KR102689870B1 - Manufacturing method of zero plane anchoring film and liquid crystal display device - Google Patents

Abstract

The present invention provides an industrial manufacturing method for a zero-plane anchoring film, a good liquid crystal display element using the same, and a liquid crystal display element manufacturing method.
A method for producing a zero-plane anchoring film, comprising a step of applying energy sufficient to polymerize the radically polymerizable compound in a state in which a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is brought into contact with a radical generating film, and 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 and a second substrate not having a radical generating film, and applying the radical polymerizable compound to the cell. This is a method for producing a functional film that includes a step of providing sufficient energy to cause a polymerization reaction.

Description

Manufacturing method of zero plane anchoring film and liquid crystal display device

The present invention relates to a manufacturing method using polymer stabilization technology that can produce a zero-plane anchoring film using a method that is inexpensive and does not involve complicated processes, and a liquid crystal display for realizing even lower voltage driving using the manufacturing method. It relates to devices and their manufacturing methods.

Recently, liquid crystal display elements have been widely used in displays of mobile phones, computers, and TVs. Liquid crystal display elements have characteristics such as thinness, light weight, and low power consumption, and are expected to be applied to further content such as VR and ultra-high-definition displays in the future. There are various display modes proposed for liquid crystal displays, such as TN (Twisted Nematic), IPS (In-Plane Switching), and VA (Vertical Alignment). All modes include a film (liquid crystal alignment film) that guides the liquid crystal to the desired alignment state. ) is being used.

In particular, for products with touch panels such as tablet PCs, smartphones, and smart TVs, IPS mode is preferred because the display is less likely to be disturbed even when touched. In recent years, FFS (Frindge Field Switching) has been used to improve contrast and viewing angle characteristics. ) and technologies using non-contact technology using photo-alignment have been used.

However, FFS has the problem that the substrate manufacturing cost is greater than that of IPS, and a display defect unique to FFS mode called Vcom shift occurs. Also, with regard to photo-alignment, compared to the rubbing method, there are merits in that the size of the device that can be manufactured can be increased and the display characteristics can be greatly improved, but there are problems in the principle of photo-alignment (if it is a decomposition type, there is a problem of decomposition product origin). poor display, burn-in due to lack of orientation if it is an isomerized type, etc.). In order to solve such problems, liquid crystal display device manufacturers and liquid crystal alignment film manufacturers are currently working on various ideas.

Meanwhile, an IPS mode using what is called zero-plane anchoring has been proposed recently, and it has been reported that using this method improves contrast and enables significantly low-voltage driving compared to the conventional IPS mode (see Patent Document 1).

Specifically, a liquid crystal alignment film having strong anchoring energy is used on one side of the substrate, and the side of the substrate provided with the electrode on the side that generates the transverse electric field is treated such that it does not have any liquid crystal alignment regulating force. This is a method of making an IPS mode liquid crystal display device using them.

Recently, a zero-surface state has been created using a thick polymer brush, etc., and a zero-surface anchoring IPS mode technology has been proposed (Reference 2). This technology has realized a significant improvement in contrast ratio and a significant decrease in driving voltage.

Japanese Patent No. 4053530 Publication Japanese Patent Laid-Open No. 2013-231757

On the other hand, there are problems that arise in principle with this technology. First, in order to stably generate a polymer brush on a substrate, it needs to be carried out under very delicate conditions, which is not realistic considering mass production. Second, although the alignment film performs important functions such as suppressing burn-in, it is difficult to control the necessary electrical properties when using a polymer brush or the like. Third, due to the driving principle, the response speed when the voltage is turned off is very slow. By setting the alignment regulation force to zero, the resistance applied to the liquid crystal during driving is eliminated, thereby significantly lowering the threshold voltage and improving luminance by reducing the area with poor alignment during driving. However, regarding the return of the liquid crystal, the liquid crystal Since the power upon return depends on the elastic force of the liquid crystal, it is thought that the speed decreases significantly compared to when an alignment film is present.

If these technical issues can be solved, it will be a great cost advantage for panel manufacturers, and it will also be beneficial in reducing battery consumption and improving image quality.

The present invention has been made to solve the problems described above, and includes a manufacturing method using polymer stabilization technology that can produce a zero-plane anchoring film, and a simple and inexpensive method at room temperature for non-contact orientation and low driving voltage. The purpose is to provide a transverse electric field liquid crystal display device and a manufacturing method thereof that can simultaneously realize fast response speed when on and off.

In order to solve the above-mentioned problems, the present inventors conducted intensive studies, found a solution that can solve the above-mentioned problems, and completed the present invention having the following gist.

That is, the present invention includes the following.

[1] Preparation of a zero-plane anchoring film, comprising a step of applying energy sufficient to polymerize the radically polymerizable compound in a state in which a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is brought into contact with a radical generating film. method.

[2] The method according to [1], wherein the radical generating film included in the first substrate is a uniaxially aligned radical generating film.

[3] The method described in [1] or [2] in which the steps for applying energy are performed in an electric field.

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

[5] The radical generating film according to any one of [1] to [3], wherein the radical generating film is obtained by applying and curing a composition of a polymer and a compound having a radical generating group to form a film, thereby immobilizing it in the 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 that causes radical polymerization is selected from polyimide precursors, polyimides, polyureas, and polyamides obtained by using a diamine component containing a diamine containing an organic group that causes radical polymerization. The method described in [6], characterized in that it is at least one type of polymer.

[8] The organic groups causing the radical polymerization are [4], [6], and [ 7] Method described in any one of:

[Formula 1]

( ^In the formula ^[ -S-, R represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms, and R ¹ and R ² are each independently a hydrogen atom, a halogen atom, or a C 1 to 4 alkoxy group. represents an alkyl group)

[Formula 2]

(In the formulas [W], [Y], and [Z], * represents a bonding site with a portion other than the polymerizable reactive group of the compound molecule, and Ar represents phenylene 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 naphthylene and biphenylene, R ⁹ and R ¹⁰ each independently represent an alkyl group with 1 to 10 carbon atoms or an alkoxy group with 1 to 10 carbon atoms, and R ⁹ and R ¹⁰ In the case of this alkyl group, Q may be bonded to each other at the terminals to form a ring 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, and * represents a group other than Q in the compound molecule. Indicates the binding site with the part.)

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

[9] The method described in [7], wherein the diamine containing an organic group that causes 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 Represents (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 that is unsubstituted or substituted with a fluorine atom, and one or more of -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 may also be substituted with any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO -, -CONH- or -NH- may be substituted with these groups, provided that they are not adjacent to each other;

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

[Formula 5]

(In ^the formula ^[ , -S-, R represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms, and R ¹ and R ² are each independently a hydrogen atom, a halogen atom, and a carbon number of 1 to 4. 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 represents a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a fluorine atom, and one or more of -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 may also be substituted with any of the groups listed below, namely -O-, -COO-, -OCO-, -NHCO- , -CONH- or -NH- may be substituted with these groups, provided that they are not adjacent to each other,

J is an organic group represented by the formula below,

[Formula 7]

(In the formulas [W], [Y], and [Z], * represents the 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 with 1 to 10 carbon atoms or an alkoxy group with 1 to 10 carbon atoms, and Q represents the following structure:

[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, and * represents a group other than Q in the compound molecule. Indicates the binding site with the part.)

R ¹² represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 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 that is compatible with liquid crystal and has one polymerizable reactive group per molecule.

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

[Formula 9]

(In the formula, * represents a bonding site with a portion other than the polymerizable reactive group of the compound molecule. R ^b represents a straight-chain alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR ^c -, - (R ^c represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms).

[12] In the liquid crystal composition containing the above liquid crystal and a radically polymerizable compound, a liquid crystal composition containing a radically polymerizable compound such that the Tg of the polymer obtained by polymerizing the radically polymerizable compound is 100°C or lower 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 that may have a radical generating film,

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

A step of filling a liquid crystal composition containing a liquid crystal and a radically polymerizable compound between the first and second substrates,

A method for manufacturing a liquid crystal cell using the method according to any one of [1] to [12].

[14] The method for manufacturing a liquid crystal cell according to [13], wherein the second substrate is a second substrate without a 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 orientation.

