect of responding with an electric field that is weaker than that of the normal driving method, and the anchoring force of the alignment film is extremely small, and thus it takes time to restore the liquid crystal. As a method of solving this, a method of zero anchoring only on the pixel electrode has been proposed (Patent Document 3). It has been reported that this makes it possible to achieve both an improvement in luminance and a response speed.

Japanese Patent No. 4053530 Japanese Unexamined Patent Publication No. 2013-231757 Japanese Patent Publication No. 2017-211566

The response speed delay during driving is suppressed by anchoring only the electrodes of the IPS comb electrode on the zero side, while in order to set the state of zero anchoring only on the electrode, it is necessary to prepare difficult techniques such as dividing different materials into very detailed areas. , It is conceivable to be a big problem for actual industrialization.

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

The present invention has been made to solve the above problems, a method of creating a region having a zero plane anchoring portion and an anchoring force in the plane of a liquid crystal alignment film, and a method of controlling anchoring energy in an arbitrary state, at room temperature An object of the present invention is to provide a transverse electric field liquid crystal display device and a method of manufacturing the same, which can simultaneously realize non-contact orientation, reduction of driving voltage, and speeding of response speed at the time of off by a simple and inexpensive method.

In order to solve the above-described problems, the inventors of the present invention have conducted intensive examinations and found what can solve the above-described problems, and have completed the present invention having the following summary.

That is, the present invention includes the following.

[1] forming a patterned radical generating film by irradiating radiation to a specific region on the radical generating film, and bringing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound into contact with the patterned radical generating film, and the state A method for producing a patterned zero-side anchoring film comprising the step of imparting sufficient energy to the liquid crystal composition for polymerization reaction of the radically polymerizable compound while maintaining.

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

[3] The method described in [1] or [2], wherein the step of applying energy is performed in an electric field.

[4] The method according to any one of [1] to [3], wherein the radical generating film is a film obtained by immobilizing an organic group causing radical polymerization.

[5] As described in any one of [1] to [3], wherein the radical-generating film is obtained by forming a film by applying and curing a composition of a compound having a radical-generating group and a polymer to form a film. One way.

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

[7] The polymer containing an organic group inducing radical polymerization is selected from a polyimide precursor, polyimide, polyurea, and polyamide obtained by using a diamine component containing a diamine containing an organic group inducing radical polymerization. The method according to [6], which is at least one type of polymer.

[8] The organic group causing radical polymerization is an organic group represented by any of the following structures [X-1] to [X-18], [W], [Y] and [Z] [4], [6] And the method described in any one of [7]:

[Formula 1]

(In formulas [X-1] to [X-18], * represents a bonding site with a moiety other than a polymerizable unsaturated bond of a compound molecule, and S ₁ and S ₂ are each independently -O-, -NR- , -S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, and 1 to 4 carbon atoms Represents the alkyl group of.)

[Formula 2]

(In formulas [W], [Y], and [Z], * represents a bonding site with a moiety other than a polymerizable unsaturated bond of the compound molecule, and Ar is a phenyl which may have an organic group and/or a halogen atom as a substituent. Represents an aromatic hydrocarbon group selected from the group consisting of ene, naphthylene and biphenylene, R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R ⁹ and R ^{When 10} is an alkyl group, they may be bonded to each other at the terminal to form a ring structure, where Q represents the following structure.

[Formula 3]

(In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O- or -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, * represents other than Q of the compound molecule It indicates the binding site to the part.)

R ₁₂ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.).

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

[Formula 4]

(In formula (6), R ⁶ is a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ )-, -CON(CH ₃ )- or -N(CH ₃ )CO-,

R ⁷ represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and one or more _{of any -CH 2} -or -CF _{2-of the alkylene group are each independently} -CH=CH-, may be substituted with a group selected from a divalent carbocyclic ring and a divalent heterocycle, and any of the following groups, namely -O-, -COO-, -OCO-, -NHCO- , -CONH- or -NH- may be substituted with these groups provided they are not adjacent to each other;

R ⁸ represents a radical polymerization reactive group selected from the following formula:

[Formula 5]

(In formulas [X-1] to [X-18], * represents a bonding site with a moiety other than the radical polymerization reactive group of the compound molecule, and S ₁ and S ₂ are each independently -O-, -NR- , -S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and R ¹ and R ² are each independently a hydrogen atom, a halogen atom, and 1 to 4 carbon atoms Represents an alkyl group of))

[Formula 6]

(In formula (7), T ₁ and T ₂ are each independently a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-,- CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )- or -N(CH ₃ )CO-,

S ⁰ represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and one or more _{of any -CH 2} -or -CF _{2-of the alkylene group are each independently} -CH=CH-, may be substituted with a group selected from a divalent carbocyclic ring and a divalent heterocycle, and any of the following groups, namely -O-, -COO-, -OCO-, -NHCO- , -CONH- or -NH- may be substituted with these groups provided they are not adjacent to each other,

J is an organic group represented by any of the following formulas,

[Formula 7]

(In formulas [W], [Y], and [Z], * _{represents a bonding site with T 2} , and Ar represents phenylene, naphthylene, and biphenylene which may have an organic group and/or a halogen atom as a substituent. Represents an aromatic hydrocarbon group selected from the group ^{consisting of, R 9} and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q represents the structure of any of the following:

[Formula 8]

(In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O- or -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, * represents other than Q of the compound molecule It indicates the binding site to the part.)

R ₁₂ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.)).

[10] The method according to any one of [1] to [9], wherein at least one of the radically polymerizable compounds is a compound having compatibility with a liquid crystal and having one polymerizable unsaturated bond per molecule.

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

[Formula 9]

(In the formula, * represents a bonding site with a moiety other than a polymerizable unsaturated bond of the compound molecule. R ^b represents a C2-C8 linear alkyl group, and E represents a single bond, -O-, -NR ^c -, Represents a bonding group selected from -S-, an ester bond and an amide bond, R ^c represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.)

[12] In the liquid crystal composition containing the liquid crystal and the radical polymerizable compound, a liquid crystal composition containing a radical polymerizable compound in which Tg of the polymer obtained by polymerizing the radical polymerizable compound is 100°C or less is used. The method described in any one of [1] to [11].

[13] a step of preparing a first substrate having a radical generating film and a second substrate which may have a radical generating film,

Creating a cell such that the radical generating film on the first substrate faces the second substrate, and

Including 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,

A method for producing a liquid crystal cell using the method described in any one of [1] to [12].

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

[15] The method for 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.

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

[17] The method for 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 a comb electrode.

[18] containing liquid crystal and radically polymerizable compounds,

At least one of the radically polymerizable compounds is a compound having compatibility with a liquid crystal and having one polymerizable unsaturated bond per molecule,

The liquid crystal composition, wherein the polymerization reactive group is selected from the following structures:

[Formula 10]

(In the formula, * represents a bonding site with a moiety other than a polymerizable unsaturated bond of the compound molecule. R ^b represents a C2-C8 linear alkyl group, and E represents a single bond, -O-, -NR ^c -, Represents a bonding group selected from -S-, an ester bond and an amide bond, R ^c represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.)

[19] A method for manufacturing a liquid crystal display device using a film that creates a zero-plane anchoring state obtained by using the method according to any one of [1] to [17].

[20] A liquid crystal display device obtained by using the method described in [19].

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

[22] The liquid crystal display device according to [20] or [21], which is a low-voltage drive transverse electric field liquid crystal display device.

Advantageous Effects of Invention According to the present invention, a zero plane anchoring film can be produced industrially and in good yield. By using the method of the present invention, a liquid crystal display device similar to the zero plane anchoring IPS mode liquid crystal display device described in Patent Documents 1 and 2 can be easily manufactured using inexpensive raw materials or conventional manufacturing methods. In addition, the liquid crystal display device obtained by the manufacturing method of the present invention has a faster response speed of liquid crystal when off than in the prior art, and it is possible to suppress the Vcom shift in low driving voltage, no bright spot, IPS mode, and even more in FFS mode. It is possible to provide a liquid crystal display device having excellent characteristics that further high definition is possible.

FIG. 1 is a diagram of a TN cell having a substrate formed with a film having a zero-side anchoring region and a zero-side anchoring region by having a UV-irradiated region and a UV-irradiated region. In the cell, a transparent region is a region with no UV irradiation and an opaque region is a region with UV irradiation.

