TW201905178A - Method for manufacturing zero-face anchor film and liquid crystal display element - Google Patents

Abstract

An object of the invention is to provide an industrial method for producing a zero surface anchoring film, a favorable liquid crystal display element that uses this film, and a method for producing the liquid crystal display element. The method for producing a zero surface anchoring film of the invention includes a step of applying sufficient energy to a liquid crystal composition containing a liquid crystal and a radical polymerizable compound to induce a polymerization reaction of the radical polymerizable compound, while the liquid crystal composition is in contact with a radical generating film. Furthermore, a method for creating a functional film includes a step of preparing a cell which has a liquid crystal composition containing a liquid crystal and a radical polymerizable compound between a first substrate that has a radical generating film and a second substrate that does not have a radical generating film, and a step of applying sufficient energy to the cell to induce a polymerization reaction of the radical polymerizable compound.

Description

Manufacturing method of zero-face anchor film and liquid crystal display element

The present invention relates to a manufacturing method using polymer stabilization technology capable of manufacturing a zero-plane anchoring film by a method that is inexpensive and does not include complicated steps, and a liquid crystal display element using the manufacturing method to achieve lower voltage driving, and a liquid crystal display element using the manufacturing method. Production method.

In recent years, liquid crystal display elements have been widely used in displays of mobile phones, computers, and televisions. Liquid crystal display elements have characteristics such as thinness, lightness, and low power consumption. In the future, they are expected to be applied to further content such as VR and ultra-high-definition displays. Various display modes such as TN (Twisted Nematic), IPS (In-Plane Switching), and VA (Vertical Alignment) have been proposed for the display mode of liquid crystal displays. All modes use a film (liquid crystal alignment film) that induces liquid crystal in a desired alignment state.

In particular, products with touch panels, such as tablet PCs, smartphones, and smart TVs, prefer to use the IPS mode that is not easily disturbed even when touched. In recent years, considering the viewpoint of improving contrast and improving viewing angle characteristics, FFS has gradually been adopted. (Frindge Field Switching) liquid crystal display element using non-contact technology using light alignment technology.

However, compared to IPS, FFS has a large manufacturing cost of the substrate, and a problem of poor display unique to the FFS mode called Vcom offset occurs. In addition, compared with the friction method, the photo-alignment method has the advantages of increasing the size of the device that can be manufactured and greatly improving the display characteristics. However, there is a problem in the principle of photo-alignment (if it is a decomposed type, there is a decomposition product. Caused by poor display, if it is an anisotropic type, there is imprinting caused by insufficient alignment force, etc.). In order to solve these problems, various efforts have been made by liquid crystal display element manufacturers and liquid crystal alignment film manufacturers.

On the other hand, in recent years, it has been proposed to use the zero-plane anchored IPS mode. By using this method, it is reported that the contrast can be improved and driven at a significantly lower voltage than the conventional IPS mode (see Patent Document 1). .

Specifically, a liquid crystal alignment film having a strong anchoring energy is used on one substrate, and a process for completely dissipating the alignment constraint force of the liquid crystal is applied to the substrate side having an electrode that generates a transverse electric field to produce an IPS mode liquid crystal Method of displaying components.

In recent years, some people have used thick polymer brushes to make the zero-plane state, and have proposed a technical proposal for the zero-plane anchoring IPS mode (Reference 2). By this technology, the contrast ratio is greatly improved, and the driving voltage is greatly reduced. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4053530 [Patent Document 2] Japanese Patent Laid-Open No. 2013-231757

[Questions to be Solved by the Invention]

On the other hand, this technology has problems that can occur in principle. The first point, for example, is to make polymer brushes stably occur on a substrate, which must be performed under very fine conditions. It is not practical to consider mass production. Second, for example, the alignment film is responsible for suppressing important functions such as imprinting, but when using a polymer brush, it is not easy to control the necessary electrical properties. The third point, for example, in terms of driving principle, the response speed becomes very slow when the voltage is Off. The alignment restraint force is zero, and the resistance during driving of the liquid crystal is eliminated. It can be expected that the threshold voltage drops drastically and the brightness of the alignment is reduced due to the decrease in the area of poor alignment during driving. The power depends on the elasticity of the liquid crystal, and it is thought that the speed will decrease significantly compared to the case with an alignment film. If such a technical problem can be solved, panel makers will have significant benefits in terms of cost, and it is also considered to be beneficial in terms of battery consumption suppression and image quality improvement. The present invention is to solve the above-mentioned problems, and an object thereof is to provide a manufacturing method using polymer stabilization technology capable of manufacturing a zero-plane anchoring film, and to achieve non-contact alignment and low drive at the same time in a simple and inexpensive method at room temperature. A horizontal electric field liquid crystal display device with a voltage and a response speed at Off time and a method for manufacturing the same. [Solution to the problem]

In order to solve the above-mentioned problems, the inventors of the present case have worked hard to find out that they can solve the above-mentioned problems and have completed the present invention having the following gist.