[16] The method for producing a liquid crystal cell according to [15], wherein the liquid crystal alignment film having the 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] Contains liquid crystal and radically polymerizable compounds,

At least one of the radically polymerizable compounds is a compound that is compatible with liquid crystal and has one polymerizable reactive group per molecule,

A liquid crystal composition, wherein the polymerizable reactive group is selected from the following structures:

[Formula 10]

(In the formula, * represents a bonding site with a portion other than the polymerizable reactive group of the compound molecule. R ^b represents a straight-chain alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR ^c -, - (R ^c represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms).

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

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

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

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

According to the present invention, a zero-surface anchoring film can be produced industrially and with good yield. 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 existing manufacturing methods. In addition, the liquid crystal display device obtained by the manufacturing method of the present invention provides a liquid crystal display device that has excellent characteristics such that the response speed of the liquid crystal when turned off is faster than that of the prior art, and furthermore, there is no low driving voltage, no bright spots, and Vcom shift is less likely to occur. can do.

The present invention is a method for producing a zero plane anchoring film, characterized in that the polymerizable compound is polymerized by UV or heat while a liquid crystal containing a specific polymerizable compound is brought into contact with a radical generating film. 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 and a second substrate that may have a radical generating film, and in the cell, A method for producing a zero plane anchoring film, including a step of providing sufficient energy to polymerize the radically polymerizable compound. Preferably, a step of preparing a first substrate with a radical generating film and a second substrate without a radical generating film, a step of creating a cell so that the radical generating film faces the second substrate, and a step of preparing a cell so that the radical generating film faces the second substrate, and Meanwhile, it is a method of manufacturing a liquid crystal cell including the step of filling a liquid crystal composition containing a liquid crystal and a radically polymerizable compound. For example, this is a method of producing a low-voltage driven IPS liquid crystal display device in which the second substrate is a substrate that does not have a radical generating film and has a liquid crystal alignment film that has been uniaxially aligned, and the first substrate is a substrate that has comb electrodes.

In the present invention, the "zero plane anchoring film" refers to a film that has no force regulating the orientation of liquid crystal molecules in the in-plane direction, or, if present, is weaker than the intermolecular force between liquid crystals, and does not uniaxially align liquid crystal molecules in any direction with this film alone. It says curtain. Additionally, this zero surface anchoring film is not limited to a solid film but also includes a liquid film covering a solid surface. Normally, liquid crystal display elements use a pair of films that regulate the orientation of liquid crystal molecules, that is, liquid crystal alignment films, but liquid crystals can also be aligned when the zero plane anchoring film and the liquid crystal alignment film are used in pairs. This is because the alignment regulating force of the liquid crystal alignment film is also transmitted in the thickness direction of the liquid crystal layer due to the intermolecular force between liquid crystal molecules, and as a result, liquid crystal molecules adjacent to the zero plane anchoring film are also aligned. Therefore, when a liquid crystal alignment film for horizontal alignment is used as the liquid crystal alignment film, a horizontal alignment state can be created throughout the liquid crystal cell. Horizontal alignment refers to a state in which the long axes of liquid crystal molecules are aligned substantially parallel to the surface of the liquid crystal alignment film, and an inclined orientation of several degrees is also included in the category of horizontal alignment.

[Radical 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 contains a group capable of generating radicals. In this 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 applying and curing such a composition to form a film, a radical generating film can be obtained in which a group capable of generating radicals is immobilized in the film. The group capable of generating radicals is preferably an organic group that induces radical polymerization.

Such organic groups that induce radical polymerization include organic groups represented by [X-1] to [X-18], [W], [Y], and [Z] represented by the following structures.

[Formula 11]

( ^In the formula ^[ -S-, R represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms, and R ¹ and R ² are each independently a hydrogen atom, a halogen atom, or a C 1 to 4 alkoxy group. represents an alkyl group)

[Formula 12]

(In the formulas [W], [Y], and [Z], * represents a bonding site with a portion other than the polymerizable reactive group of the compound molecule, and Ar represents phenylene 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 naphthylene and biphenylene, R ⁹ and R ¹⁰ each independently represent an alkyl group with 1 to 10 carbon atoms or an alkoxy group with 1 to 10 carbon atoms, and R ⁹ and R ¹⁰ In the case of this alkyl group, Q may be bonded to each other at the terminals to form a ring structure.

[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, and * represents a group other than Q in the compound molecule. Indicates the binding site with the part.)

R ¹² represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 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, etc. are preferable.

In order to obtain the radical generating film used in the present invention, when using a polymer having an organic group that causes radical polymerization, to obtain a polymer having a group capable of generating radicals, methacrylic group, acrylic group, and vinyl group are used as monomer components. , a monomer having a photoreactive side chain containing at least one selected from an allyl group, a coumarin group, a styryl group, and a cinnamoyl group, or a monomer having a site in the side chain that is decomposed by ultraviolet irradiation and generates a radical is used. It is preferable to manufacture it this way. On the other hand, monomers that generate radicals are thought to have problems such as spontaneous polymerization, which results in unstable compounds. Therefore, from the viewpoint of ease of synthesis, polymers derived from diamines having radical generating sites are preferred. , more preferably polyimide precursors such as polyamic acid and polyamic acid ester, polyimide, polyurea, polyamide, etc.

Specifically, such diamine containing a radical generation site is a diamine having a side chain capable of polymerization by generating a radical, and includes diamine represented by the following general formula (6), but is limited to this. That is not the case.

[Formula 14]

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

R ⁷ represents a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a fluorine atom, and one or more of -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 may also be substituted with any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO -, -CONH- or -NH- may be substituted with these groups, provided that they are not adjacent to each other;

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

[Formula 15]

(In ^the formula ^[ , -S-, R represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms, and R ¹ and R ² are each independently a hydrogen atom, a halogen atom, and a carbon number of 1 to 4. (represents an alkyl group of).

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

Diamines having a photoreactive group containing at least one member selected from the group consisting of a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group, specifically include the following compounds. can be mentioned, but are not limited to these.

[Formula 16]

(In the formula, J ¹ is a single bond, -O-, -COO-, -NHCO-, or -NH-, and J ² is a single bond, or 1 carbon atom unsubstituted or substituted by a fluorine atom Represents an alkylene group of ~20.)

Diamines having a site as a side chain that is decomposed by ultraviolet irradiation and generates radicals include, but are not limited to, diamines represented by the following general formula (7).

[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 represents a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a fluorine atom, and one or more of -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 may also be substituted with any of the groups listed below, namely -O-, -COO-, -OCO-, -NHCO- , -CONH- or -NH- may be substituted with these groups, provided that they are not adjacent to each other,

J is an organic group represented by the formula below,

[Formula 18]

(In the formulas [W], [Y], and [Z], * represents the 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 with 1 to 10 carbon atoms or an alkoxy group with 1 to 10 carbon atoms, and Q represents the following structure:

[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, and * represents a group other than Q in the compound molecule. Indicates the binding site with the part.)

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

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

In particular, in consideration of ease of synthesis, high versatility, characteristics, etc., the structure represented by the following formula is most preferable, but is not limited to these.

[Formula 20]

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

The above diamines may be used one type or in a mixture of two or more types depending on characteristics such as liquid crystal orientation when used as a radical generating film, sensitivity in a polymerization reaction, voltage holding characteristics, and accumulated charge.

The diamine having a site where such radical polymerization occurs is preferably used in an amount of 5 to 50 mol% of the total diamine components used in the synthesis of the polymer contained in the radical generating film-forming composition, more preferably 10 to 50 mol%. It is 40 mol%, especially preferably 15 to 30 mol%.

In addition, when the polymer used in the radical generating film of the present invention is obtained from diamine, diamines other than the diamine having the above radical-generating site may be used together as the diamine component, as long as the effect of the present invention is not impaired. You 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-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2 , 5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis ( 3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4- Bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy) ) Benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4- Aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]dianiline, 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)]dianiline, 1,4-phenylenebis[(4-aminophenyl)methanone], 1,4-phenylene Bis[(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-aminophenyl)isophthalamide, 9, 10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylsulfone, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2, 2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl) Hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl) ) Propane, 2,2'-bis (3-amino-4-methylphenyl) propane, trans-1,4-bis (4-aminophenyl) cyclohexane, 3,5-diaminobenzoic acid, 2,5-diamino Benzoic acid, bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy) Si) propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)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)dodecane, 1,12-bis Aromatic diamines such as (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-diaminoctane, 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 butyloxycarbonyl urea, etc. diamine; diamines having a nitrogen-containing unsaturated heterocyclic ring structure such as N-p-aminophenyl-4-p-aminophenyl(tertiary butyloxycarbonyl)aminomethylpiperidine; and diamines having an N-Boc group such as N-tertiarybutoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine.