The present invention is a liquid crystal containing a specific polymerizable compound in the radical generating film through a process of forming a radical generating film having an anchoring force on a substrate and irradiating radiation to the radical generating film in a region where the anchoring force is desired to be maintained. This is a method for producing a film having a patterned zero-side anchoring region and a strong anchoring region, characterized in that the polymerizable compound is polymerized by UV or heat in a contacted state. More specifically, a step of preparing a cell having a liquid crystal composition containing a liquid crystal and a radically polymerizable compound between a first substrate having a radical generating film treated by radiation and a second substrate which may have a radical generating film , And imparting sufficient energy to polymerize the radical polymerizable compound to the cell. A method for producing a film in which a zero plane anchoring region and a strong anchoring region are patterned. Preferably, a step of preparing a first substrate having a radical generating film subjected to radiation irradiation treatment, a second substrate having no radical generating film, a step of creating a cell such that the radical generating film faces the second substrate, and the first substrate It is a manufacturing method of a liquid crystal cell including a step of filling a liquid crystal composition containing a liquid crystal and a radical polymerizable compound between the second substrates. For example, this is a method for producing a low voltage driving IPS liquid crystal display device in which the second substrate does not have a radical generating film and has a liquid crystal alignment film subjected to uniaxial alignment treatment, and the first substrate is a substrate having comb electrodes.

In the present invention, the term ``zero plane anchoring film'' means that there is no alignment regulating force of liquid crystal molecules in the in-plane direction, or even weaker than the intermolecular force between liquid crystals, and this film alone does not uniaxially align the liquid crystal molecules in any direction. Say the membrane. In addition, this zero plane anchoring film is not limited to a solid film, and a liquid film covering the solid surface is also included. In general, in a liquid crystal display device, a film that regulates the alignment of liquid crystal molecules, that is, a liquid crystal alignment film is used in pairs to align the liquid crystal, but the zero-plane anchoring film and the liquid crystal alignment film are also used in pairs to align the liquid crystal. This is because the alignment regulating force of the liquid crystal alignment layer is transmitted also 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 that are close to the zero plane anchoring layer are also aligned. Therefore, when the liquid crystal alignment layer for horizontal alignment is used for the liquid crystal alignment layer, a horizontal alignment state can be created in the entire liquid crystal cell. The horizontal alignment refers to a state in which the major axes of the liquid crystal molecules are arranged substantially parallel to the surface of the liquid crystal alignment film, and an inclined alignment of several degrees is also included in the category of the horizontal alignment.

[Radial Generating Film Forming Composition]

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 a radical. In that case, the composition may contain a polymer to which a group capable of generating radicals is bonded, or may be a composition of a compound having a group capable of generating radicals and a polymer serving as a base resin. By coating and curing such a composition to form a film, a radical-generating film immobilized in a giga film capable of generating radicals can be obtained. The group capable of generating a radical is preferably an organic group causing radical polymerization.

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

[Formula 11]

(In formulas [X-1] to [X-18], * represents a bonding site with a moiety other than a polymerizable unsaturated bond of a compound molecule, and S ₁ and S ₂ are each independently -O-, -NR- , -S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, and 1 to 4 carbon atoms Represents the alkyl group of.)

[Formula 12]

(In formulas [W], [Y], and [Z], * represents a bonding site with a moiety other than a polymerizable unsaturated bond of the compound molecule, and Ar is a phenyl which may have an organic group and/or a halogen atom as a substituent. Represents an aromatic hydrocarbon group selected from the group consisting of ene, naphthylene and biphenylene, R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R ⁹ and R ^{When 10} is an alkyl group, it may be bonded to each other at the ends to form a ring structure, Q represents any of the following structures:

[Formula 13]

(In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O- or -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, * represents other than Q of the compound molecule It indicates the binding site to the part.)

R ₁₂ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.).

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

In order to obtain the radical-generating film used in the present invention, in the case of using a polymer having an organic group causing radical polymerization, in order to obtain a polymer having a group capable of generating radicals, as a monomer component, a methacrylic group, an acrylic group, a vinyl group , Allyl group, coumarin group, styryl group, and a monomer having a photoreactive side chain containing at least one selected from a cinnamoyl group, or a monomer decomposing by ultraviolet irradiation and having a radical generating site in the side chain It is preferable to manufacture. On the other hand, the radical-generating monomer itself has problems such as spontaneous polymerization, and becomes an unstable compound, so from the viewpoint of ease of synthesis, a polymer derived from diamine having a radical-generating site is preferable. More preferably, polyimide precursors such as polyamic acid and polyamic acid ester, polyimide, polyurea, polyamide, and the like are preferable.

Such a radical-generating site-containing diamine is specifically, for example, a diamine having a side chain capable of generating a radical and polymerizing, and includes a diamine represented by the following general formula (6), but is limited thereto. no.

[Formula 14]

(In formula (6), R ⁶ is a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ )-, -CON(CH ₃ )- or -N(CH ₃ )CO-,

R ⁷ represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and one or more _{of any -CH 2} -or -CF _{2-of the alkylene group are each independently} -CH=CH-, may be substituted with a group selected from a divalent carbocyclic ring and a divalent heterocycle, and any of the following groups, namely -O-, -COO-, -OCO-, -NHCO- , -CONH- or -NH- may be substituted with these groups provided they are not adjacent to each other;

R ⁸ represents a radical polymerization reactive group selected from the following formula:

[Formula 15]

(In formulas [X-1] to [X-18], * represents a bonding site with a moiety other than the radical polymerization reactive group of the compound molecule, and S ₁ and S ₂ are each independently -O-, -NR- , -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₁₂ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, R ₁ And R ₂ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.)).

The bonding position of two amino groups (-NH _{2) in formula (6) is not limited.}

Specifically, with respect to the bonding group of the side chain, the positions of 2 and 3 on the benzene ring, the positions of 2 and 4, the positions of 2 and 5, the positions of 2 and 6, the positions of 3 and 4, and the positions of 3 and 5 are mentioned. I can. Among them, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2 and 4, positions 2 and 5, or positions 3 and 5 are preferable. If the ease in synthesizing diamine is also added, the positions 2 and 4 or the positions 3 and 5 are more preferable.

As a diamine having a photoreactive group containing at least one selected from the group consisting of a methacrylic group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group and a cinnamoyl group, specifically, the following compounds Although can be mentioned, it is not limited to these.

[Formula 16]

(Wherein, J ¹ is a single bond, a bonding group selected from -O-, -COO-, -NHCO-, or -NH-, and J ² is a single bond, or 1 carbon number unsubstituted or substituted by a fluorine atom. It shows the alkylene group of -20.)

The diamine which is decomposed by ultraviolet irradiation and has a site for generating a radical as a side chain includes a diamine represented by the following general formula (7), but is not limited thereto.

[Formula 17]

(In formula (7), T ₁ and T ₂ are each independently a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-,- CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )- or -N(CH ₃ )CO-,

S ⁰ represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and one or more _{of any -CH 2} -or -CF _{2-of the alkylene group are each independently} -CH=CH-, may be substituted with a group selected from a divalent carbocyclic ring and a divalent heterocycle, and any of the following groups, namely -O-, -COO-, -OCO-, -NHCO- , -CONH- or -NH- may be substituted with these groups provided they are not adjacent to each other,

J is an organic group represented by any of the following formulas,

[Formula 18]

(In formulas [W], [Y], and [Z], * _{represents a bonding site with T 2} , and Ar represents phenylene, naphthylene, and biphenylene which may have an organic group and/or a halogen atom as a substituent. Represents an aromatic hydrocarbon group selected from the group ^{consisting of, R 9} and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q represents the structure of any of the following:

[Formula 19]

(In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O- or -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, * represents other than Q of the compound molecule It indicates the binding site to the part.)

R ₁₂ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.)).

The bonding position of two amino groups (-NH ₂ ) in the above formula (7) is not limited. Specifically, with respect to the bonding group of the side chain, the positions of 2 and 3 on the benzene ring, the positions of 2 and 4, the positions of 2 and 5, the positions of 2 and 6, the positions of 3 and 4, and the positions of 3 and 5 are mentioned. I can. Among them, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2 and 4, positions 2 and 5, or positions 3 and 5 are preferable. If the ease in synthesizing diamine is also added, the positions 2 and 4 or the positions 3 and 5 are more preferable.

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

[Formula 20]

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

The above-described diamine may be used alone or in combination of two or more depending on characteristics such as liquid crystal orientation when used as a radical generating film, sensitivity in polymerization reaction, voltage retention characteristics, and accumulated charge.

As for the diamine having a site where such radical polymerization occurs, it is preferable to use an amount of 5 to 50 mol% of the total diamine component used for synthesizing the polymer to be contained in the radical generating film-forming composition, and more preferably 10 to It is 40 mol%, and particularly preferably 15 to 30 mol%.