That is, the present invention includes the following. [1] A method for manufacturing a zero-plane anchoring film, including the following steps: in a state where a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is brought into contact with a radical-generating film, and given to polymerize the radically polymerizable compound The full energy of the reaction. [2] The method for manufacturing a zero-plane anchoring film according to [1], wherein the first substrate has a radical-generating film that is a radical-generating film subjected to uniaxial alignment treatment. [3] The method for manufacturing a zero-plane anchoring film according to [1] or [2], wherein the step of applying energy is performed without an electric field. [4] The method for producing a zero-plane anchoring film according to any one of [1] to [3], wherein the radical-generating film is a film formed by immobilizing an organic group that induces radical polymerization. [5] The method for manufacturing a zero-plane anchoring film according to any one of [1] to [3], wherein the radical-generating film is formed by combining a compound having a radical generating group and a polymer It is obtained by coating and curing to form a film and fixing it in the film. [6] The method for producing a zero-plane anchoring film according to any one of [1] to [3], wherein the radical generating film is composed of a polymer containing an organic group that induces radical polymerization. [7] The method for producing a zero-plane anchoring film as described in [6], wherein the polymer containing an organic group that induces radical polymerization is a diamine component containing a diamine containing an organic group that induces radical polymerization The obtained polymer is at least one polymer selected from the group consisting of a polyimide precursor, polyimide, polyurea, and polyimide. [8] The method for manufacturing a zero-plane anchoring film according to any one of [4], [6], and [7], wherein the organic group that induces radical polymerization is the following structure [X-1] ~ [X -18], an organic group represented by [W], [Y], [Z]; In the formulae [X-1] to [X-18], * represents a bonding site with a portion other than the polymerizable reactive group of the compound molecule, and S ¹ and S ² each independently represent -O-, -NR-,- S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, and a carbon number 1 to 4 Alkyl group 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 an organic group and / or a halogen atom as a substituent. An aromatic hydrocarbon group in the group consisting of phenylene, naphthyl, and phenylene, R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms When R ⁹ and R ¹⁰ are alkyl groups, they may be bonded to each other at the ends to form a ring structure; Q represents the following structure; 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 compound other than Q in a compound molecule. Bonding site; R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. [9] The method for producing a zero-plane anchoring film according to [7], wherein the diamine containing an organic group that induces radical polymerization has a structure represented by the following general formula (6) or the following general formula (7) Diamine In formula (6), R ⁶ represents a single bond, -CH _2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N ( CH ₃ )-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-, R ⁷ represents a single bond, or an unsubstituted or fluorine-substituted alkylene group having 1 to 20 carbon atoms. Any one or more of -CH ₂ -or -CF ₂ -of the alkyl group may be independently replaced with a group selected from the group consisting of -CH = CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and Alternatively, any one of the following lists may be substituted, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other and are replaced with these groups. R ⁸ represents a radical polymerization reactive group selected from the following formula; In the formulae [X-1] to [X-18], * represents a bonding site with a portion other than the radical polymerization reactive group of the compound molecule, and S ¹ and S ² each independently represent -O-, -NR- , -S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, and a carbon number 1 ~ 4 alkyl group; 【Chemical 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 unsubstituted or fluorine-substituted alkylene having 1 to 20 carbon atoms Group, any one or more of -CH ₂ -or -CF ₂ -of the alkylene group may be independently replaced by a member selected from the group consisting of -CH = CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring In addition, any of the following groups may be used, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other. Substituted by these groups, J is an organic group represented by the formula: [化 7] In the formulas [W], [Y], and [Z], * represents a bonding site with T ² , and Ar represents an organic group and / or a halogen atom as a substituent selected from the group consisting of phenylene, naphthyl, And an aromatic hydrocarbon group in the group consisting of and biphenyl, R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q represents the following structure; 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 compound other than Q in a compound molecule. Bonding site; R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. [10] The method for producing a zero-plane anchoring film according to any one of [1] to [9], wherein at least one of the radically polymerizable compound is compatible with liquid crystal in one molecule A compound having one polymerizable reactive group. [11] The method for producing a zero-plane anchoring film according to [10], wherein the polymerizable reactive group of the radical polymerizable compound is selected from the following structures, [Chem. 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 linear alkyl group having 2 to 8 carbon atoms, and E represents a single bond selected from -O-, -NR ^c- , -S-, a bonding group in an ester bond and an amidine bond; R ^c represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. [12] The method for producing a zero-plane anchoring film according to any one of [1] to [11], wherein the liquid crystal composition containing a liquid crystal and a radically polymerizable compound uses the radical polymerizable A liquid crystal composition of a radically polymerizable compound having a polymer having a Tg of 100 ° C or lower obtained by polymerizing the compound. [13] A method for manufacturing a liquid crystal cell using the zero-plane anchoring film according to any one of [1] to [12], including the following steps: preparing a first substrate having a radical generating film and also A second substrate having a free radical generating film; a unit cell is formed so that the free radical generating film on the first substrate faces the second substrate; and a liquid crystal and radical polymerization are filled between the first substrate and the second substrate Liquid crystal composition of a sexual compound. [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 coated with a liquid crystal alignment film having uniaxial alignment. [16] The method for manufacturing a liquid crystal cell according to [15], wherein the liquid crystal alignment film with 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 a radical generating film is a substrate having a comb-shaped electrode. [18] A liquid crystal composition containing a liquid crystal and a radical polymerizable compound. At least one of the radical polymerizable compounds is a compound having a polymerizable reactive group in one molecule that is compatible with liquid crystal. The polymerizable reactive group is selected from the following structures; In the formula, * represents a bonding site with a portion other than the polymerizable reactive group of the compound molecule; R ^b represents a linear alkyl group having 2 to 8 carbon atoms, and E represents a single bond selected from -O-, -NR ^c- , -S-, a bonding group in an ester bond and an amidine bond; R ^c represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. [19] A method for manufacturing a liquid crystal display element, using a film made of a zero-plane anchored state obtained by a method such as any one of [1] to [17]. [20] A liquid crystal display element obtained by using the method for manufacturing a liquid crystal display element such as [19]. [21] The liquid crystal display element according to [20], wherein the first substrate or the second substrate has an electrode. [22] A liquid crystal display element such as [20] or [21] is a low voltage driven transverse electric field liquid crystal display element. [Effect of the invention]