The above other diamines may be used one type or in a mixture of two or more types depending on characteristics such as liquid crystal orientation when used as a radical generating film, sensitivity in a polymerization reaction, voltage holding characteristics, and accumulated charge.

In the synthesis when the polymer is a polyamic acid, the tetracarboxylic dianhydride reacted with the above 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'-bi Phenyl 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-di) Carboxyphenyl)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, oxydiphthal 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-tetra Hydrofuran tetracarboxylic acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid, 2,3,5-tricarboxy cyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetra Hydro-1-naphthalenesuccinic acid, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid, bicyclo[4,3,0]nonane-2,4,7,9-tetra Carboxylic acid, bicyclo[4,4,0]decane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]decane-2,4,8,10-tetracarboxylic acid, tricarboxylic acid Cyclo[6.3.0.0<2,6>]undecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4-(2,5-dioxotetrahydro furan-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-2:3,5:6 dicarboxylic acid, 1,2,4,5-cyclo and dianhydrides of tetracarboxylic acid such as hexane tetracarboxylic acid.

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

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

Specific examples of aliphatic tetracarboxylic acid diester 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 di. Alkyl 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 dialkyl 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-tricarboxycyclopentyl acetic 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-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dialkyl ester, etc. are mentioned.

Aromatic tetracarboxylic acid dialkyl esters include pyromellitic acid dialkyl ester, 3,3',4,4'-biphenyl tetracarboxylic acid dialkyl ester, and 2,2',3,3'-biphenyl tetracarboxylic acid dialkyl ester. Dialkyl ester of this acid, 2,3,3',4-biphenyl tetracarboxylic acid dialkyl ester, 3,3',4,4'-benzophenone tetracarboxylic acid dialkyl ester, 2,3,3',4 '-benzophenone tetracarboxylic acid dialkyl ester, bis(3,4-dicarboxyphenyl) ether dialkyl ester, bis(3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-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, there is no particular limitation on the diisocyanate reacted with the above diamine component, and it can be used depending on availability, etc. The specific structure of diisocyanate is shown below.

[Formula 21]

In the formula, R ²² and R ²³ represent aliphatic hydrocarbons having 1 to 10 carbon atoms.

The aliphatic diisocyanates shown in K-1 to K-5 are poor in reactivity but have the advantage of improving solvent solubility, and the aromatic diisocyanates shown in K-6 to K-7 are highly reactive and improve heat resistance. Although it is effective, it has the drawback of lowering solvent solubility. In terms of versatility and properties, K-1, K-7, K-8, K-9, and K-10 are particularly preferred, K-12 is preferred from the perspective of electrical properties, and K-13 is preferred from the perspective of liquid crystal orientation. Particularly desirable. Diisocyanate may be used in combination of one or more types, and it is preferable to apply various types depending on the characteristics desired to be obtained.

In addition, some of the diisocyanate may be replaced 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 can be formed by chemical imidization. It can be used in the same form as .

In the synthesis when the polymer is polyamide, the structure of the dicarboxylic acid to be reacted is not particularly limited, but specific examples are as follows. Specific examples of aliphatic dicarboxylic acids include 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- Dicarboxylic acids such as dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, and suberic acid can be mentioned.

Alicyclic dicarboxylic acids include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1 ,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1, 2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1 ,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic 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 Examples include this acid, 2,6-spiro[3.3]heptanedicarboxylic acid, 1,3-adamantane diacetic acid, and camphor acid.

Aromatic dicarboxylic acids include o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, Tetramethyl terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1 ,4-Anthraquinonedicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 4,4"-terphenyldicarboxylic acid Main acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid Levonic acid, 4,4'-diphenyl etherdicarboxylic acid, 4,4'-bibenzyldicarboxylic acid, 4,4'-stilbendicarboxylic acid, 4,4'-toranedicarboxylic acid (4,4 '-tolandicarboxylic acid), 4,4'-carbonyl dibenzoic acid, 4,4'-sulfonyl dibenzoic acid, 4,4'-dithioicenzoic acid, p-phenylene diacetic acid, 3,3'-p-phenyl Lendipropionic acid, 4-carboxycinnamic 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'-(oxydi-p-phenylene)] dibutyric acid, (isopropylidene di-p-phenylene di) Dicarboxylic acids such as oxy)inbutyric acid and bis(p-carboxyphenyl)dimethylsilane can be mentioned.

Dicarboxylic acids containing heterocycles include 1,5-(9-oxofluorene)dicarboxylic acid, 3,4-furanedicarboxylic acid, 4,5-thiazoledicarboxylic acid, and 2-phenyl-4. ,5-thiazoledicarboxylic acid, 1, 2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridine Dicarboxylic acid, 2,4-pyridine dicarboxylic acid, 2,5-pyridine dicarboxylic acid, 2,6-pyridine dicarboxylic acid, 3,4-pyridine dicarboxylic acid, 3,5-pyridine dicarboxylic acid, etc. I can hear it.

The above-mentioned various dicarboxylic acids may have an acid dihalide or anhydrous structure. These dicarboxylic acids are particularly preferably dicarboxylic acids that can give polyamides with 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'-diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, Levonic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis(phenyl)propanedicarboxylic acid, 4,4-terphenyldicarboxylic acid Levonic acid, 2,6-naphthalenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, or their acid dihalides are preferably used. Some of these compounds exist as isomers, and a mixture containing them may be used. Additionally, two or more types of compounds may be used together. In addition, dicarboxylic acids used in the present invention are not limited to the above exemplary compounds.

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

The reaction between the diamine component and the tetracarboxylic dianhydride component is advantageous in that it proceeds relatively easily in an organic solvent and does not generate by-products.

The organic solvent used in the above reaction is not particularly limited as long as it dissolves the produced polymer. Furthermore, even if it is an organic solvent in which the polymer does not dissolve, it may be used by mixing with the solvent as long as the produced polymer does not precipitate. Additionally, since moisture in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polymer, it is preferable to use a dehydrated and dried organic solvent.

Organic solvents include, 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, dimethyl sulfoxide Seed, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoa Milketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol mono. Acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono Ethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3 -Methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, Methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl , 3-methoxybutyl propionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, etc. These organic solvents may be used individually or in mixture.

When reacting the diamine component and the tetracarboxylic dianhydride component in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is added as is or as dispersed or dissolved in the organic solvent. A method of adding a diamine component to a solution in which the tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, a method of adding the tetracarboxylic dianhydride component and the diamine component alternately, etc. may be mentioned. You can use any method. In addition, when the diamine component or tetracarboxylic dianhydride component consists of multiple types of compounds, they may be reacted in a premixed state, may be reacted individually sequentially, or may be mixed and reacted individually to form a high molecular weight substance. You can also do this.

The temperature when reacting the diamine component and the tetracarboxylic dianhydride component can be any temperature, for example, -20 to 100°C, preferably in the range of -5 to 80°C. In addition, the reaction can be performed at any concentration, for example, the total amount of the diamine component and the tetracarboxylic dianhydride component relative to the reaction solution is 1 to 50 mass%, preferably 5 to 30 mass%.

In the above polymerization reaction, the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component can be any value depending on the molecular weight of the polyamic acid to be obtained. As with a normal polycondensation reaction, the closer this molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced. A preferable range is 0.8 to 1.2.

The method for synthesizing the polymer used in the present invention is not limited to the above method, and when synthesizing polyamic acid, the corresponding tetracarboxylic dianhydride is replaced with the tetracarboxylic dianhydride as in the general method for synthesizing polyamic acid. The corresponding polyamic acid can also be obtained by using a tetracarboxylic acid derivative such as tetracarboxylic acid or tetracarboxylic dihalide and reacting it by a known method. Additionally, when synthesizing polyurea, diamine and diisocyanate may be reacted. When producing polyamic acid ester or polyamide, a component selected from diamine, tetracarboxylic acid diester, and dicarboxylic acid is converted to an acid halide in the presence of a known condensing agent or by a known method, Just react with diamine.

Methods for imidizing the above-described polyamic acid to produce a polyimide include thermal imidization in which a solution of the polyamic acid is heated as is, and catalytic imidization in which a catalyst is added to the polyamic acid solution. Moreover, the imidization ratio from polyamic acid to polyimide is preferably 30% or more, and more preferably 30 to 99%, since the voltage retention rate can be increased. On the other hand, from the viewpoint of suppressing whitening characteristics, that is, precipitation of polymer in the varnish, 70% or less is preferable. Considering both characteristics, 40 to 80% is more preferable.