In addition, when the polymer used for the radical generating film of the present invention is obtained from diamine, as long as the effect of the present invention is not impaired, other diamines other than the diamine having the radical generating site may be used in combination as a diamine component. I can. Specifically, for example, 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-diaminophenol , 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4' -Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy -4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3, 4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3 ,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diamino Diphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4, 4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3 -Aminophenyl)silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4' -Diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3 ,3'-diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3 '-Diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2 '-Diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminona Phthalene, 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, 4,4'-[1,4-phenylenebis(methylene) ]Daniline, 4,4'-[1,3-phenylenebis(methylene)]dianiline, 3,4'-[1,4-phenylenebis(methylene)]dianiline, 3,4'-[ 1,3-phenylenebis(methylene)]dianiline, 3,3'-[1,4-phenylenebis(methylene)]dianiline, 3,3'-[1,3-phenylenebis(methylene) ]Daniline, 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,N'-(1,4-phenylene)bis(4-aminobenzamide), N, N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1, 3-phenylene) bis(3-aminobenzamide), N,N'-bis(4-aminophenyl) terephthalamide, N,N'-bis(3-aminophenyl) terephthalamide, N,N'-bis (4-aminophenyl)isophthalamide, N,N'-bis(3-ami) Nophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylsulfone, 2,2'-bis[4-(4-amino Phenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2 '-Bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2, 2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, trans-1,4-bis(4-aminophenyl)cyclohexane, 3,5-dia Minobenzoic 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-amino Phenoxy)pentane, 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, 1,12-bis(4-aminophenoxy) ) Aromatic diamines such as dodecane and 1,12-bis(3-aminophenoxy)dodecane; Alicyclic diamines such as bis(4-aminocyclohexyl)methane and bis(4-amino-3-methylcyclohexyl)methane; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1, Aliphatic diamines such as 9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane; Having a urea structure such as 1,3-bis[2-(p-aminophenyl)ethyl]urea, 1,3-bis[2-(p-aminophenyl)ethyl]-1-tertiary butyloxycarbonylurea Diamine; Diamines having a nitrogen-containing unsaturated heterocyclic structure such as N-p-aminophenyl-4-p-aminophenyl (tertiary butyloxycarbonyl) aminomethylpiperidine; Diamines having an N-Boc group such as N-tertiarybutoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine, and the like.

The other diamines described above may be used alone or in combination of two or more depending on characteristics such as liquid crystal orientation when used as a radical generating film, sensitivity in polymerization reaction, voltage retention characteristics, and accumulated charge.

In the synthesis when the polymer is a polyamic acid, the tetracarboxylic dianhydride to be reacted with the diamine component is not particularly limited. Specifically, 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 ,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3 ,4-dicarboxyphenyl)dimethylsilane, bis(3,4-dicarboxyphenyl)diphenylsilane, 2,3,4,5-pyridine tetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl) Pyridine, 3,3',4,4'-diphenylsulfone tetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid , Oxydiphthalic tetracarboxylic acid, 1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid, 1,2, 3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,3-dimethyl-1,2,3 ,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cycloheptane tetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid, 2, 3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic 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-2,4,7,9-tetra Carboxylic 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-butane tetracarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, bicyclo[2, 2,2]Octo-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>]dodeca-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2:3,5 : A dianhydride of tetracarboxylic acid, such as 6 dicarboxylic acid and 1,2,4,5-cyclohexane tetracarboxylic acid, is mentioned.

Of course, tetracarboxylic dianhydride may also be used alone or in combination of two or more depending on characteristics such as liquid crystal orientation when used as a radical generating film, sensitivity in polymerization reaction, voltage retention characteristics, and accumulated charge.

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

Specific examples of aliphatic tetracarboxylic acid diesters include 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1, 3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2 ,3,4-cyclopentane tetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexane tetracarboxylic acid dialkyl ester, 3,4- Dicarboxy-1-cyclohexylsuccinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dialkyl ester, 1,2,3,4-butane tetracarboxylic acid di Alkyl ester, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3',4,4'-dicyclohexyl tetracarboxylic acid dialkyl ester, 2,3 ,5-tricarboxycyclopentylacetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.0< 2,5>]Nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-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-dioxotetrahydro Furan-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dialkyl ester, etc. are mentioned.

As aromatic tetracarboxylic acid dialkyl ester, pyromellitic acid dialkyl ester, 3,3',4,4'-biphenyl tetracarboxylic acid dialkyl ester, 2,2',3,3'-biphenyl tetracarboxylic acid dialkyl Ester, 2,3,3',4-biphenyl tetracarboxylic acid dialkyl ester, 3,3',4,4'-benzophenone tetracarboxylic acid dialkyl ester, 2,3,3',4'-benzophenone tetra Carboxylic acid dialkyl ester, bis(3,4-dicarboxyphenyl)ether dialkyl ester, bis(3,4-dicarboxyphenyl)sulfone dialkyl ester, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl ester, etc. are mentioned.

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

[Formula 21]

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

Aliphatic diisocyanates represented by K-1 to K-5 are inferior in reactivity, but have the merit of improving solvent solubility, and aromatic diisocyanates such as those represented by K-6 to K-7 are rich in reactivity and improve heat resistance. Although there is an effect, a drawback of reducing solvent solubility is mentioned. From the viewpoint of versatility and characteristics, K-1, K-7, K-8, K-9, K-10 are particularly preferred, and K-12 from the viewpoint of electrical properties, and K-13 from the viewpoint of liquid crystal orientation. It is particularly preferred. The diisocyanate may be used in combination of one or more, and it is preferable to apply various kinds of diisocyanates depending on the characteristics desired to be obtained.

In addition, some diisocyanates may be substituted with the tetracarboxylic dianhydride described above, and may be used in the same form as a copolymer of polyamic acid and polyurea, or a copolymer of polyimide and polyurea by chemical imidization. You can use the same form.

In the synthesis when the polymer is polyamide, the structure of the dicarboxylic acid to be reacted is not particularly limited, but a specific example is given below as follows. As specific examples of aliphatic dicarboxylic acids, malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethyl And dicarboxylic acids such as glutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, and suberic acid.

As alicyclic dicarboxylic acid, 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutane Dicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclo Butene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclo Hexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-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]octanedicarboxylic acid , 1,3-adamantanedicarboxylic acid, 4,8-dioxo-1,3-adamantanedicarboxylic acid, 2,6-spiro[3.3]heptanedicarboxylic acid, 1,3-adamantanediacetic acid, camphoric acid And the like.

As aromatic dicarboxylic acids, o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethyl terephthalic acid, tetra Methyl terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4-anthraquinonedi Carboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 4,4"-terphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid , 4,4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4, 4'-bibenzyldicarboxylic acid, 4,4'-stylbendicarboxylic acid, 4,4'-tolandicarboxylic acid, 4,4'-carbonyl benzoic acid, 4,4'- Sulfonyl benzoic acid, 4,4'-dithiobenzoic acid, p-phenylene diacetic acid, 3,3'-p-phenylenedipropionic acid, 4-carboxypic acid, p-phenylenediacrylic acid, 3,3'-[4 ,4'-(methylenedi-p-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene)]dipropionic acid, 4,4'-[4,4 Dicarboxylic acids such as'-(oxydi-p-phenylene)] dibutyric acid, (isopropylidenedi-p-phenylenedioxy) dibutyric acid, and bis(p-carboxyphenyl) dimethylsilane. have.

Examples of dicarboxylic acids containing heterocycles include 1,5-(9-oxofluorene)dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4,5-thiazoledi Carboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridine di Carboxylic acid, 2,5-pyridine dicarboxylic acid, 2,6-pyridine dicarboxylic acid, 3,4-pyridine dicarboxylic acid, 3,5-pyridine dicarboxylic acid, etc. are mentioned.

The above various dicarboxylic acids may have an acid dihalide or an anhydrous structure. These dicarboxylic acids are particularly preferably dicarboxylic acids capable of imparting a polyamide having a linear structure in order to maintain the orientation of the liquid crystal molecules. Among these, terephthalic acid, isoterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4 ,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis(phenyl)propanedicarboxylic acid, 4,4-terphenyldicarboxylic acid, 2,6-naphthalene Dicarboxylic acids, 2,5-pyridine dicarboxylic acids, or acid dihalides thereof are preferably used. Although isomers exist in some of these compounds, a mixture containing them may be sufficient. Moreover, you may use 2 or more types of compounds together. In addition, the dicarboxylic acids used in the present invention are not limited to the above exemplary compounds.

Reaction of a raw material diamine (also referred to as a ``diamine component'') and a raw material tetracarboxylic dianhydride (also referred to as a ``tetracarboxylic dianhydride component''), a tetracarboxylic acid diester, a diisocyanate, and a component selected from dicarboxylic acid Thus, in obtaining a polyamic acid, a polyamic acid ester, a polyurea, or a polyamide, a known synthetic method can be used. In general, it is a method of reacting at least one component selected from a diamine component and a tetracarboxylic dianhydride component, a tetracarboxylic acid diester, a diisocyanate, and a dicarboxylic acid in an organic solvent.

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

The organic solvent used for the reaction is not particularly limited as long as the resulting polymer is dissolved. Moreover, even if it is an organic solvent in which a polymer does not dissolve, you may use it by mixing with the said solvent as long as the produced polymer does not precipitate. In addition, since moisture in the organic solvent inhibits the polymerization reaction and furthermore causes hydrolysis of the resulting polymer, it is preferable to use a dehydration-dried organic solvent.

As an organic solvent, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, N-methylcaprolactam, dimethylsulfoxide Seed, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl Ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoiso Propyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate , Diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxy butanol, Diisopropyl ether, ethylisobutyl 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, lactic acid Tyl, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxypropionic acid Ethyl, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxypropionic acid butyl, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1 -Hexanol, etc. are mentioned. These organic solvents may be used individually or may be mixed and used.