According to the present invention, a zero-plane anchoring film can be produced industrially with a good yield. By using the method of the present invention, a liquid crystal display element similar to the zero-plane anchored IPS mode liquid crystal display element described in Patent Documents 1 and 2 can be easily manufactured using inexpensive raw materials and existing manufacturing methods. In addition, the liquid crystal display element obtained by the manufacturing method of the present invention can provide better liquid crystal response speed when it is off than conventional techniques, and has low driving voltage, no bright spots, and is not prone to Vcom shift. Characteristics of liquid crystal display elements.

The present invention relates to a method for manufacturing a zero-plane anchoring film, which is characterized in that the radical-generating film is brought into contact with a liquid crystal containing a specific polymerizable compound, and the polymerizable compound is polymerized by UV or heat. More specifically, it relates to a method for manufacturing a zero-plane anchoring film, which includes the following steps: preparing a liquid crystal and a free radical between a first substrate having a radical generating film and a second substrate having a radical generating film; A unit cell of the liquid crystal composition of the polymerizable compound; and sufficient energy is given to the unit cell to cause the radical polymerizable compound to undergo a polymerization reaction. Preferably, it is a method for manufacturing a liquid crystal cell, which has the following steps: preparing a first substrate with a free radical generating film and a second substrate without a free radical generating film; fabricating a crystal with the free radical generating film facing the second substrate And a liquid crystal composition containing a liquid crystal and a radical polymerizable compound is filled between the first substrate and the second substrate. For example, a method for manufacturing a low-voltage driving IPS liquid crystal display element, the second substrate does not have a radical generating film, and is a substrate having a liquid crystal alignment film subjected to uniaxial alignment processing, and the first substrate is a substrate having a comb-shaped electrode.

In the present invention, the "zero-plane anchoring film" means that the liquid crystal molecules in the in-plane direction have no alignment binding force at all, or even if there is, the intermolecular force of the liquid crystals is weaker than that of the liquid crystals. This film alone cannot make the liquid crystal molecules Film with uniaxial alignment in either direction. The zero-plane anchoring film is not limited to a solid film, and includes a liquid film covering a solid surface. Generally, in a liquid crystal display element, a film that restricts the alignment of liquid crystal molecules, that is, a liquid crystal alignment film is used in pairs to align liquid crystals. However, the use of the zero-plane anchor film and the liquid crystal alignment film in pairs can also align liquid crystals. . The reason is that the alignment constraint force of the liquid crystal alignment film is transmitted to the thickness direction of the liquid crystal layer through the intermolecular force of the liquid crystal molecules, and as a result, the liquid crystal molecules near the zero-plane anchoring film are also aligned. Therefore, when the liquid crystal alignment film uses a liquid crystal alignment film for horizontal alignment, the entire liquid crystal cell can be horizontally aligned. Horizontal alignment refers to a state in which the long axes of the liquid crystal molecules are aligned substantially parallel to the liquid crystal alignment film surface, and even if there is an oblique alignment of about several degrees, it is included in the category of horizontal alignment.

[Radical-generating film-forming composition] In order to form the radical-generating film-forming composition of the radical-generating film used in the present invention, a component contains a polymer and a radical capable of generating radicals. In this case, the composition may contain a polymer having a radical capable of generating a radical bonded thereto, or a composition of a compound having a radical capable of generating a radical and a polymer serving as a base resin. By coating such a composition and curing to form a film, a radical generating film based on immobilization in the film capable of generating radicals can be obtained. The radical capable of generating radicals is preferably an organic radical which can induce radical polymerization.

Examples of such an organic group that induces radical polymerization include organic groups represented by the following structures: [X-1] to [X-18], [W], [Y], and [Z]. [Chemical 11] In the formulas [X-1] to [X-18], * represents a bonding site with a portion other than the polymerizable reactive group of the compound molecule, and S ¹ and S ² each independently represent -O-, -NR-,- S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, and a carbon number 1 to 4 Alkyl group 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 an organic group and / or a halogen atom as a substituent. An aromatic hydrocarbon group in the group consisting of phenylene, naphthyl, and phenylene, R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms When R ⁹ and R ¹⁰ are alkyl groups, the ends may be bonded to each other to form a ring structure. Q represents the following structure. [Chemical 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 compound other than Q in a compound molecule. Bonding site. R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

The polymer is preferably at least one polymer selected from the group consisting of a polyimide precursor, and a polyimide, polyurea, polyimide, polyacrylate, polymethacrylate, and the like. .