The temperature when thermally imidizing a polyamic acid in a solution is usually 100 to 400°C, preferably 120 to 250°C, and it is preferably carried out while removing water generated by the imidization reaction to the outside of the system.

Catalytic imidization of polyamic acid can be performed by adding a basic catalyst and an acid anhydride to a solution of polyamic acid and stirring the solution at usually -20 to 250°C, preferably 0 to 180°C. The amount of the basic catalyst is usually 0.5 to 30 mol times the amic acid group, preferably 2 to 20 mol times, and the amount of the acid anhydride is usually 1 to 50 mol times the amic acid group, preferably 3 to 30 mol times the amount. Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine, and among them, pyridine is preferable because it has an appropriate basicity to proceed with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among these, acetic anhydride is preferred because it facilitates purification after completion of the reaction. The imidization rate by catalyst imidization can be controlled by adjusting the catalyst amount, reaction temperature, reaction time, etc.

When recovering the produced polymer from the polymer reaction solution, the reaction solution may be added to a poor solvent to cause precipitation. Poor solvents used to produce precipitates include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated by adding it to a poor solvent can be recovered by filtration and then dried under normal or reduced pressure, at room temperature or by heating. Additionally, if the precipitation-recovered polymer is re-dissolved in an organic solvent and the reprecipitation-recovery operation is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of poor solvents at this time include alcohols, ketones, hydrocarbons, etc., and it is preferable to use three or more types of poor solvents selected from these because the purification efficiency is further increased.

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

The molecular weight of the polymer of the composition for forming a radical generating film is the weight measured by GPC (Gel Permeation Chromatography) method when considering the strength of the radical generating film obtained by applying the radical generating film, workability during film formation, uniformity of the film, etc. The average molecular weight is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

When the radical generating film used in the present invention is obtained by immobilizing it in the film by applying and curing a composition of a polymer and a compound having a radical generating group to form a film, the polymer is a polyimide precursor manufactured according to the above production method. , and a polymer selected from the group consisting of polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, etc., wherein the diamine having a site where radical polymerization occurs is included in the radical generating film-forming composition. You may use at least one type of polymer obtained by using a diamine component that is 0 mol% of the total diamine component used in synthesis. Compounds having a group that generates radicals to be added at that time include the following.

A compound that generates radicals with heat is a compound that generates radicals by heating to a decomposition temperature or higher. Such radical thermal polymerization initiators include, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), and hydroperoxides. (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxide, etc.) peroxycyclohexane, etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohexanoic acid-tert-amyl ester, etc.), Persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile and 2,2'-di(2-hydroxyethyl)azobisisobutyronitrile, etc.) I can hear it. Such radical thermal polymerization initiators may be used individually, or may be used in combination of two or more types.

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. 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-hydroxycyclohexylphenyl ketone, iso Propyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzantrone, 2-methyl-1-[4-( methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,4-dimethylaminoethyl benzoate, 4 -Dimethylaminobenzoic acid isoamyl, 4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(t-butylperoxycarbonyl)benzophenone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl) Ryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl) -s-triazine, 4-[p-N,N-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-dimethylaminosti Ryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o- Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra Kiss (4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1, 2'-biimidazole, 2,2'bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carboxylic Bazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, bis(5-2,4-cyclopentadiene -1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetra(t-butylperoxycarboxylic Bornyl)benzophenone, 3,3',4,4'-tetra(t-hexylperoxycarbonyl)benzophenone, 3,3'-di(methoxycarbonyl)-4,4'-di(t- Butylperoxycarbonyl)benzophenone, 3,4'-di(methoxycarbonyl)-4,3'-di(t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarboxyl) Bornyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone , or 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene)-1-(2-benzoyl)ethanone. These compounds may be used individually, or two or more may be mixed and used.

Furthermore, even when the radical generating film is made of a polymer containing an organic group that induces radical polymerization, it may contain a compound having a group that generates the radical 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 that dissolves or disperses the radical generator and other components. There is no particular limitation on such organic solvents, and examples include organic solvents such as those exemplified in the above synthesis of polyamic acid. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N -Dimethylpropanamide and the like are preferred from the viewpoint of solubility. In particular, N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is preferred, but a mixed solvent of two or more types may be used.

In addition, it is preferable to use a solvent that improves the uniformity and smoothness of the coating film by mixing it with an organic solvent in which the components contained in the radical-generating film-forming composition have high solubility.

Solvents that improve the uniformity and smoothness of the coating film include, for example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, and butyl cell. Rosolve acetate, ethyl cellosolve acetate, butylcarbitol, ethylcarbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol mono. Acetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl Ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene Glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, Amylacetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate. , ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxyethyl propionate, 3- Ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropyl propionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2 -Propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, Dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate ester, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, 2-ethyl-1-hexalactate Nols, etc. may be mentioned. You may mix multiple types of these solvents. When using these solvents, it is preferable that it is 5-80 mass % of the whole solvent contained in a liquid crystal aligning agent, More preferably, it is 20-60 mass %.

The radical generating film-forming composition may contain components other than those mentioned above. Examples include compounds that improve film thickness uniformity and 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 film strength of the radical-generating film-forming composition. Compounds that further improve the quality, etc. can be mentioned.

Compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, Ftop EF301, EF303, EF352 (manufactured by Dochem Products), Megapak F171, F173, R-30 (manufactured by Dainippon Ink), Florad FC430, FC431 (manufactured by Sumitomo 3M) ), Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass), etc. When these surfactants are used, the 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 polymer contained in the radical generating film-forming composition.

Specific examples of compounds that improve adhesion between the radical-generating film-forming composition and the substrate include functional silane-containing compounds and epoxy group-containing compounds. 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-trimethoxysilylpropyltriethylenetriamine 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 diyl. Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl ether 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.

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

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

[Radical generation film]

The radical generating film of the present invention can be obtained using the radical generating film forming composition. For example, the cured film obtained by applying the radical-generating film-forming composition used in the present invention to a substrate, followed by drying and baking, can also be used as a radical-generating film as is. In addition, it is also possible to rub this cured film, irradiate it with polarized light or light of a specific wavelength, treat it with an ion beam, or irradiate UV to the liquid crystal display element after liquid crystal filling as an alignment film for PSA.

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

Specific examples include glass plates, polycarbonate, poly(meth)acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) Examples include substrates on which transparent electrodes are formed on plastic plates such as acrylonitrile, triacetylcellulose, diacetylcellulose, and acetate butylate cellulose.

For substrates that can be used for IPS-type liquid crystal display devices, electrode patterns such as standard IPS comb electrodes or PSA fishbone electrodes, or protrusion patterns such as MVA can be used.

Additionally, in high-performance devices such as TFT-type devices, devices such as transistors formed between an electrode for driving liquid crystal and a substrate are 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 can also be used as long as it is only used on one side. possible. At that time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.

Methods for applying the radical-generating film-forming composition include spin coating, printing, inkjet, spray, and roll coating. However, transfer printing is widely used industrially in terms of productivity. It is also suitably used in the present invention.

The drying process after applying the radical generating film-forming composition is not absolutely necessary, but it is preferable to include the drying process when the time from application to firing is not constant for each substrate, or when firing is not carried out immediately after application. do. This drying only requires that the solvent has been removed to the extent that the shape of the coating film is not deformed by transportation of the substrate, etc., and the drying means is not particularly limited. For example, a method of drying on a hot plate at a temperature of 40°C to 150°C, preferably 60°C to 100°C, for 0.5 to 30 minutes, preferably 1 to 5 minutes, is included.

The coating film formed by applying the radical generating film-forming composition by the above method can be fired to form a cured film. At that time, the firing temperature can be carried out at any temperature, usually 100°C to 350°C, but is preferably 140°C to 300°C, more preferably 150°C to 230°C, and even more preferably 160°C to 220°C. am. The firing time can be generally any time from 5 minutes to 240 minutes. Preferably it is 10 to 90 minutes, and more preferably 20 to 90 minutes. Heating can be performed using a commonly known method, for example, a hot plate, hot air circulation oven, IR oven, belt furnace, etc.

The thickness of this cured film can be selected as needed, but is preferably 5 nm or more, and more preferably 10 nm or more because it is easy to obtain reliability of the liquid crystal display element. Moreover, when the thickness of the cured film is preferably 300 nm or less, and more preferably 150 nm or less, it is suitable because the power consumption of the liquid crystal display element does not become extremely large.