When reacting a diamine component and a tetracarboxylic dianhydride component in an organic solvent, a solution obtained by dispersing or dissolving the diamine component in an organic solvent is stirred, and the tetracarboxylic dianhydride component is added as it is or dispersed or dissolved in an organic solvent. Conversely, 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, etc. can be mentioned. Also works. In addition, when the diamine component or the tetracarboxylic dianhydride component is made of a plurality of compounds, the reaction may be carried out in a premixed state, or may be individually sequentially reacted, or individually reacted low molecular weight compounds are mixed and reacted to obtain a high molecular weight compound. You can do it.

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

In the above polymerization reaction, the ratio of the total number of moles of the tetracarboxylic acid dianhydride component to the total number of moles of the diamine component can be selected as an arbitrary value depending on the molecular weight of the polyamic acid to be obtained. Similar to a normal polycondensation reaction, the molecular weight of the polyamic acid to be produced increases as the molar ratio is closer to 1.0. In a preferred range, it 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 in the case of synthesizing polyamic acid, instead of the above tetracarboxylic dianhydride, as in the general polyamic acid synthesis method, the corresponding structure The corresponding polyamic acid can also be obtained by using a tetracarboxylic acid derivative such as tetracarboxylic acid or tetracarboxylic acid dihalide, and reacting by a known method. Moreover, when synthesizing a polyurea, what is necessary is just to make a diamine and a diisocyanate react. When preparing polyamic acid ester or polyamide, diamine, a component selected from tetracarboxylic acid diester and dicarboxylic acid, in the presence of a known condensing agent, or after inducing an acid halide by a known method, diamine and Just react.

As a method of imidizing the above-described polyamic acid to form a polyimide, thermal imidation in which a solution of polyamic acid is heated as it is, and catalytic imidization in which a catalyst is added to a solution of polyamic acid are exemplified. Moreover, it is preferable that it is 30% or more, and it is more preferable that it is 30-99% of the imidation ratio from polyamic acid to polyimide from the point which can raise a voltage retention. On the other hand, from the viewpoint of whitening properties, that is, suppressing the precipitation of the polymer in the varnish, 70% or less is preferable. When both characteristics are added, 40-80% is more preferable.

When the polyamic acid is thermally imidized in a solution, the temperature is usually 100 to 400°C, preferably 120 to 250°C, and it is preferable to perform while removing water generated by the imidation reaction outside 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 at -20 to 250°C, preferably at 0 to 180°C. The amount of the basic catalyst is usually 0.5 to 30 mole times, preferably 2 to 20 mole times of the amic acid group, and the amount of the acid anhydride is usually 1 to 50 mole times, preferably 3 to 30 mole times of the amic acid group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferable because it has a suitable basicity to advance the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, acetic anhydride is preferable because purification after completion of the reaction becomes easy. The imidation rate by catalytic imidization can be controlled by adjusting the amount of catalyst, reaction temperature, reaction time, and the like.

When the produced polymer is recovered from the reaction solution of the polymer, the reaction solution may be added to a poor solvent to precipitate. Examples of poor solvents used for precipitation generation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer injected into the poor solvent and precipitated may be collected by filtration and then dried at room temperature or heated under normal pressure or reduced pressure. Further, if the polymer recovered by precipitation is re-dissolved in an organic solvent and the operation of reprecipitation recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and when three or more types of poor solvents selected from these are used, the purification efficiency is further increased, so it is preferable.

In addition, when the radical-generating film is made of a polymer containing an organic group that induces radical polymerization, the composition for forming a radical-generating film used in the present invention may contain a polymer other than a polymer containing an organic group that induces radical polymerization. do. In that case, the content of the other polymer in all components of the polymer is preferably 5 to 95% by mass, and more preferably 30 to 70% by mass.

The molecular weight of the polymer contained in the radical-generating film-forming composition is the weight measured by the GPC (Gel Permeation Chromatography) method when considering the strength of the radical-generating film obtained by applying the radical-generating film, the workability when forming the film, and the uniformity of the film. As an average molecular weight, 5,000 to 1,000,000 are preferable, More preferably, it is 10,000 to 150,000.

The radical-generating film used in the present invention is a polymer obtained by immobilizing in the film by coating and curing a composition of a compound having a radical-generating group and a polymer to form a film, and a polyimide precursor prepared according to the above production method. , And a polymer selected from the group consisting of polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, etc., wherein a diamine having a site where radical polymerization occurs is contained in the radical generating film-forming composition. You may use at least 1 type of polymer obtained using the diamine component which is 0 mol% of the whole diamine component used for synthesis. The following are mentioned as a compound which has a group which generates a radical added at that time.

As a compound that generates radicals by heat, it is a compound that generates radicals by heating above the decomposition temperature. Such radical thermal polymerization initiators include, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroper Oxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxy ketone Dehydration (dibutylperoxycyclohexane, etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl Esters, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile and 2,2'-di(2-hydroxyethyl) azobisisobutyro Nitrile, etc.) can be mentioned. Such radical thermal polymerization initiators may be used alone, or may be used in combination of two or more.

The compound that generates radicals with light is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, and 2,4-diethylthioxanthone , 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, iso Propyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-( Methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,4-dimethylaminobenzoate ethyl, 4 -Dimethylaminobenzoic acid isoamyl, 4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(t-butylperoxycarbonyl)benzophenone, 2,4,6 -Trimethylbenzoyl diphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl )-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2 -(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)- s-triazine, 4-[pN,N-di(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5 -(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl )Benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis (4-Ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2 '-Biimidazole, 2,2'-bis (2,4-dib Lomophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5 ,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl )-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-( 1H-pyrrol-1-yl)-phenyl) titanium, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t- Hexylperoxycarbonyl)benzophenone, 3,3'-di(methoxycarbonyl)-4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4'-di(methoxycar) Bornyl)-4,3'-di(t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzo Phenone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazole-2( 3H)-ylidene)-1-(2-benzoyl)ethanone, etc. are mentioned. These compounds may be used alone or in combination of two or more.

Further, even when the radical-generating film is made of a polymer containing an organic group that induces radical polymerization, the compound having a group that generates a radical may be contained for the purpose of promoting radical polymerization when energy is applied.

The radical-generating film-forming composition may contain a polymer component and, if necessary, an organic solvent for dissolving or dispersing a radical generator and other components. There is no restriction|limiting in particular in such an organic solvent, For example, the organic solvent as exemplified in the synthesis|combination of the said polyamic acid is mentioned. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N -Dimethylpropanamide and the like are preferable from the viewpoint of solubility. In particular, N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is preferable, but two or more types of mixed solvents may be used.

Moreover, it is preferable to mix and use a solvent which improves the uniformity and smoothness of a coating film with an organic solvent with high solubility of the contained component of a radical-generating film-forming composition.

As a solvent to improve the uniformity or smoothness of the coating film, for example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl Cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl Ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol mono Acetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether , 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxy butanol, diisopropyl ether, ethylisobutyl 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- acetate Butyl, propylene glycol acetate monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxy Toxoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxypropionic acid butyl, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy Cy-2-propanol, propylene glycol monoacetate, Propylene glycol diacetate, propylene glycol-1-monomethylether-2-acetate, propylene glycol-1-monoethylether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate Ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, 2-ethyl-1-hexanol, and the like. You may mix multiple types of these solvents. When using these solvents, it is preferable that it is 5 to 80 mass% of the whole solvent contained in a liquid crystal aligning agent, More preferably, it is 20 to 60 mass %.

Components other than the above may be contained in the radical generating film-forming composition. Examples thereof include compounds that improve film thickness uniformity or surface smoothness when the radical-generating film-forming composition is applied, compounds that improve adhesion between the radical-generating film-forming composition and the substrate, and the film strength of the radical-generating film-forming composition. The compound etc. which further improve are mentioned.

As a compound which improves the uniformity of the film thickness and surface smoothness, a fluorine-type surfactant, a silicone-type surfactant, a nonionic surfactant, etc. are mentioned. More specifically, for example, Ftop EF301, EF303, EF352 (manufactured by Dochem Products), Megapac F171, F173, R-30 (manufactured by Dinippon Ink), Florade FC430, FC431 (manufactured by Sumitomo 3M) ), Asahigard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Corporation), and the like. When these surfactants are used, their usage ratio is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total amount of the polymer 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 group-containing compound, and the like. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetri Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltri Ethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol di Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetragly Cidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane, 3-(N ,N-diglycidyl)aminopropyltrimethoxysilane, etc. are mentioned.

In addition, in order to further increase the film strength of the radical generating film, a phenol compound such as 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane and tetra(methoxymethyl)bisphenol may be added. . In the case of using these compounds, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the polymer contained in the radical-generating film-forming composition.