In order to obtain the radical-generating film used in the present invention, when using the aforementioned polymer having an organic radical that induces radical polymerization, in order to obtain a polymer having a radical capable of generating a radical, it is preferable to use A monomer having a photoreactive side chain selected from at least one of a methacrylic group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamon group, and the side chain is decomposed by ultraviolet irradiation. And it is better to produce the monomer of the site that generates free radicals. On the other hand, considering the problems such as the monomers that generate free radicals that polymerize spontaneously, they can become unstable compounds. Therefore, considering the ease of synthesis, it is preferable to use polymers derived from diamines that have free-radical generating sites. Ideally, polyimide precursors such as polyamidic acid and polyamidate, polyamidoimide, polyurea, polyamidoimide, and the like are more preferred.

Such a diamine containing a radical generating site is, for example, a diamine having a side chain capable of generating radicals and polymerizing, such as a diamine represented by the following general formula (6), but is not limited thereto. [Chemical 14] In formula (6), R ⁶ represents a single bond, -CH _2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N ( CH ₃ )-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-, R ⁷ is a single bond, or an unsubstituted or fluorine-substituted alkylene group having 1 to 20 carbon atoms. Any one or more of -CH ₂ -or -CF ₂ -of the alkyl group may be independently substituted with a group selected from the group consisting of -CH = CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, In addition, any of the groups listed below can be used, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other on the condition that these groups To replace; R ⁸ represents a radical polymerization reactive group selected from the following formula: [化 15] . In the formulae [X-1] to [X-18], * represents a bonding site with a portion other than the radical polymerization reactive group of the compound molecule, and S ¹ and S ² each independently represent -O-, -NR- , -S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, and a carbon number 1 ~ 4 alkyl.

In formula (6), the bonding position of two amine groups (-NH ₂ ) is not limited. Specifically, the positions of 2,3 on the benzene ring, 2,4, 2,5, 2,6, 3,4, 3 , The position of 5. Among them, from the viewpoint of the reactivity when synthesizing polyamic acid, the positions of 2,4, 2,5, or 3,5 are preferred. If the ease of synthesizing diamine is also considered, the positions of 2, 4 or 3, 5 are more preferable.

As a diamine having a photoreactive group containing at least one selected from the group consisting of a methacrylic group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamyl group, Specific examples include the following compounds, but are not limited thereto. [Chemical 16] In the formula, J ¹ represents a bonding group selected from a single bond, -O-, -COO-, -NHCO-, or -NH-, and J ² represents a single bond, or an unsubstituted or fluorine atom-substituted carbon number 1 ~ 20 alkylene.

Examples of the diamine having a side chain which is decomposed by ultraviolet irradiation and generate radicals include, but are not limited to, the diamine represented by the following general formula (7). [Chem. 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 is a single bond, or an unsubstituted or fluorine-substituted alkylene having 1 to 20 carbon atoms Or any one of -CH ₂ -or -CF ₂ -of the alkylene group may be independently substituted with one selected from the group consisting of -CH = CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring. Furthermore, any one of the following groups, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- is not adjacent to each other, Group substitution, J is an organic group represented by the formula: [Chem. 18] In the formulas [W], [Y], and [Z], * represents a bonding site with T ² , and Ar represents an organic group and / or a halogen atom may be used as a substituent. Among the aromatic hydrocarbon groups in the group consisting of and biphenyl, R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q represents the following structure. [Chemical 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 compound other than Q in a compound molecule. Bonding site. R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

The bonding position of the two amine groups (-NH ₂ ) in the above formula (7) is not limited. Specifically, the positions of 2,3 on the benzene ring, 2,4, 2,5, 2,6, 3,4, 3 , The position of 5. Among them, it is preferable to consider the viewpoint of reactivity when synthesizing polyamic acid, the position of 2,4, the position of 2,5, or the position of 3,5. If the ease of synthesizing diamine is also considered, the position of 2,4, or the position of 3,5 is more preferable.

In particular, considering the ease of synthesis, the height of general use, and characteristics, the structure represented by the following formula is the most ideal but not limited to these. [Chemical 20] In the formula, n is an integer of 2-8.

These diamines can be used alone or in combination of two or more depending on the characteristics of liquid crystal alignment, sensitivity during polymerization, voltage holding characteristics, and stored charge when forming a radical-generating film.

Such a diamine having a site for generating radical polymerization is preferably used in an amount of 5 to 50 mole% of the entire diamine component used in the synthesis of the polymer contained in the radical-generating film-forming composition, and more preferably It is preferably 10 to 40 mol%, particularly preferably 15 to 30 mol%.