As described above, a first substrate having a radical generating film can be obtained, but the radical generating film can also be subjected to uniaxial alignment treatment. Methods for performing uniaxial orientation treatment include a photo-alignment method, an oblique vapor deposition method, rubbing, and uniaxial orientation treatment using a magnetic field.

When performing an orientation treatment by rubbing in one direction, for example, the substrate is moved so that the rubbing cloth and the film come into contact while rotating the rubbing roller around which the rubbing cloth is wound. In the case of the first substrate of the present invention on which comb electrodes are formed, the direction is selected depending on the electrical properties of the liquid crystal, but in the case of using liquid crystal with positive dielectric anisotropy, the rubbing direction is the direction in which the comb electrodes extend. It is desirable to do this in approximately the same direction.

The second substrate of the present invention is similar to 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) are formed by forming a radical It is obtained by arranging the generated film and the liquid crystal alignment film to face each other, fixing them with a sealant with a spacer in between, and sealing them by injecting a liquid crystal composition containing a liquid crystal and a radically polymerizable compound. At that time, the size of the spacer used is usually 1 to 30 μm, but is preferably 2 to 10 μm. Additionally, by making the rubbing direction of the first substrate and the rubbing direction of the second substrate parallel, it can be used in IPS mode or FFS mode, and by arranging it so that the rubbing directions are orthogonal, it can be used in twisted nematic mode.

The method of injecting the liquid crystal composition containing the liquid crystal and the radically polymerizable compound is not particularly limited, and includes a vacuum method of reducing the pressure inside the manufactured liquid crystal cell and then injecting a mixture containing the liquid crystal and the polymerizable compound, liquid crystal and polymerization. A dropping method in which a mixture containing a chemical compound is added dropwise and then sealed is included.

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

In the production 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 radically polymerizable compound, but for example, it is a compound having one or two or more polymerizable reactive groups in one molecule. . Preferably, it is a compound having one polymerizable reactive group per molecule (hereinafter, it may be referred to as “compound having a monofunctional polymerizable group”, “compound having a monofunctional polymerizable group”, etc.). The polymerizable reactive group is preferably a radical polymerizable reactive group, for example, a vinyl bond.

It is preferable that at least one of the radically polymerizable compounds is a compound that is compatible with liquid crystal and has one polymerizable reactive group per molecule, that is, a compound having a monofunctional radically polymerizable group.

Incidentally, the polymerizable group of the radically polymerizable compound is preferably a polymerizable group selected from the following structures.

[Formula 22]

(In the formula, * represents a bonding site with a portion other than the polymerizable reactive group of the compound molecule. R ^b represents a straight-chain alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR ^c -, - S-, ester bond, and amide bond. R ^c represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.

In addition, in the liquid crystal composition containing the liquid crystal and the radically polymerizable compound, it is preferable to contain a radically polymerizable compound whose Tg of the polymer obtained by polymerizing the radically polymerizable compound is 100°C or lower.

Compounds having a monofunctional radical polymerizable group have a reactive group capable of performing radical polymerization in the presence of an organic radical, for example, t-butyl methacrylate, hexyl methacrylate, and 2-ethylhexyl methacrylate. , methacrylate-based monomers such as nonyl methacrylate, lauryl methacrylate, and n-octyl methacrylate; Acrylate-based 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-, p-t-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, vinyl monomers such as methacrylamide, etc.) and halogenated vinyls (e.g., vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloroprene, vinyl fluoride, etc.), but are not limited to these. These various radically polymerizable monomers may be used individually or in combination of two or more types. Moreover, it is preferable that these have compatibility with liquid crystal.

Moreover, as the radically 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-, ester bond, and amide bond. represents a linking group. In the sentence, R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

It is preferable that at least one of the radically polymerizable compounds is a compound that is compatible with liquid crystal and has one polymerizable reactive group per molecule, that is, a compound having a monofunctional radically polymerizable group.

In addition, the radical polymerizable compound represented by the formula (1) is one in which E is an ester bond (a bond represented by -C(=O)-O- or -O-C(=O)-). It is preferable from the viewpoint of ease of use, compatibility with liquid crystal, 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), R ^a and R ^b each independently represent a straight-chain alkyl group having 2 to 8 carbon atoms.

The content of the radically 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% by mass or less.

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

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

Next, sufficient energy to cause a polymerization reaction of the radically polymerizable compound is provided to the liquid crystal cell into which the mixture (liquid crystal composition) containing the liquid crystal and the radically polymerizable compound is introduced. This can be performed, for example, by applying heat or UV irradiation, and the radically polymerizable compound is polymerized in situ, thereby developing the desired properties. Among these, UV irradiation is preferable because the use of UV enables oriented patterning and enables a polymerization reaction to occur in a shorter time. In addition, when using in twisted nematic mode, a chiral dopant may be introduced into the liquid crystal cell as needed in addition to the liquid crystal composition.

Additionally, heating may be performed during UV irradiation. The heating temperature when performing UV irradiation is preferably in the temperature range at which the introduced liquid crystal exhibits liquid crystallinity, and is usually 40°C or higher, and heating below the temperature at which the liquid crystal changes to an isotropic phase is preferred. .

Here, in the case of UV irradiation, it is preferable to select the UV irradiation wavelength at the wavelength with the best reaction quantum yield of the reacting polymerizable compound, and the UV irradiation amount is usually 0.01 to 30 J, but is preferably 10 J or less. A smaller amount of UV irradiation is more suitable because it can suppress a decrease in reliability due to destruction of members constituting the liquid crystal display, and improves manufacturing tact by reducing the UV irradiation time.

In addition, when polymerization is carried out only by heating rather than by UV irradiation, the heating is preferably performed in a temperature range that is lower than the decomposition temperature of the liquid crystal as the temperature at which the polymerizable compound reacts. Specifically, for example, it is 100°C or higher and 150°C or lower.

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

＜Liquid crystal display device＞

A liquid crystal display element can be produced using the liquid crystal cell obtained in this way.

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

Additionally, a backlight, a polarizer, a λ/4 plate, a transparent electrode, a polarizing film, a color filter layer, etc. are installed in this liquid crystal cell according to a conventional method as necessary, thereby forming a transmission type liquid crystal display element.

Example

Although the present invention will be specifically described by way of examples, the present invention is not limited to these examples. The abbreviations of the compounds used in the polymerization of polymers and the preparation of film-forming compositions and methods for evaluating their properties are as follows:

[Formula 25]

NMP: N-methyl-2-pyrrolidone;

GBL: γ-butylactone;

BCS: Butylcellosolve.

＜Viscosity measurement＞

For the polyamic acid solution, the viscosity at 25°C was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample volume of 1.1 mL, and a condenser TE-1 (1°34', R24).

＜Measurement of imidization rate＞

20 mg of 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 mass% TMS (tetramethylsilane) mixture) was added. , and was completely dissolved by applying ultrasound. The 500 MHz proton NMR of this solution was measured with a measuring device (JNW-ECA500, manufactured by Nippon Electronics Datum Co., Ltd.).

The imidization rate is determined by setting a proton derived from a structure that does not change before and after imidization as a reference proton, and using the peak integrated value of this proton and the peak integrated value of the proton derived from NH of the amide group that appears around 9.5 to 10.0 ppm. It was obtained using the formula below.

Imidation rate (%) = (1-α·x/y) × 100

Wherein, It is the ratio of the number of standard protons.

<Preparation of composition for polymerization and radical generation film formation>

Synthesis Example 1

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

Measure 1.62 g (15.00 mmol) of DA-1 and 3.96 g (15.00 mmol) of DA-2 into a 100 ml four-necked flask equipped with a nitrogen introduction tube, air cooling tube, and mechanical stirrer, and add 48.2 g of NMP. It was stirred under a nitrogen atmosphere to completely dissolve. After confirming dissolution, 3.75 g (15.00 mmol) of TC-2 was added, and reaction was performed at 60°C in a nitrogen atmosphere for 3 hours. The temperature was returned to room temperature again, 2.71 g (13.80 mmol) of TC-1 was added, and reaction was performed at 40°C in a 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 with 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. , 3.76 g (47.53 mmol) of pyridine was added, stirred at room temperature for 30 minutes, and then stirred 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, the solid was added into 300 ml of methanol, and washed with stirring for 30 minutes in total twice. The solid was recovered by filtration, air dried, and then dried in a vacuum oven at 60°C. By performing this, polyimide (PI-1) with a number average molecular weight of 11300, a weight average molecular weight of 32900, and an imidization rate of 53% was obtained.