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

[Radial Generation Film]

The radical generating film of the present invention is obtained by using the radical generating film forming composition. For example, a cured film obtained by applying the radical-generating film-forming composition used in the present invention to a substrate and then drying and firing may be used as a radical-generating film as it is. Moreover, it is also possible to rub this cured film, irradiate polarized light or light of a specific wavelength, or the like, perform treatment such as an ion beam, or irradiate UV to a liquid crystal display element after liquid crystal filling as an alignment film for PSA.

The substrate on which the radical generating film-forming composition is applied is not particularly limited as long as it is a substrate having high transparency, but a substrate on which a transparent electrode for driving a liquid crystal is formed on the substrate is preferable.

For example, glass plate, polycarbonate, poly(meth)acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyether ketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) A plastic plate such as acrylonitrile, triacetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose, etc. may include a substrate on which a transparent electrode is formed.

For a substrate that can be used for an IPS type liquid crystal display element, an electrode pattern such as a standard IPS comb electrode or a PSA fishbone electrode, or a protrusion pattern such as MVA may be used.

Further, in a high-function device such as a TFT-type device, a transistor-like device formed between an electrode for driving a liquid crystal and a substrate is used.

When a transmissive liquid crystal display device is intended, it is common to use a substrate as described above, but when a reflective liquid crystal display device is intended, an opaque substrate such as a silicon wafer is also used if it is only on one side of the substrate. It is possible. In that case, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.

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

The drying process after applying the radical-generating film-forming composition is not necessarily required, but if the time from application to firing is not constant for each substrate, or if it is not fired immediately after application, it is preferable to include a drying process. Do. For this drying, the solvent should be removed so that the shape of the coating film is not deformed by conveyance of the substrate or the like, and the drying means is not particularly limited. For example, a method of drying for 0.5 to 30 minutes, preferably 1 to 5 minutes on a hot plate having a temperature of 40°C to 150°C, preferably 60°C to 100°C is mentioned.

The coating film formed by applying the radical generating film-forming composition by the above method may be fired to form a cured film. In that case, the firing temperature can be usually performed at an arbitrary temperature of 100°C to 350°C, preferably 140°C to 300°C, more preferably 150°C to 230°C, still more preferably 160°C to 220°C. to be. The firing time can be fired in an arbitrary time of usually 5 minutes to 240 minutes. It is preferably 10 to 90 minutes, more preferably 20 to 90 minutes. For heating, a conventionally known method, for example, a hot plate, a hot air circulation oven, an IR oven, a belt furnace, or the like can be used.

Although the thickness of this cured film can be selected as needed, preferably 5 nm or more, more preferably 10 nm or more, since it is easy to obtain the reliability of a liquid crystal display element, it is suitable. In addition, when the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, the power consumption of the liquid crystal display element is not extremely large, so it is suitable.

Although the first substrate having the radical generating film can be obtained as described above, the radical generating film can be subjected to a uniaxial alignment treatment. As a method of performing the uniaxial alignment treatment, a photo-alignment method, an oblique vapor deposition method, rubbing, and a uniaxial alignment treatment using a magnetic field may be mentioned.

In the case of performing alignment treatment by rubbing in one direction, for example, the substrate is moved so that the rubbing cloth and the film come into contact with each other while rotating the rubbing roller wound around the rubbing cloth. In the case of the first substrate of the present invention on which the comb electrode is formed, the direction is selected according to the electrical properties of the liquid crystal, but in the case of using a liquid crystal having positive dielectric anisotropy, the rubbing direction is in which the comb electrode is extended. It is preferable to set it in almost the same direction as the direction.

As a step of creating the zero anchoring portion and the strong anchoring portion, a method of irradiating radiation in an arbitrary pattern through a photo mask or the like is exemplified. This is a step in which the radical generation site is eliminated by irradiating radiation to the radical generation film in advance so as not to become a zero anchoring state. As the radiation for performing this step, polarized light or light of a specific wavelength, ion beam, and the like can be mentioned. It is particularly preferable to irradiate light with a wavelength at which the absorbance of the portion corresponding to the photo radical generation site is highest.

The second substrate of the present invention is the same as the first substrate except that it does not have a radical generating film. It is preferable to use a substrate having a conventionally known liquid crystal alignment film.

<liquid crystal cell>

In the liquid crystal cell of the present invention, after forming a radical generating film on a substrate by the above method, a substrate having the radical generating film (first substrate) and a substrate having a known liquid crystal alignment film (second substrate) It is obtained by arranging the generation film and the liquid crystal aligning film so as to face each other, fixing a sealing agent with a spacer therebetween, and injecting and sealing a liquid crystal composition containing a liquid crystal and a radically polymerizable compound. At that time, the size of the spacer to be used is usually 1 to 30 µm, but preferably 2 to 10 µm.

The method of injecting a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is not particularly limited, and a vacuum method in which a mixture containing a liquid crystal and a polymerizable compound is injected after reducing the pressure inside the produced liquid crystal cell, polymerization with liquid crystal And a dropping method in which a mixture containing the compound is added dropwise and then sealed.

<Liquid crystal and liquid crystal composition containing a radically polymerizable compound>

In the preparation of the liquid crystal display device 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, but, for example, a compound having one or two or more polymerizable unsaturated bonds per molecule to be. Preferably, it is a compound having one polymerizable unsaturated bond per molecule (hereinafter sometimes referred to as "a compound having a monofunctional polymerization reactive group", "a compound having a monofunctional polymerization reactive group", etc.). The polymerizable unsaturated bond is preferably a radical polymerizable unsaturated bond, and is, for example, a vinyl bond.

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

In addition, as the polymerization reactive group of the radical polymerizable compound, a polymerizable group selected from the following structures is preferable.

[Formula 22]

(In the formula, * represents a bonding site with a moiety other than a polymerizable unsaturated bond of the compound molecule. R ^b represents a C2-C8 linear alkyl group, and E represents a single bond, -O-, -NR ^c -, Represents a bonding group selected from -S-, an ester bond and an amide bond, R ^c represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.)

Further, in the liquid crystal composition containing the liquid crystal and the radical polymerizable compound, it is preferable to contain a radical polymerizable compound in which the Tg of the polymer obtained by polymerizing the radical polymerizable compound is 100°C or less.

A compound having a monofunctional radical polymerization reactive group is one having an unsaturated bond capable of performing radical polymerization in the presence of an organic radical, such as t-butyl methacrylate, hexyl methacrylate, and 2-ethylhexyl methacrylate. Methacrylate monomers such as rate, 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, styrene derivatives (e.g., o-, m-, p-methoxystyrene, o-, m-, pt-butoxystyrene, o-, m-, p-chloromethylstyrene, etc.), vinyl esters (E.g., vinyl acetate, vinyl propionate, vinyl benzoate, 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 (eg, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloroprene, vinyl fluoride, etc.), and other vinyl monomers, but the present invention is not limited thereto. These various radical polymerizable monomers may be used alone or in combination of two or more. Moreover, it is preferable that these have compatibility with liquid crystal

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

[Formula 23]

In formula (1), R ^a and R ^b each independently represent a straight-chain alkyl group having 2 to 8 carbon atoms, and E is selected from a single bond, -O-, -NR ^c -, -S-, an ester bond, and an amide bond. Represents a bonding group, and R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

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

And, as the radically polymerizable compound represented by the above formula (1), in the formula, E is an ester bond (a bond represented by -C(=O)-O- or -OC(=O)-). It is preferable from the viewpoints of ease, compatibility with liquid crystals, and polymerization reactivity, and specifically, a compound having the following structure is preferable, but is not particularly limited.

[Formula 24]

In formulas (1-1) and (1-2), Ra and Rb each independently represent a straight-chain alkyl group having 2 to 8 carbon atoms.

Further, in the liquid crystal composition containing the liquid crystal and the radical polymerizable compound, it is preferable to contain a radical polymerizable compound in which the Tg of the polymer obtained by polymerizing the radical polymerizable compound is 100°C or less.

These various radical polymerizable monomers may be used alone or in combination of two or more. Moreover, it is preferable that these have compatibility with a 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, and preferably 50% by mass or less, based on the total mass of the liquid crystal and the radically polymerizable compound. More preferably, it is 20 mass% or less.

It is preferable that the polymer obtained by polymerizing the radical polymerizable compound has a Tg of 100°C or less.

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

Next, the liquid crystal cell into which the mixture (liquid crystal composition) containing the liquid crystal and the radical polymerizable compound has been introduced is given energy sufficient for polymerization reaction of the radical polymerizable compound. This can be carried out, for example, by applying heat or by UV irradiation, and the radical polymerizable compound is polymerized on the spot, whereby desired properties are expressed. Among them, UV irradiation is preferred because the use of UV enables oriented patterning and polymerization reaction in a shorter time.

Further, at the time of UV irradiation, heating may be performed. The heating temperature at the time of UV irradiation is preferably within a temperature range in which the introduced liquid crystal exhibits liquid crystallinity, and is usually 40° C. or higher, and heating at a temperature below the temperature at which the liquid crystal changes to an isotropic phase is preferable. .