In addition, when the polymer used in the radical generating film of the present invention is obtained from a diamine, other diamines other than the diamine having a site where a radical is generated may be used as the diamine, as long as the effect of the present invention is not hindered. Use ingredients together. 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-di Aminophenol, 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'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4 ' -Diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diamine Diphenyl ether, 4,4'-sulfofluorenyl diphenylamine, 3,3'-sulfofluorenyl diphenylamine, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl -Bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 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'-di Aminodiphenyl) 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'-Diaminodione Benzophenone, 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-amino) Phenoxy) benzene, 4,4 '-[1,4-phenylenebis (methylene)] diphenylamine, 4,4'-[1,3-phenylenebis (methylene)] di Aniline, 3,4 '-[1,4-phenylenebis (methylene)] diphenylamine, 3,4'-[1,3-phenylenebis (methylene)] diphenylamine, 3, 3 '-[1,4-phenylenebis (methylene)] diphenylamine, 3,3'-[1,3-phenylenebis (methylene)] diphenylamine, 1,4-phenylene Bis [(4-aminophenyl) methanone], 1,4-phenylphenylbis [(3-aminophenyl) methanone], 1,3-phenylphenylbis [(4-amino Phenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4 -Phenylene bis (3-aminobenzoate), 1,3-phenylene bis (4-aminobenzoate), 1,3-phenylene bis (3-aminobenzoate) Acid ester), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) ) Terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N '-(1,4- (Phenylene) bis (4-aminobenzidine), N, N '-(1,3-phenylene) bis (4-aminobenzidine), N, N'-(1, 4-phenylene) bis (3-aminobenzylamine), N, N '-(1,3-phenylene) bis (3-aminobenzidine), N, N'-bis (4-aminophenyl) p-xylylenediamine, N, N'-bis (3-aminophenyl) p-xylylenediamine, N, N'-bis (4-aminophenyl) M-xylylenediamine, N, N'-bis (3-aminophenyl) m-xylylenediamine, 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis ( 4-aminophenoxy) diphenylphosphonium, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [4- (4-amino (Phenoxy) 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, transformer-1,4-bis (4-aminophenyl) cyclohexane, 3,5-diaminobenzene Formic acid, 2,5-diaminobenzene Acid, bis (4-aminophenoxy) methane, 1,2-bis (4-aminophenoxy) ethane, 1,3-bis (4-aminophenoxy) propane, 1,3 -Bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5 -Bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1, 6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7-bis (3-aminophenoxy) heptane, 1 , 8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10-bis (4-aminophenoxy) decane, 1,10-bis (3-aminophenoxy) decane , 1,11-bis (4-aminophenoxy) undecane, 1,11-bis (3-aminophenoxy) undecane, 1,12-bis (4-aminophenoxy) ) Aromatic diamines such as dodecane, 1,12-bis (3-aminophenoxy) dodecane; bis (4-aminocyclohexyl) methane, bis (4-amino-3-methyl) Cyclohexyl) cycloaliphatic diamines such as methane; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diamino Alkanes, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diamine Aliphatic diamines such as dodecane; 1,3-bis [2- (p-aminophenyl) ethyl] urea, 1,3-bis [2- (p-aminophenyl) ethyl] -1- Tertiary butoxycarbonylurea and other diamines with urea structure; N-p-aminophenyl-4-p-aminophenyl (tertiary butoxycarbonyl) aminomethylpiperidine and other nitrogen-containing unsaturated Diamine with heterocyclic structure; N-tertiary butoxycarbonyl-N- (2- (4-aminophenyl) ethyl) -N- (4-aminobenzyl) amine, etc. with N-Boc group Diamine and so on.

The other diamines described above can be used singly or in combination of two or more depending on characteristics such as liquid crystal alignment, sensitivity during polymerization, voltage holding characteristics, and accumulated charge when forming a radical-generating film.

In the synthesis when the polymer is polyamic acid, the tetracarboxylic dianhydride that reacts with the above diamine component is not particularly limited. Specific examples include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4 '-Biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) 碸, Bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2- Bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4 , 5-pyridine tetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9,10 -Fluorene tetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, oxydiphthalatetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid Carboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3 1,4-cyclobutane tetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclo Butane tetracarboxylic acid, 1,2,3,4-cycloheptane tetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, 3 , 4-dicarboxy-1-cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, Bicyclic [3,3,0] octane-2,4,6,8-tetracarboxylic acid, bicyclic [4,3,0] nonane-2,4,7,9-tetracarboxylic acid, bicyclic [4, 4,0] decane-2,4,7,9-tetracarboxylic acid, bicyclic [4,4,0] decane-2,4,8,10-tetracarboxylic acid, tricyclic [6.3.0.0 ＜ 2 , 6 ＞] Undecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl ) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, bicyclic [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-Dioxotetrahydrofuranyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo [6,2,1,1,0 <2,7>] Dodecane-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxy norbornane-2: 3,5: 6 dicarboxylic acid, 1,2,4,5-cyclohexane Tetracarboxylic acid and other dianhydrides.

Of course, tetracarboxylic dianhydride can also be used singly or in combination of two or more due to characteristics such as liquid crystal alignment, sensitivity during polymerization, voltage holding characteristics, and accumulated charge when forming a radical-generating film.

In the synthesis when the polymer is a polyamidate, the structure of the dicarboxylic acid dialkyl ester reacted with the diamine component is not particularly limited, and specific examples thereof are as follows. Specific examples of the aliphatic tetracarboxylic acid diesters include, for example, 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl esters, 1,2-dimethyl-1,2,3,4-cyclo Butane 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 Dialkyl 2,2,4,5-cyclohexanetetracarboxylic acid, dialkyl 3,4-dicarboxy-1-cyclohexyl succinate, 3,4-dicarboxy-1,2,3,4-tetracarboxylic acid Di-1-hydronaphthalene succinate, dialkyl 1,2,3,4-butane tetracarboxylate, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid Dialkyl esters, 3,3 ', 4,4'-dicyclohexyltetracarboxylic acid dialkyl esters, 2,3,5-tricarboxycyclopentyl diacetate, cis-3,7-dibutyl Cyclooctane-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclic [4.2.1.0 ＜ 2,5 ＞] nonane-3,4,7,8-tetracarboxylic acid Acid-3,4: 7,8-dialkyl ester, hexacyclic [6.6.0.1 <2,7> .0 <3,6> .1 <9,14> .0 <10,13>] hexadecane -4,5,11,12-tetracarboxylic acid-4,5: 11,12-dialkyl ester, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4 -Tetrahydronaphthalene-1,2-dicarboxylic acid dialkyl and the like.