Synthesis Example 2

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

Measure 1.62 g (15.00 mmol) of DA-1 and 4.96 g (15.00 mmol) of DA-3 into a 100 ml four-necked flask equipped with a nitrogen introduction tube, air cooling tube, and mechanical stirrer, and add 51.90 g of NMP. It was stirred under a nitrogen atmosphere to completely dissolve. After confirming dissolution, 3.75 g (15.00 mmol) of TC-2 was added, and reaction was performed at 60°C in a nitrogen atmosphere for 3 hours. The temperature was returned to room temperature again, 2.64 g (13.5 mmol) of TC-1 was added, and reaction was performed at 40°C in a 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 with 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 8.38 g (81.4 mmol) of acetic anhydride was added while stirring. , 3.62 g (45.8 mmol) of pyridine was added, stirred at room temperature for 30 minutes, and then stirred 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, the solid was added into 300 ml of methanol, and washed with stirring for 30 minutes twice in total. The solid was recovered by filtration, air dried, and then dried in a vacuum oven at 60°C. Polyimide (PI-2) with a number average molecular weight Mn of 13100, a weight average molecular weight Mw of 34000, and an imidization rate of 55% was obtained.

Synthesis Example 3

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

Measure 1.62 g (15.00 mmol) of DA-1 and 5.65 g (15.00 mmol) of DA-4 into a 100 ml four-necked flask equipped with a nitrogen introduction tube, air cooling tube, and mechanical stirrer, and add 55.4 g of NMP. It was stirred under a nitrogen atmosphere to completely dissolve. After confirming dissolution, 3.75 g (15.00 mmol) of TC-2 was added, and reaction was performed at 60°C in a nitrogen atmosphere for 3 hours. The temperature was returned to room temperature, 2.82 g (14.40 mmol) of TC-1 was added, and reaction was performed at 40°C under a 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 with 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 8.36 g (81.2 mmol) of acetic anhydride was added while stirring. , 3.65 g (46.1 mmol) of pyridine was added, stirred at room temperature for 30 minutes, and then stirred 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, the solid was added into 300 ml of methanol, and washed with stirring for 30 minutes twice in total. The solid was recovered by filtration, air dried, and then dried in a vacuum oven at 60°C. Polyimide (PI-3) was obtained with a number average molecular weight Mn of 12900, a weight average molecular weight Mw of 31000, and an imidization rate 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 the mixture was stirred at 50°C to completely dissolve. Additionally, 6.7 g of NMP and 6.7 g of BCS were added and stirred for an additional 3 hours to obtain a radical generating film-forming composition according to the present invention: AL1 (solid content: 6.0 mass%, NMP: 66 mass%, BCS: 30 mass%). got it

Preparation of radical-generating film-forming composition: 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 the mixture was stirred at 50°C to completely dissolve. Additionally, 6.7 g of NMP and 6.7 g of BCS were added and stirred for an additional 3 hours to obtain a radical generating film-forming composition according to 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 the mixture was stirred at 50°C to completely dissolve. Additionally, 6.7 g of NMP and 6.7 g of BCS were added and stirred for an additional 3 hours to obtain 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]

＜Manufacturing of liquid crystal display elements＞

A liquid crystal display element was produced with the structure shown in Table 3 using AL1 to AL3 obtained above and SE-6414 (manufactured by Nissan Chemical Industries, Ltd.), which is a liquid crystal aligning agent for horizontal alignment.

[Table 3]

(First substrate)

The first substrate (hereinafter also referred to as the IPS substrate) is an alkali-free glass substrate with 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 with an electrode width of 10 μm and a spacing between electrodes of 10 μm is formed to form a pixel. The size of each pixel is 10 mm vertically and approximately 5 mm horizontally.

AL1 to AL3 or SE-6414 were filtered through a 1.0 μm filter, then applied to the electrode formation surface of the IPS substrate by spin coating and dried on a hot plate at 80°C for 1 minute. Next, AL1 to AL3 were fired at 150°C for 20 minutes, and SE-6414 was fired at 220°C for 20 minutes to obtain a coating film with a film thickness of 100 nm.

In the rubbing treatment “with”, rubbing was performed so that the rubbing direction was parallel to the comb electrode. Rubbing was performed using rayon fabric: YA-20R manufactured by Yoshikawa Kako under the 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. However, only for the film coated with SE-6414, the rotation speed was set to 1000 rpm. After the rubbing treatment, ultrasonic irradiation was performed for 1 minute in pure water and dried at 80°C for 10 minutes.

(second substrate)

The second substrate (also called back ITO substrate) is an alkali-free glass substrate with a size of 30 mm x 35 mm and a thickness of 0.7 mm, and an ITO film is formed on the back side (the side facing the outside of the cell). Additionally, a column-shaped spacer with a height of 4 μm is formed on the surface (the surface facing the inside of the cell).

AL1, AL2 or SE-6414 was filtered through a 1.0 μm filter, then applied to the electrode formation surface of the IPS substrate by spin coating and dried on a hot plate at 80°C for 1 minute. Next, AL1 and AL2 were baked at 150°C for 20 minutes, and SE-6414 was baked at 220°C for 20 minutes to form a coating film with a film thickness of 100 nm, followed by rubbing treatment. The rubbing treatment was performed using rayon fabric: YA-20R manufactured by Yoshikawa Kako under the conditions of a roll diameter of 120 mm, a rotation speed of 1000 rpm, a moving speed of 50 mm/sec, and a pressing amount of 0.4 mm. However, for the film coated with AL1 or AL2, the rotation speed was set to 300 rpm. After the rubbing treatment, ultrasonic irradiation was performed for 1 minute in pure water and dried at 80°C for 10 minutes.

(Production of liquid crystal cell)

Using the above-mentioned two types of substrates with a liquid crystal alignment film (a first substrate and a second substrate), the surrounding area was sealed leaving a liquid crystal injection port, and an empty cell with a cell gap of about 4 μm was produced. At this time, when the first substrate is not subjected to a rubbing treatment, the direction of the comb electrode of the first substrate is combined so that the rubbing direction of the second substrate is parallel, and when the first substrate is subjected to a rubbing treatment, the first substrate and the second substrate are combined. The two substrates were combined so that the rubbing directions were antiparallel.

A liquid crystal (MLC-3019 manufactured by Merck & Co., Ltd. with 10 wt% of HMA added) was vacuum-injected into this empty cell at room temperature, and then the injection port was sealed to form a liquid crystal cell. The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element. After that, the obtained liquid crystal cell was subjected to heat treatment at 120°C for 20 minutes.

With UV treatment, the liquid crystal cell was irradiated with ultraviolet rays using a high-pressure mercury lamp through a band-pass filter with a wavelength of 313 nm so that the exposure amount was 1000 mJ.

<Evaluation of liquid crystal orientation>

The orientation of the liquid crystal cell was confirmed using a polarizer set with Cross Nicol. Those that were oriented without defects were rated ○, those with slight orientation defects were rated △, and those that were not oriented were rated ×.

＜Measurement of V-T curve and evaluation of driving threshold voltage and maximum luminance voltage＞

A white LED backlight and a luminance meter are set so that the optical axes are aligned, and in between, a liquid crystal cell (liquid crystal display element) with a polarizer attached so that the luminance is the lowest is set, and a voltage of up to 8 V is applied at 1 V intervals. The V-T curve was measured by measuring the luminance. From the obtained V-T curve, the driving threshold voltage and the voltage at which luminance is maximum were estimated.

<Evaluation of response speed of liquid crystal display>

Using the device used to measure the V-T curve above, connect the luminance meter to an oscilloscope and measure the response speed (Ton) when the voltage that reaches the maximum luminance is applied and the response speed (Toff) when the voltage is set to 0. did.

[Table 4]

In comparing Cell-1 to Cell-20 using a horizontal alignment film rubbed on the back ITO substrate (second substrate) side, Cell-11 using a radical generating film on the IPS substrate (first substrate) side and UV treatment. , Cell-12, Cell-16, and Cell-17 were confirmed to have good liquid crystal orientation and that the driving threshold voltage and maximum luminance voltage were decreasing. In addition, while the Toff value increased in Cell-11 and Cell-12 where the radical generating film was not rubbed, the increase in Toff value was greatly improved in Cell-16 and Cell-17 where the radical generating film was rubbed. It has been confirmed that it exists.