Here, as for the UV irradiation wavelength in the case of UV irradiation, it is preferable to select a wavelength in which the reaction quantum yield of the reacting polymerizable compound is best, and the UV irradiation amount is usually 0.01 to 30 J, but preferably 10 J or less. , The smaller the amount of UV irradiation is suitable because the reduction in reliability due to destruction of the members constituting the liquid crystal display can be suppressed, and the UV irradiation time can be reduced, thereby improving the manufacturing tact.

In addition, heating in the case of polymerization only by heating, not UV irradiation, is a temperature at which the polymerizable compound reacts, and is preferably performed in a temperature range below the decomposition temperature of the liquid crystal. Specifically, it is, for example, 100°C or more and 150°C or less.

When energy sufficient for polymerization reaction of the radically polymerizable compound is given, it is preferable that no voltage is applied and in an electric field state.

<Liquid crystal display element>

A liquid crystal display element can be produced using the liquid crystal cell thus obtained.

For example, by providing a reflective electrode, a transparent electrode, a λ/4 plate, a polarizing film, a color filter layer, and the like in this liquid crystal cell according to a conventional method, as necessary, a reflective liquid crystal display element can be obtained.

In addition, by providing a backlight, a polarizing plate, a λ/4 plate, a transparent electrode, a polarizing film, a color filter layer, and the like in the liquid crystal cell according to a conventional method, as necessary, a transmission type liquid crystal display element can be obtained.

Example

Although the present invention will be specifically described by way of examples, the present invention is not limited to these examples. The symbol of the compound used in the polymerization of the polymer and the preparation of the film-forming composition and the method of evaluation of properties are as follows.

[Formula 25]

NMP: N-methyl-2-pyrrolidone,

GBL: γ-butyrolactone,

BCS: Butyl Cellosolve.

<Viscosity measurement>

About the polyamic acid solution, the viscosity of 25 degreeC was measured with the sample volume 1.1 mL and the controller TE-1 (1 degree 34' R24) using the E-type viscometer TVE-22H (manufactured by Toki Sangyo).

<Measurement of imidation rate>

20 mg of the polyimide powder was placed in an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Chemical Co., Ltd.), and 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) mixture) was added. , And completely dissolved by applying ultrasonic waves. The 500 MHz proton NMR of this solution was measured with a measuring device (JNW-ECA500 manufactured by Nippon Denshi Datum).

The imidation rate is determined using a proton derived from a structure that does not change before and after imidation as a reference proton, and the integrated peak value of this proton and the integrated value of the proton peak derived from NH of the amide group appearing around 9.5 to 10.0 ppm are used. It was determined by the following equation.

Imidation rate (%) = (1-α·x/y)×100

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

<Polymer polymerization and preparation of radical generating film-forming composition>

Synthesis Example 1

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

To a 100 ml 4-neck flask equipped with a nitrogen introduction tube, air cooling tube, and mechanical stirrer, measure 1.62 g (15.00 mmol) of DA-1 and 3.96 g (15.00 mmol) of DA-2, and add 48.2 g of NMP. It was stirred under a nitrogen atmosphere and completely dissolved. After confirming the dissolution, 3.75 g (15.00 mmol) of TC-2 was added and reacted at 60° C. for 3 hours in a nitrogen atmosphere. It returned to room temperature again, 2.71 g (13.80 mmol) of TC-1 was added, and it was made to react at 40 degreeC in nitrogen atmosphere for 12 hours. The polymerization viscosity was confirmed, TC-1 was further added so that the polymerization viscosity was 1000 mPa·s, and a polymerization solution having a polyamic acid concentration of 20% by mass was obtained.

In a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, 60 g of the polyamic acid solution obtained above was weighed, 111.4 g of NMP was added to prepare a 7 mass% solution, and 9.10 g (88.52 mmol) of acetic anhydride was added while stirring. And 3.76 g (47.53 mmol) of pyridine were added, followed by stirring at room temperature for 30 minutes, followed by stirring at 55° C. for 3 hours to react. After completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500 ml of methanol while stirring to precipitate a solid. The solid was recovered by filtration, and the solid was further added to 300 ml of methanol, stirred and washed twice for 30 minutes, and the solid was recovered by filtration, air-dried, and then dried in a vacuum oven at 60°C. By performing, the number average molecular weight of 11300, the weight average molecular weight of 32900, and the imidation ratio of 53% of polyimide (PI-1) were obtained.

Synthesis Example 2

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

1.62 g (15.00 mmol) DA-1 and 4.96 g (15.00 mmol) DA-3 were measured in a 100 ml 4-neck flask equipped with a nitrogen inlet tube, an air cooling tube, and a mechanical stirrer, and 51.90 g of NMP was added. It was stirred under a nitrogen atmosphere and completely dissolved. After confirming the dissolution, 3.75 g (15.00 mmol) of TC-2 was added and reacted at 60° C. for 3 hours in a nitrogen atmosphere. It returned to room temperature again, 2.64 g (13.5 mmol) of TC-1 was added, and it was made to react at 40 degreeC in nitrogen atmosphere for 12 hours. The polymerization viscosity was confirmed, TC-1 was further added so that the polymerization viscosity was 1000 mPa·s, and a polymerization solution having a polyamic acid concentration of 20% by mass was obtained.

To a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, weigh 60 g of the polyamic acid solution obtained above, add 111.4 g of NMP to prepare a 7 mass% solution, and add 8.38 g (81.4 mmol) of acetic anhydride while stirring And 3.62 g (45.8 mmol) of pyridine were added and stirred at room temperature for 30 minutes, followed by stirring at 55° C. for 3 hours to react. After completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500 ml of methanol while stirring to precipitate a solid. The solid was recovered by filtration, and the solid was further added to 300 ml of methanol, stirred and washed twice for 30 minutes, and the solid was recovered by filtration, air-dried, and then dried in a vacuum oven at 60°C. The number average molecular weight Mn was 13100, the weight average molecular weight Mw was 34000, and the imidation ratio was 55% of polyimide (PI-2).

Synthesis Example 3

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

In a 100 ml 4-neck flask equipped with a nitrogen inlet tube, an air cooling tube, and a mechanical stirrer, measure 1.62 g (15.00 mmol) DA-1 and 5.65 g (15.00 mmol) DA-4, and add 55.4 g of NMP. It was stirred under a nitrogen atmosphere and completely dissolved. After confirming the dissolution, 3.75 g (15.00 mmol) of TC-2 was added and reacted at 60° C. for 3 hours in a nitrogen atmosphere. It returned to room temperature again, 2.82 g (14.40 mmol) of TC-1 was added, and it was made to react at 40 degreeC under nitrogen atmosphere for 12 hours. The polymerization viscosity was confirmed, TC-1 was further added so that the polymerization viscosity was 1000 mPa·s, and a polymerization solution having a polyamic acid concentration of 20% by mass was obtained.

To a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, weigh 60 g of the polyamic acid solution obtained above, add 111.4 g of NMP to prepare a 7% by mass solution, and add 8.36 g (81.2 mmol) of acetic anhydride while stirring And 3.65 g (46.1 mmol) of pyridine were added, followed by stirring at room temperature for 30 minutes, followed by stirring at 55° C. for 3 hours to react. After completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500 ml of methanol while stirring to precipitate a solid. The solid was recovered by filtration, and the solid was further added to 300 ml of methanol, stirred and washed twice for 30 minutes, and the solid was recovered by filtration, air-dried, and then dried in a vacuum oven at 60°C. The number average molecular weight Mn was 12900, the weight average molecular weight Mw was 31000, and the imidation ratio obtained the polyimide (PI-3) of 51%.

Radical Generating Film Forming Composition: Preparation of AL1

In a 50 ml Erlenmeyer flask equipped with a magnetic stirrer, 2.0 g of the polyimide powder (PI-1) obtained in Synthesis Example 1 was weighed, 18.0 g of NMP was added, and stirred at 50°C to completely dissolve. Further, by adding 6.7 g of NMP and 6.7 g of BCS, and stirring for an additional 3 hours, the radical-generating film-forming composition according to the present invention: AL1 (solid content: 6.0 mass%, NMP: 66 mass%, BCS: 30 mass%) Got it.

Radical Generation Film Forming Composition: Preparation of AL2

In a 50 ml Erlenmeyer flask equipped with a magnetic stirrer, 2.0 g of the polyimide powder (PI-2) obtained in Synthesis Example 2 was weighed, 18.0 g of NMP was added, and stirred at 50°C to completely dissolve. Further, by adding 6.7 g of NMP and 6.7 g of BCS and stirring for an additional 3 hours, the radical-generating film-forming composition of the present invention: AL2 (solid content: 6.0 mass%, NMP: 66 mass%, BCS: 30 mass%) Got it.