Examples of the aromatic dicarboxylic acid dialkyl esters include pyromellitic acid dialkyl esters, 3,3 ', 4,4'-biphenyltetracarboxylic acid dialkyl esters, and 2,2', 3,3'-biphenyl tetracarboxylic acid. Dialkyl carboxylate, 2,3,3 ', 4-biphenyltetracarboxylic acid dialkyl ester, 3,3', 4,4'-benzophenone tetracarboxylic acid dialkyl ester, 2,3,3 ' , 4'-benzophenonetetracarboxylic acid dialkyl esters, bis (3,4-dicarboxyphenyl) ether dialkyl esters, bis (3,4-dicarboxyphenyl) fluorenedialkyl esters, 1,2, 5,6-naphthalenetetracarboxylic acid dialkyl esters, 2,3,6,7-naphthalenetetracarboxylic acid dialkyl esters, and the like.

In the synthesis when the polymer is polyurea, the diisocyanate that reacts with the diamine component is not particularly limited, and can be used in accordance with availability and the like. The specific structure of the diisocyanate is shown below. [Chemical 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 ~ K-5 have poor reactivity but have the benefit of better solvent solubility. The aromatic diisocyanates shown in K-6 ~ K-7 are rich in reactivity and heat resistant It has the effect of improving the properties, but has the disadvantage of low solvent solubility. Considering the versatility and characteristics, K-1, K-7, K-8, K-9, and K-10 are particularly preferred. When considering electrical characteristics, K-12 is ideal. From the viewpoint of liquid crystal alignment, K -13 is better. Diisocyanates can be used in combination of more than one kind, and it is better to use them according to the characteristics to be obtained. In addition, a part of the diisocyanate can be substituted with the tetracarboxylic dianhydride described above, and it can be used in the form of a copolymer of polyamic acid and polyurea, or it can be chemically fluorinated to form polyfluorene and polyimide. A polyurea copolymer is used in such a form.

In the synthesis when the polymer is polyamine, the structure of the reacted dicarboxylic acid is not particularly limited, and specific examples thereof are listed below. Specific examples of the aliphatic dicarboxylic acid include malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyl adipic acid, Dicarboxylic acids such as trimethyladipate, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, and suberic acid.

Examples of the alicyclic dicarboxylic acid include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, and 1,2-cyclobutanedicarboxylic acid. 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-cyclohexane Hexanedicarboxylic acid, 1,4- (2-norbornene) dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo [2.2.2] octane-1,4-dicarboxylic acid, Bicyclo [2.2.2] octane-2,3-dicarboxylic acid, 2,5-dioxo-1,4-bicyclo [2.2.2] octane dicarboxylic acid, 1,3-adamantane dicarboxylic acid Acid, 4,8-dioxo-1,3-adamantane dicarboxylic acid, 2,6-spiro [3.3] heptane dicarboxylic acid, 1,3-adamantane diacetic acid, camphoric acid, and the like.

Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, and 5-aminoisophthalic acid. , 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6 -Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracene dicarboxylic acid, 1,4-anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4'-biphenyl Benzenedicarboxylic acid, 1,5-biphenyldicarboxylic acid, 4,4 "-bitriphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenyl Ethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4 ' -Bibenzyl dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 4,4'-ethynylbisbenzoic acid, 4,4'-carbonyldibenzoic acid, 4,4'- Sulfonyl dibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylene diacetic acid, 3,3'-p-phenylene dipropionic acid, 4-carboxycinnamic acid, p-phenylene diacrylic acid , 3,3 '-[4,4'-(Methylenebis-p-phenylene)] dipropionic acid, 4,4 '-[4,4 -(Oxydi-p-phenylene)] dipropionic acid, 4,4 '-[4,4'-(oxydi-p-phenylene)] dibutyric acid, (isopropylidene-di-phenylene) Dicarboxylic acids such as dioxy) dibutyric acid and bis (p-carboxyphenyl) dimethylsilane.

Examples of the heterocarboxylic acid-containing dicarboxylic acid include 1,5- (9-oxofluorene) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, and 2-phenyl-4, 5-thiazoledicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5- Diazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4 -Pyridine dicarboxylic acid, 3,5-pyridine dicarboxylic acid, and the like.

The above-mentioned various dicarboxylic acids may have a fluorene dihalide or an anhydride structure. If these dicarboxylic acids are dicarboxylic acids capable of imparting polyamines with a linear structure, they are preferable in maintaining the alignment of liquid crystal molecules. Among them, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis (phenyl ) Propanedicarboxylic acid, 4,4-bitriphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, or the like dihalides are preferred. These compounds also have isomers, and may include mixtures thereof. Moreover, you may use 2 or more types of compounds together. The dicarboxylic acids used in the present invention are not limited to the exemplified compounds described above.

A diamine (also referred to as a "diamine component") as a raw material, and a tetracarboxylic dianhydride (also referred to as a "tetracarboxylic dianhydride component"), a tetracarboxylic diester, and a diisocyanate selected from the raw materials When reacting with a component in a dicarboxylic acid to obtain polyamidic acid, polyamidate, polyurea, polyamidamine, a known synthetic method can be used. Generally, there is a method of reacting a diamine component with one or more components selected from a tetracarboxylic dianhydride component, a tetracarboxylic acid diester, a diisocyanate, and a dicarboxylic acid in an organic solvent.