As a supplementary experiment in addition to the above, a liquid crystal cell was created in which AL1 was used on both the back ITO substrate (second substrate) and the IPS substrate (first substrate), and neither the first nor the second substrate was subjected to rubbing treatment. In this liquid crystal cell, before UV irradiation, alignment defects and bright points (flow orientation) along the flow direction at the time of liquid crystal injection were observed, but after UV irradiation, the flow orientation completely disappeared, and domains (schlieren) derived from the liquid crystal were confirmed. It has been done. From this, it was suggested that when a radical generating film and a liquid crystal containing a polymerizable compound are used together, the radical generating film loses its ability to regulate liquid crystal orientation by irradiating UV, and a zero-plane anchoring film is formed on the radical generating film.

In addition, in the comparison of liquid crystal cells Cell-21 to Cell-24, Cell-21 and Cell-23 without UV irradiation showed uniaxial orientation in the rubbing direction, but Cell-22 and Cell-24 with UV irradiation showed uniaxial orientation in the rubbing direction. changed to an unoriented state, generating a liquid crystal domain (schlieren). This suggests that even when the radical generating film is rubbed, a zero-plane anchoring film is formed on the radical generating film by irradiating UV.

However, when observing Cell-22 and Cell-24 while rotating them under cross nicols, a slight change in brightness and darkness occurred, indicating that this zero-plane anchoring film is not completely devoid of orientation regulating force, but that regulating force is due to the intermolecular force between liquid crystals. It is weaker than that, and it is suggested that this regulating force alone does not uniaxially align the liquid crystal molecules in any direction. From this, it is believed that the significant improvement in the Toff value in Cell-16 and Cell-17 is due to the weak regulatory force described above.

Polymerizable Compound Synthesis Example 1

Synthesis of 2-(heptanoyloxymethyl)acrylic acid ethyl ester

[Formula 26]

Step 1: Synthesis of 2-hydroxymethylacrylic acid ethyl ester

In a 500 ml four-necked flask equipped with a nitrogen inlet tube, measure 10 mg of 4-methoxyphenol and 21.88 g (195.1 mmol) of DABCO (1,4-diazabicyclo[2.2.2]octane), and add 50 ml of pure water. Then, 11.52 g (390.1 mmol) of paraformaldehyde was added while stirring at 10°C or lower in a nitrogen atmosphere, and the mixture was stirred for 1 hour. After confirming that the state had changed from a slurry state to a solution state, 300 ml of acetonitrile was added, 19.53 g (195.1 mmol) of ethyl acrylate was added dropwise, and reaction was carried out at 50°C for 5 hours. After completion of the reaction, the reaction solution was transferred to a separation funnel, and 50 ml of n-hexane was added. After confirming that it was divided into three layers, the lower two layers were recovered and this operation was performed three times. Additionally, 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, dried, filtered and concentrated to obtain 22.9 g (175.6 mmol, yield 90%) of a colorless and transparent oily liquid. The structure was confirmed to be the target using a nuclear magnetic resonance spectrum ( ^1H -NMR spectrum). The measurement data is shown below.

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

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

In a 500 ml four-necked flask equipped with a nitrogen inlet tube, 19.9 g (152.9 mmol) of 2-hydroxymethylacrylic acid obtained by the above method was measured, 300 ml of THF and 23.2 g (229.3 mmol) of triethylamine were added, and nitrogen was added. While maintaining the temperature below 10°C under an atmosphere, 25.0 g (168.2 mmol) of heptanoyl chloride was added dropwise and allowed to react for 6 hours. After completion of the reaction, the precipitated triethylamine hydrochloride was removed by filtration, the reaction solution was concentrated, re-dissolved in 300 ml of ethyl acetate, washed three times with 100 ml of 10% potassium carbonate aqueous solution, and three times with 50 ml of pure water. After drying with anhydrous magnesium sulfate, it was filtered and concentrated to obtain a light yellow viscous body. It was further purified by flash column chromatography (developing solvent: ethyl acetate: n-hexane = 20:80), and the solvent was removed and vacuum dried to obtain 32.2 g (133.0 mmol: yield 87%) of a colorless, transparent oily liquid. got it The structure was confirmed to be the target using a nuclear magnetic resonance spectrum ( ^1H -NMR spectrum). The measurement data is shown below.

^1H 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 2

Synthesis of 2-(heptanoyloxymethyl)acrylic acid butyl ester

[Formula 27]

Step 1: Synthesis of 2-hydroxymethylacrylic acid butyl ester

In the same operation as the first step, ethyl acrylate was replaced with butyl acrylate and synthesis was performed, and 24.3 g of a colorless and transparent oil was obtained (26.2 g: yield 85%). The structure was confirmed to be the target using a nuclear magnetic resonance spectrum ( ^1H -NMR spectrum). The measurement data is shown below.

^1H NMR (400MHz, CDCl ₃ )δ: 6.81(1H), 5.80(1H), 4.31(2H), 4.17(1H), 1.98(1H), 1.67-1.64(2H), 1.42-1.38(2H), 0.93(3H)

Second process: Synthesis of 2-(heptanoyloxymethyl)acrylic acid butyl ester

2-Hydroxymethyl acrylic acid in the second step was changed to 2-((heptanoyloxy)methyl)acrylic acid butyl ester obtained by the above method, and the synthesis was performed in the same manner to obtain 34.2 g of a colorless and transparent oily liquid ( 126.7: Yield 82.8%) was obtained. The structure was confirmed to be the target using a nuclear magnetic resonance spectrum ( ^1H -NMR spectrum). The measurement data is shown below.

^1H NMR (400MHz, CDCl ₃ )δ: 6.36(1H), 5.81(1H), 4.80(2H), 4.19-4.16(2H), 2.35-2.31(2H), 1.64-1.58(4H), 1.40-1.25 (8H), 0.96-0.83(6H)

Polymerizable Compound Synthesis Example 3

Synthesis of dihexyl itaconate

[Formula 28]

In a four-necked flask equipped with a Dean-Stark tube, measure 23.8 g (182.9 mmol) of itaconic acid, 35.5 g (347.5 mmol) of 1-hexanol, 500 ml of cyclohexane, 0.9 g (9.1 mmol) of concentrated sulfuric acid, and dibutyl hydroxyl. 0.04 g (1.82 mmol) of toluene (BHT) was added, and a dehydration condensation reaction was performed at 110°C for 24 hours in a nitrogen atmosphere. After completion of the reaction, 100 ml of n-hexane was added to the reaction solution, washed three times with 100 g of 10% aqueous sodium carbonate solution and three times with 100 ml of pure water, and dried over anhydrous magnesium sulfate. After filtration and concentration, vacuum drying was performed to obtain 48.6 g (162.8 mmol: yield 89%) of a colorless and transparent oily liquid. The structure was confirmed to be the target using a nuclear magnetic resonance spectrum ( ^1H -NMR spectrum). The measurement data is shown below.

^1H 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)

(Production of liquid crystal cell)

After creating an empty cell according to the above (creation of a liquid crystal cell), the above polymerizable compound was added to the empty cell in an optimal amount of liquid crystal compositions LC-1 to LC-4 (MLC-3019 manufactured by Merck & Co., Ltd.). ), one was vacuum injected at a vacuum degree of about 300 Pa at room temperature, and the other was vacuum injected after degassing for 1 hour at a vacuum degree of about 1 Pa, and the injection port was sealed to make a liquid crystal cell. The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element. After that, the obtained liquid crystal cell was subjected to heat treatment at 120°C for 10 minutes. Next, a test was performed in the same manner as above.

In addition, liquid crystal compositions LC-1 to LC-4 are obtained by adding the polymerizable compounds listed in the table below to MLC-3019 in the amounts introduced below.

[Table 5]

＜Evaluation results of orientation＞

[Table 6]

Liquid crystals incorporating IDBu and IDHex (LC-1, LC-2) and liquid crystals incorporating C2C6 and C4C6 showed very good orientation even when carried out at a relatively high degree of vacuum.

＜Evaluation results of electro-optical properties＞

Next, the driving threshold voltage, voltage at maximum luminance, and response speed of the cells using the liquid crystal with the zero anchoring orientation described above in which the radical generating film is not rubbed are summarized below.

[Table 7]

When a polymerizable compound was used, a decrease in driving voltage was confirmed regardless of the presence or absence of rubbing treatment, and the response speed also tended to improve by performing rubbing treatment.

Therefore, it was found that the polymerizable compound can simultaneously achieve zero anchoring under high vacuum and the effect of improving response speed by rubbing.