Non-radical-generating film-forming composition: Preparation of AL3

In a 50 ml Erlenmeyer flask equipped with a magnetic stirrer, 2.0 g of the polyimide powder (PI-3) obtained in Synthesis Example 3 was weighed, 18.0 g of NMP was added, and stirred at 50°C to completely dissolve. Further, by adding 6.7 g of NMP and 6.7 g of BCS and stirring for an additional 3 hours, a non-radical-generating film-forming composition for comparison: AL3 (solid content: 6.0 mass%, NMP: 66 mass%, BCS: 30 mass%) Got it.

[Table 1]

[Table 2]

[Table 3]

<Preparation of polymerizable compound>

Polymerizable Compound Synthesis Example 1

Synthesis of 2-(heptanoyloxymethyl)acrylic acid ethyl ester

[Formula 26]

First Step: Synthesis of 2-hydroxymethylacrylic acid ethyl ester

To a 500 ml four-necked flask equipped with a nitrogen introduction tube, 10 mg of 4-methoxyphenol and 21.88 g (195.1 mmol) of DABCO (1,4-diazabicyclo[2.2.2]octane) were weighed, and pure water ) Was added, and paraformaldehyde 11.52 g (390.1 mmol) was added while stirring at 10° C. or less in a nitrogen atmosphere, followed by stirring for 1 hour. When it was confirmed that it changed from a slurry state to a solution state, 300 ml of acetonitrile was added, and 19.53 g (195.1 mmol) of ethyl acrylate was added dropwise, followed by reaction at 50°C for 5 hours. After completion of the reaction, the reaction solution was transferred to a separation lot, and 50 ml of n-hexane was added. It was confirmed that it was divided into three layers, the lower two layers were recovered, and this operation was performed three times. Further, hydrochloric acid was added so that the pH was 4 to 5, and extraction was performed using ethyl acetate. Anhydrous magnesium sulfate was added to the extracted solution, stirred and dried, and then filtered and concentrated to obtain 22.9 g (175.6 mmol, yield 90%) of a colorless and transparent oily liquid. Structure was confirmed to be the desired compound by nuclear magnetic resonance spectra ⁽¹ H-NMR spectrum). The measurement data are shown below.

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

Second step: Synthesis of 2-(heptanoyloxymethyl)acrylic acid ethyl ester

To a 500 ml four-necked flask equipped with a nitrogen introduction tube, 19.9 g (152.9 mmol) of 2-hydroxymethylacrylic acid ethyl ester obtained by the above method was weighed, and 300 ml of THF and 23.2 g (229.3 mmol) of triethylamine were added. , While maintaining at 10°C or less under a nitrogen atmosphere, 25.0 g (168.2 mmol) of heptanoyl chloride was added dropwise, followed by reaction for 6 hours. After completion of the reaction, the precipitated triethylamine hydrochloride was removed by filtration, the reaction solution was concentrated, redissolved with 300 ml of ethyl acetate, washed three times with 100 ml of a 10% potassium carbonate aqueous solution, washed three times with 50 ml of pure water, After drying over anhydrous magnesium sulfate, it was filtered and concentrated to obtain a pale yellow viscous body. Further, it was purified by flash column chromatography (developing solvent: ethyl acetate:n-hexane=20:80), and solvent removal and vacuum drying were performed to obtain 32.2 g (133.0 mmol: yield: 87%) of a colorless and transparent oily liquid. Got it. Structure was confirmed to be the desired compound by nuclear magnetic resonance spectra ⁽¹ H-NMR spectrum). The measurement data are shown below.

¹ H NMR (400MHz, CDCl ₃ )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 itaconic acid

[Formula 27]

In a four-necked flask with a Dean Stark tube, 23.8 g (182.9 mmol) of itaconic acid and 35.5 g (347.5 mmol) of 1-hexanol were weighed and taken, 500 ml of cyclohexane, 0.9 g (9.1 mmol) of concentrated sulfuric acid, and dibutylhydroxy Toluene (BHT) 0.04 g (1.82 mmol) was added, followed by a nitrogen atmosphere, followed by dehydration and condensation reaction at 110° C. for 24 hours. After completion of the reaction, 100 ml of n-hexane was added to the reaction solution, washed three times with 100 g of 10% sodium carbonate aqueous solution and three times with 100 ml of pure water, and dried over anhydrous magnesium sulfate. After filtration and concentration, and vacuum drying, 48.6 g (162.8 mmol: yield 89%) of a colorless and transparent oily liquid was obtained. Structure was confirmed to be the desired compound by nuclear magnetic resonance spectra ⁽¹ H-NMR spectrum). The measurement data are shown below.

¹ H NMR (400MHz, CDCl ₃ ) δ: 6.30 (1H), 5.65 (1H), 4.20-4.00 (4H), 3.32 (2H), 1.64-1.58 (4H), 1.40-1.25 (12H), 0.96-0.83 (6H)

<Manufacture of liquid crystal display device>

Using the AL1-AL3 obtained above and SE-6414 (manufactured by Nissan Chemical Industry Co., Ltd.) which is a liquid crystal aligning agent for horizontal alignment, a liquid crystal display element was produced in the configuration 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 30 mm x 35 mm and a thickness of 0.7 mm. On the substrate, an ITO (Indium-Tin-Oxide) electrode having a comb-shaped pattern having an electrode width of 10 μm and an electrode-to-electrode spacing of 10 μm is formed to form a pixel. Each pixel has a size of 10 mm in length and about 5 mm in width.

After filtering AL1 to AL3 or SE-6414 with a 1.0 μm filter, it was applied to the electrode-forming surface of the IPS substrate by spin coating, and dried on a hot plate at 80° C. for 1 minute. Subsequently, AL1 to AL3 were fired at 220°C for 20 minutes and SE-6414 at 220°C for 20 minutes to obtain a coating film having a thickness of 100 nm, respectively.

This substrate with a coating film was shielded from light with a metal plate so that half of the substrate was not exposed to light, and ultraviolet rays were irradiated with a high-pressure mercury lamp through a band pass filter having a wavelength of 313 nm so that the exposure amount was 5000 mJ. Hereafter, this operation is called primary UV treatment.

After the exposure treatment, the rubbing was performed so that the rubbing direction was inclined by 5° from the longitudinal direction of the comb electrode. The rubbing was performed using a rayon cloth manufactured by Kako Yoshikawa: YA-20R, under conditions of a roll diameter of 120 mm, a rotation speed of 300 rpm, a moving speed of 50 mm/sec, and a pressing amount of 0.4 mm. After the rubbing treatment, ultrasonic irradiation was performed in pure water for 1 minute, and dried at 80°C for 10 minutes.

(Second substrate)

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

SE-6414 was applied to the glass surface of the rear ITO substrate with a 1.0 µm filter, applied by a spin coating method, and dried on a hot plate at 80°C for 1 minute. Next, AL1 and AL2 were fired at 220°C for 20 minutes, and SE-6414 was fired at 220°C for 20 minutes to obtain a coating film having a thickness of 100 nm, respectively, followed by rubbing treatment. For the rubbing treatment, a rayon fabric manufactured by Kako Yoshikawa: YA-20R was used, and rubbing was performed under conditions of a roll diameter of 120 mm, a rotational speed of 1000 rpm, a movement speed of 50 mm/sec, and a pressing amount of 0.4 mm. After the rubbing treatment, ultrasonic irradiation was performed in pure water for 1 minute, and dried at 80°C for 10 minutes.

(Production of liquid crystal cell)

Using the two types of substrates (the first substrate and the second substrate) with the liquid crystal alignment film, the liquid crystal injection port was left and the periphery was sealed to produce an empty cell having a cell gap of about 4 μm. At this time, the rubbing direction of the 1st board|substrate and 2nd board|substrate becomes antiparallel, and the thing which cross|intersects by 85 degree was created, respectively.

In this empty cell, a liquid crystal (one obtained by adding each additive to the positive liquid crystal MLC-3019 for IPS manufactured by Merck and MLC3018U for TN manufactured by Merck) was vacuum-injected at room temperature, and then the injection port was sealed to form a liquid crystal cell. did. The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element and a TN mode liquid crystal display element. Then, the obtained liquid crystal cell was heat-treated at 120 degreeC for 10 minutes.

As the secondary UV treatment, a high-pressure mercury lamp was used and irradiation was performed 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 was 5000 mJ. Hereinafter, the details of the created cell are shown in Table 4 below.

[Table 4]

<Visual evaluation of liquid crystal orientation>

The orientation of the TN mode liquid crystal cell was confirmed using the polarizing plate set with Cross Nicol. In the case of not performing UV treatment, since the alignment regulating force of the one-side alignment layer is lost (that is, it becomes a zero anchoring state), it cannot be sufficiently twisted by the regulating force of the chiral dopant in the liquid crystal. On the other hand, since the UV-treated region loses polymerization reactivity, the anchoring power is maintained. Thus, a twist orientation occurs. As a result, two kinds of orientation states occur in the pixel. As shown in Fig. 1, when the UV-irradiated region is in TN orientation (white), the non-UV-irradiated region is in horizontal orientation (black), it is set as ○, and when there is no change in each region, it is set as x. .