The reaction between the diamine component and the tetracarboxylic dianhydride component is relatively easy to proceed in an organic solvent and does not generate by-products, which is advantageous from this viewpoint.

The organic solvent used in the above reaction is not particularly limited as long as it can dissolve the polymer produced. Moreover, even if it is an organic solvent which does not dissolve a polymer, it can mix and use with the said solvent within the range which does not precipitate the produced polymer. In addition, the water in the organic solvent will hinder the polymerization reaction and cause the polymer to be hydrolyzed. Therefore, it is better to use the organic solvent after dehydration and drying.

Organic solvents, such as: 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-dimethylpropanehydrazone, N -Methylcaprolactam, dimethylmethylene, tetramethylurea, pyridine, dimethylfluorene, hexamethylmethylene, γ-butyrolactone, isopropanol, methoxymethylpentanol, Dipentene, ethylpentanone, methyl nonyl ketone, methyl ethyl ketone, methyl isopentanone, methyl isoacetone, methyl cyperidine, ethyl cyperidine, methyl cyperidine acetate, butyl Kisaithre acetate, ethylsaithre acetate, butylcarbitol, ethylcarbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethyl acetate Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-third 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 mono Acetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3- Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, Butyl ether, diisobutanone, methylcyclohexene, propyl ether, dihexyl ether, di Hexane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethyl carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, Propylene glycol acetate monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethyl Propoxylic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2- Pentanone, 2-ethyl-1-hexanol, and the like. These organic solvents may be used alone or in combination.

When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, the following methods can be cited: the solution obtained by dispersing or dissolving the diamine component in an organic solvent is stirred, and the tetracarboxylic dianhydride component is directly added, Or a method of adding or dispersing it in an organic solvent, a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride component in an organic solvent, As a method of alternately adding a diamine component, any of these methods can be used. In addition, when the diamine component or the tetracarboxylic dianhydride component is composed of a plurality of types of compounds, they can be reacted in a pre-mixed state, or they can be individually reacted sequentially, or the low-molecular-weight bodies subjected to individual reactions can be mixed React and make a high molecular weight body.

The temperature at which the diamine component reacts with the tetracarboxylic dianhydride component can be selected at any temperature, for example: -20 to 100 ° C, preferably in the range of -5 to 80 ° C. The reaction can be carried out at any concentration. For example, the total amount of the diamine component and the tetracarboxylic dianhydride component is 1 to 50% by mass, and preferably 5 to 30% by mass with respect to the reaction solution.

In the above polymerization reaction, the ratio of the total mole number of the tetracarboxylic dianhydride component to the total mole number of the diamine component can be selected according to the molecular weight of the polyamic acid to be obtained. As with the usual polycondensation reaction, the closer this mole ratio is to 1.0, the larger the molecular weight of the polyamino acid produced. The ideal range is 0.8 ~ 1.2.

The method for synthesizing the polymer used in the present invention is not limited to the method described above. When synthesizing the polyamino acid, the same method as the general method for synthesizing the polyamino acid can be used. A tetracarboxylic acid derivative such as a carboxylic acid or a tetracarboxylic sulfonium dihalide is reacted by a known method to obtain a corresponding polyamino acid. In the synthesis of polyurea, the diamine and the diisocyanate may be reacted. In the production of polyamidate or polyamidoamine, a diamine and a component selected from the group consisting of a tetracarboxylic diester and a dicarboxylic acid may be obtained in the presence of a known condensing agent, or after being derivatized into a phosphonium halide by a known method. To react with diamine.

The method for making the polyimide into a polyimide can include the following methods: hot imidization by directly heating a solution of the polyamic acid, and adding a contact to the solution of the polyamic acid. The catalyst of the media is imidization. In addition, from the viewpoint of making the voltage retention rate high from the fluorinated imidization rate of the conversion of polyamic acid to polyimide, 30% or more is preferable, and 30 to 99% is more preferable. On the other hand, considering the whitening property, that is, the viewpoint of suppressing the precipitation of the polymer in the varnish, it is preferably 70% or less. Considering the characteristics of both sides, 40 ~ 80% is more ideal.

The temperature at which the polyamidic acid is subjected to thermal hydrazine immobilization in a solution is usually 100-400 ° C, preferably 120-250 ° C. It is advisable to discharge the water generated by the fluorimide reaction outside the system for comparison. good.

The catalyst of polyamic acid can be imidized by adding alkaline catalyst and acid anhydride to the solution of polyamic acid. Usually, the temperature is -20 ~ 250 ℃, preferably 0 ~ 180 ℃. The amount of alkaline catalyst is usually 0.5 to 30 mol times, preferably 2 to 20 mol times, and the amount of acid anhydride is usually 1 to 50 mol times of glutamic acid group. It is 3 to 30 mole times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has moderate alkalinity for the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. When acetic anhydride is used, it is easy to purify the reaction after completion of the reaction, and is therefore preferable. The rate of amidine imidization obtained by the catalyst amidine can be controlled by adjusting the amount of catalyst, reaction temperature, reaction time, and the like.