Industrial applicability

According to the present invention, a zero-surface anchoring film can be produced industrially with good yield from inexpensive raw materials. Additionally, the liquid crystal display element obtained by the method of the present invention is useful as a vertically aligned liquid crystal display element, such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display.

Claims (24)

A liquid crystal composition containing a liquid crystal and a radically polymerizable compound is brought into contact with a radical generating film, and a step of providing sufficient energy to polymerize the radically polymerizable compound,
A method of producing a zero-plane anchoring film, wherein the radical generating film is a film formed by immobilizing an organic group that causes radical polymerization. According to claim 1,
A method in which the first substrate has a radical-generating film, and the radical-generating film is a uniaxially aligned radical-generating film. The method of claim 1 or 2,
A method of performing steps for imparting energy in a non-electrical field. delete The method of claim 1 or 2,
A method characterized in that the radical generating film is obtained by applying and curing a composition of a polymer and a compound having a radical generating group to form a film, thereby immobilizing it in the film. The method of claim 1 or 2,
A method characterized in that the radical generating film is made of a polymer containing an organic group that induces radical polymerization. According to claim 6,
The polymer containing an organic group that causes radical polymerization is at least one selected from polyimide precursors, polyimides, polyureas, and polyamides obtained by using a diamine component containing a diamine containing an organic group that causes radical polymerization. A method characterized in that it is a polymer of. According to claim 1,
A method wherein the organic group causing the radical polymerization is selected from organic groups represented by any of the following structures [X-1] to [X-18], [W], [Y], and [Z]:
[Formula 29]

( ^In the formula ^[ or -S-, R represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a carbon number of 1. Represents an alkyl group of ~4.)
[Formula 30]

(In the formulas [W], [Y], and [Z], * represents a bonding site with a portion other than the polymerizable reactive group of the compound molecule, and Ar represents phenylene 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 naphthylene and biphenylene, R ⁹ and R ¹⁰ each independently represent an alkyl group with 1 to 10 carbon atoms or an alkoxy group with 1 to 10 carbon atoms, and R ⁹ and R ¹⁰ In the case of this alkyl group, Q may be bonded to each other at the terminals to form a ring structure, and Q is selected from organic groups represented by any of the following structures:
[Formula 31]

(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, and * represents a group other than Q in the compound molecule. Indicates the binding site with the part.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms.) According to claim 6,
A method wherein the organic group causing the radical polymerization is selected from organic groups represented by any of the following structures [X-1] to [X-18], [W], [Y], and [Z]:
[Formula 29]

( ^In the formula ^[ or -S-, R represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a carbon number of 1. Represents an alkyl group of ~4.)
[Formula 30]

(In the formulas [W], [Y], and [Z], * represents a bonding site with a portion other than the polymerizable reactive group of the compound molecule, and Ar represents phenylene 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 naphthylene and biphenylene, R ⁹ and R ¹⁰ each independently represent an alkyl group with 1 to 10 carbon atoms or an alkoxy group with 1 to 10 carbon atoms, and R ⁹ and R ¹⁰ In the case of this alkyl group, Q may be bonded to each other at the terminals to form a ring structure, and Q is selected from organic groups represented by any of the following structures:
[Formula 31]

(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, and * represents a group other than Q in the compound molecule. Indicates the binding site with the part.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms.) According to claim 7,
A method wherein the organic group causing the radical polymerization is selected from organic groups represented by any of the following structures [X-1] to [X-18], [W], [Y], and [Z]:
[Formula 29]

( ^In the formula ^[ or -S-, R represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a carbon number of 1. Represents an alkyl group of ~4.)
[Formula 30]

(In the formulas [W], [Y], and [Z], * represents a bonding site with a portion other than the polymerizable reactive group of the compound molecule, and Ar represents phenylene 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 naphthylene and biphenylene, R ⁹ and R ¹⁰ each independently represent an alkyl group with 1 to 10 carbon atoms or an alkoxy group with 1 to 10 carbon atoms, and R ⁹ and R ¹⁰ In the case of this alkyl group, Q may be bonded to each other at the terminals to form a ring structure, and Q is selected from organic groups represented by any of the following structures:
[Formula 31]

(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, and * represents a group other than Q in the compound molecule. Indicates the binding site with the part.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms.) According to claim 7,
A method characterized in that the diamine containing an organic group that causes radical polymerization is a diamine having a structure represented by the following general formula (6) or the following general formula (7):
[Formula 32]

(In formula (6), R ⁶ is a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N Represents (CH ₃ )-, -CON(CH ₃ )- or -N(CH ₃ )CO-,
R ⁷ represents a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a fluorine atom, and one or more of the -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 may also be substituted with any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO -, -CONH- or -NH- may be substituted with these groups, provided that they are not adjacent to each other;
R ⁸ is selected from radical polymerization reactive groups represented by any of the following formulas:
[Formula 33]

(In ^the formula ^[ , or -S-, R represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a carbon number. Represents alkyl groups of 1 to 4.))
[Formula 34]

(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 represents a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a fluorine atom, and one or more of any -CH ₂ - or -CF ₂ - of the alkylene group is each independently - CH = CH-, may be substituted with a group selected from a divalent carbocyclic ring and a divalent heterocycle, and may also be substituted with any of the groups listed below, namely -O-, -COO-, -OCO-, -NHCO- , -CONH- or -NH- may be substituted with these groups, provided that they are not adjacent to each other,
J is selected from organic groups represented by any of the following formulas,
[Formula 35]

(In the formulas [W], [Y], and [Z], * represents the 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 with 1 to 10 carbon atoms or an alkoxy group with 1 to 10 carbon atoms, and Q is selected from an organic group represented by any of the structures below. Selected:
[Formula 36]

(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, and * represents a group other than Q in the compound molecule. Indicates the binding site with the part.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms.)). The method of claim 1 or 2,
A method wherein at least one of the radically polymerizable compounds is a compound that is compatible with liquid crystal and has one polymerizable reactive group per molecule. According to claim 12,
The method wherein the polymerizable reactive group of the radically polymerizable compound is selected from the following structures:
[Formula 37]

(In the formula, * represents a bonding site with a portion other than the polymerizable reactive group of the compound molecule. R ^b represents a straight-chain alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR ^c -, - (R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). The method of claim 1 or 2,
In the liquid crystal composition containing the above liquid crystal and a radically polymerizable compound, a liquid crystal composition containing a radically polymerizable compound such that the 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 that may have a radical generating film, wherein the radical generating film is a film in which an organic group that causes radical polymerization is immobilized,
A step of creating a cell so that the radical generating film on the first substrate faces the second substrate;
A step of filling a liquid crystal composition containing a liquid crystal and a radically polymerizable compound between the first and second substrates,
A method for producing a liquid crystal cell using the method according to claim 1 or 2. According to claim 15,
A method of manufacturing a liquid crystal cell, wherein the second substrate is a second substrate that does not have a radical generating film. According to claim 16,
A method of manufacturing a liquid crystal cell, characterized in that the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial orientation. According to claim 17,
A method for producing a liquid crystal cell, wherein the liquid crystal alignment film having the uniaxial orientation is a liquid crystal alignment film for horizontal alignment. According to claim 15,
A method of manufacturing a liquid crystal cell wherein the first substrate having the radical generating film is a substrate having a comb electrode. A liquid crystal cell comprising a first substrate having a radical generating film and a second substrate that may have a radical generating film, and between the first and second substrates being filled with a liquid crystal composition containing a liquid crystal and a radically polymerizable compound. ego,
Here, the radical generating film on the first substrate is positioned to face the second substrate, and the radical generating film is a film in which an organic group that causes radical polymerization is immobilized,
At least one of the radically polymerizable compounds is a compound that is compatible with liquid crystal and has one polymerizable reactive group per molecule,
A liquid crystal cell wherein the polymerizable reactor is selected from the following structures:
[Formula 38]

(In the formula, * represents a bonding site with a portion other than the polymerizable reactive group of the compound molecule. R ^b represents a straight-chain alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR ^c -, - (R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). A method of manufacturing a liquid crystal display device using a film producing a zero plane anchoring state obtained using the method according to claim 1 or 2. A liquid crystal display device obtained using the method described in claim 21. According to claim 22,
A liquid crystal display device in which the first or second substrate has electrodes. According to claim 22,
A liquid crystal display device, which is a low-voltage driven transverse electric field liquid crystal display device.