[Table 5]

In the case of using a liquid crystal without additives in the liquid crystal, and in the case of using a material that does not generate radicals due to light, alignment patterning, that is, a change in alignment regulating force, did not occur even after performing the primary UV treatment. In this respect, it can be seen that the combination of the optical radical generating film and the additive of the present invention is important.

<Evaluation of electro-optical properties>

Using cells 13 to 24 (horizontal alignment cells), the V-T curve was measured to measure the change in the threshold voltage and the mode efficiency. To measure the VT curve, a white LED backlight and a luminance meter are set so that the optical axis is aligned, and a liquid crystal cell (liquid crystal display element) attached with a polarizing plate is set so that the luminance is the smallest between them, and the voltage is up to 8V at 1V intervals. Was applied and the luminance in the voltage was measured. The value of the drive threshold voltage was estimated from the obtained V-T curve. The mode efficiency was measured by calculating the luminance at Vmax of the liquid crystal cell to the luminance of the LED transmitted light at the time of parallel Nicole of the polarizing plate as a ratio.

The anchoring measurement was roughly approximated by the Frederiks transition method from the magnitude of the threshold voltage.

[Table 6]

Since the cells 13 to 24 are horizontally oriented cells, there is no change to the naked eye even when the cells are in the zero anchoring orientation. Meanwhile, changes in the threshold voltage and luminance of the V-T curve were observed in the first UV-exposed and unexposed portions. From this verification as well, it can be seen that by performing the primary exposure, regions having different anchoring powers can be created in the pixel.

Industrial availability

Advantageous Effects of Invention According to the present invention, an inexpensive raw material can be produced industrially and in a high yield in the zero plane region with different anchoring. Moreover, the liquid crystal display element obtained by the method of this invention is useful as a liquid crystal display element of a vertical alignment system, such as a PSA type liquid crystal display and an SC-PVA type liquid crystal display.

Claims (22)

A step of forming a patterned radical generating film by irradiating radiation to a specific region on the radical generating film, and bringing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound into contact with the patterned radical generating film and maintaining the state And applying sufficient energy to the liquid crystal composition for polymerization reaction of the radically polymerizable compound, wherein the method for producing a patterned zero surface anchoring film. The method of claim 1,
The method, wherein the radical generating film is a radical generating film subjected to a uniaxial alignment treatment. The method according to claim 1 or 2,
The method of performing the step of imparting energy in an electric field. The method according to any one of claims 1 to 3,
The method, characterized in that the radical generating film is a film formed by immobilizing an organic group causing radical polymerization. The method according to any one of claims 1 to 3,
The method characterized in that the radical-generating film is obtained by immobilizing in the film by coating and curing a composition of a compound having a radical-generating group and a polymer to form a film. The method according to any one of claims 1 to 3,
The method, characterized in that the radical generating film is made of a polymer containing an organic group that causes radical polymerization. The method of claim 6,
At least one selected from polyimide precursors, polyimides, polyureas, and polyamides obtained by using a diamine component including a diamine containing an organic group inducing radical polymerization in the polymer containing an organic group causing radical polymerization Method characterized in that it is a polymer of. The method according to any one of claims 4, 6 and 7,
The method in which the organic group causing radical polymerization is an organic group represented by any of the following structures [X-1] to [X-18], [W], [Y] and [Z]:
[Formula 1]

(In formulas [X-1] to [X-18], * represents a bonding site with a moiety other than a polymerizable unsaturated bond of a compound molecule, and S ₁ and S ₂ are each independently -O-, -NR- , -S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, and 1 to 4 carbon atoms Represents the alkyl group of.)
[Formula 2]

(In formulas [W], [Y], and [Z], * represents a bonding site with a moiety other than a polymerizable unsaturated bond of the compound molecule, and Ar is a phenyl which may have an organic group and/or a halogen atom as a substituent. Represents an aromatic hydrocarbon group selected from the group consisting of ene, naphthylene and biphenylene, R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R ⁹ and R ^{When 10} is an alkyl group, they may be bonded to each other at the terminal to form a ring structure, where Q represents the following structure.
[Formula 3]

(In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O- or -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, * represents other than Q of the compound molecule It indicates the binding site to the part.)
R ₁₂ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.). The method of claim 7,
A method characterized in that the diamine containing an organic group causing radical polymerization is a diamine having a structure represented by the following general formula (6) or the following general formula (7):
[Formula 4]

(In formula (6), R ⁶ is a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ )-, -CON(CH ₃ )- or -N(CH ₃ )CO-,
R ⁷ represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and one or more _{of any -CH 2} -or -CF _{2-of the alkylene group are each independently} -CH=CH-, may be substituted with a group selected from a divalent carbocyclic ring and a divalent heterocycle, and any of the following groups, namely -O-, -COO-, -OCO-, -NHCO- , -CONH- or -NH- may be substituted with these groups provided they are not adjacent to each other;
R ⁸ represents a radical polymerization reactive group selected from the following formula:
[Formula 5]

(In formulas [X-1] to [X-18], * represents a bonding site with a moiety other than the radical polymerization reactive group of the compound molecule, and S ₁ and S ₂ are each independently -O-, -NR- , -S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, and 1 to 4 carbon atoms Represents an alkyl group of))
[Formula 6]

(In formula (7), T ₁ and T ₂ are each independently a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-,- CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )- or -N(CH ₃ )CO-,
S ⁰ represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and one or more _{of any -CH 2} -or -CF _{2-of the alkylene group are each independently} -CH=CH-, may be substituted with a group selected from a divalent carbocyclic ring and a divalent heterocycle, and any of the following groups, namely -O-, -COO-, -OCO-, -NHCO- , -CONH- or -NH- may be substituted with these groups provided they are not adjacent to each other,
J is an organic group represented by any of the following formulas,
[Formula 7]

(In formulas [W], [Y], and [Z], * _{represents a bonding site with T 2} , and Ar represents phenylene, naphthylene, and biphenylene which may have an organic group and/or a halogen atom as a substituent. Represents an aromatic hydrocarbon group selected from the group ^{consisting of, R 9} and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q represents the structure of any of the following:
[Formula 8]

(In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O- or -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, * represents other than Q of the compound molecule It represents the binding site to the part.)
R ₁₂ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.)). The method according to any one of claims 1 to 9,
The method, wherein at least one of the radically polymerizable compounds is a compound having compatibility with a liquid crystal and having one polymerizable unsaturated bond per molecule. The method of claim 10,
The method, wherein the polymerization reactive group of the radically polymerizable compound is selected from the following structures.
[Formula 9]

(In the formula, * represents a bonding site with a moiety other than a polymerizable unsaturated bond of the compound molecule. R ^b represents a C2-C8 linear alkyl group, and E represents a single bond, -O-, -NR ^c -, Represents a bonding group selected from -S-, an ester bond and an amide bond, R ^c represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.) The method according to any one of claims 1 to 11,
In a liquid crystal composition containing the liquid crystal and a radically polymerizable compound, a liquid crystal composition containing a radically polymerizable compound in which Tg of the polymer obtained by polymerizing the radically polymerizable compound is 100°C or less is used. . A step of preparing a first substrate having a radical generating film and a second substrate which may have a radical generating film,
Creating a cell such that the radical generating film on the first substrate faces the second substrate, and
Including 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,
A method for producing a liquid crystal cell using the method according to any one of claims 1 to 12. The method of claim 13,
A method of manufacturing a liquid crystal cell in which the second substrate is a second substrate having no radical generating film. The method of claim 14,
The method for manufacturing a liquid crystal cell, wherein the second substrate is a substrate coated with a liquid crystal alignment layer having uniaxial alignment. The method of claim 15,
The method for producing a liquid crystal cell, wherein the liquid crystal alignment film having uniaxial alignment is a liquid crystal alignment film for horizontal alignment. The method according to any one of claims 13 to 16,
A method of manufacturing a liquid crystal cell in which the first substrate having the radical generating film is a substrate having a comb electrode. It contains liquid crystal and radical polymerizable compounds,
At least one of the radically polymerizable compounds is a compound having compatibility with a liquid crystal and having one polymerizable unsaturated bond per molecule,
The liquid crystal composition, wherein the polymerization reactive group is selected from the following structures:
[Formula 10]

(In the formula, * represents a bonding site with a moiety other than a polymerizable unsaturated bond of the compound molecule. R ^b represents a C2-C8 linear alkyl group, and E represents a single bond, -O-, -NR ^c -, Represents a bonding group selected from -S-, an ester bond and an amide bond, R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) A method for manufacturing a liquid crystal display element using a film that creates a zero-plane anchoring state obtained by using the method according to any one of claims 1 to 17. A liquid crystal display device obtained by using the method according to claim 19. The method of claim 20,
A liquid crystal display device, wherein the first substrate or the second substrate has an electrode. The method of claim 20 or 21,
A liquid crystal display element which is a low-voltage drive transverse electric field liquid crystal display element.

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