When the polymer produced is recovered from the polymer reaction solution, the reaction solution can be charged into a poor solvent and precipitated. Examples of the poor solvent used for the precipitation include methanol, acetone, hexane, butyl cyperidine, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer added to the poor solvent to precipitate it can be filtered and recovered, and then can be dried at room temperature or under normal pressure or reduced pressure. In addition, if the polymer recovered by precipitation is dissolved in an organic solvent and reprecipitation is performed, and the operation is repeated 2 to 10 times, impurities in the polymer can be reduced. Poor solvents at this time are, for example, alcohols, ketones, hydrocarbons, etc. If three or more kinds of poor solvents selected among them are used, the purification efficiency will be better, which is preferable.

When the above-mentioned radical-generating film is composed 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 a polymer containing an organic group that induces radical polymerization. Other polymers. At this time, it is desirable that the content of other polymers in the entire polymer composition is 5 to 95% by mass, and more preferably 30 to 70% by mass.

The molecular weight of the polymer contained in the radical-generating film-forming composition is determined by considering the strength of the radical-generating film obtained by coating the radical-generating film, the workability during coating film formation, and the uniformity of the coating film. A weight average molecular weight determined by GPC (Gel, Permeation, and Chromatography) method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

When a radical-generating compound and a polymer composition are coated and hardened to form a film, and the radical-generating film used in the present invention is obtained by immobilization in the film, the polymer is selected from those produced by the above-mentioned production method. Polyimide precursors, and polymers in the group consisting of polyimide, polyurea, polyimide, polyacrylate, polymethacrylate, etc., can be used to generate free-radical polymerized parts in appliances. The diamine is at least one polymer obtained from 0 mole% of the diamine component of the entire diamine component used in the synthesis of the polymer contained in the radical-generating film-forming composition. Examples of the compound having a radical generating group added at this time are as follows.

A compound that generates a radical by heat is a compound that generates a radical by heating above a decomposition temperature. Such radical thermal polymerization initiators include, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), and difluorenyl peroxides (acetamidine peroxide, benzamidine peroxide). Etc.), hydrogen peroxides (hydrogen peroxide, third butyl hydroperoxide, cumene hydrogen peroxide, etc.), dialkyl peroxides (di third butyl peroxide, dicumene Peroxides, lauryl diperoxide, etc.), ketal peroxides (dibutyl cyclohexane peroxide, etc.), alkyl peresters (neodecanoic acid-third butyl peroxide, peroxidation) Trimethylacetic acid-third butyl ester, 2-ethylcyclohexane tripentyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (Azobisisobutyronitrile, 2,2'-bis (2-hydroxyethyl) azobisisobutyronitrile, etc.). Such a radical thermal polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

The compound that generates radicals by light is not particularly limited as long as it is a compound that starts radical polymerization by irradiation with light. Examples of such a radical photopolymerization initiator include benzophenone, mignonone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylphenylacetone, 2-hydroxy-2-methyl-4'-isopropylphenylacetone , 1-hydroxycyclohexyl phenone, cumene benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl Acetophenone, camphorquinone, benzoxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2- Porphyrin-1-one, 2-benzyl-2-dimethylamino-1- (4- (Phenolinylphenyl) -butanone-1,4-dimethylaminobenzoate, 4-dimethylaminoisobenzoate, 4,4'-bis (third butylperoxycarbonyl) di Benzophenone, 3,4,4'-tris (third butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzyl diphenylphosphine oxide, 2- (4'-methyl (Oxystyryl) -4,6-bis (trichloromethyl) -s-tri , 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-tri , 2- (2 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-tri , 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-tri , 2- (4'-pentoxystyryl) -4,6-bis (trichloromethyl) -s-tri , 4- [p-N, N-bis (ethoxycarbonylmethyl)]-2,6-bis (trichloromethyl) -s-tris , 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-tri , 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-tri , 2- (p-dimethylaminostyryl) benzo Azole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorobenzene) ) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'- (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-dimethylamine Propylpropanyl) carbazole, 3,6-bis (2-methyl-2- (Porphyrinyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenone, bis (5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro -3- (1H-pyrrole-1-yl) -phenyl) titanium, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) benzophenone, 3,3', 4,4 '-Tetrakis (third hexylperoxycarbonyl) benzophenone, 3,3'-bis (methoxycarbonyl) -4,4'-bis (third butylperoxycarbonyl) benzophenone, 3,4 '-Bis (methoxycarbonyl) -4,3'-bis (third butylperoxycarbonyl) benzophenone, 4,4'-bis (methoxycarbonyl) -3,3'-bis (section Tributylperoxycarbonyl) benzophenone, 2- (3-methyl-3H-benzothiazol-2-ylidene) -1-naphth-2-yl-ethanone, or 2- (3-methyl -1,3-benzothiazole-2 (3H) -subunit) -1- (2-benzylidene) ethanone and the like. These compounds may be used alone or in combination of two or more.

Further, even when the radical generating film is composed of a polymer having an organic group containing an induced radical polymerization, a compound having a radical generating group may be contained in order to promote radical polymerization when energy is given.

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

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

Solvents for better uniformity and smoothness of coating film, such as: isopropanol, methoxymethylpentanol, methylcythrene, ethylcythrene, butylcythrene, methylcythrene Threoacetate, butylcythreone acetate, ethylcythrene acetate, butylcarbitol, ethylcarbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol Alcohol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-third butyl ether, dipropylene glycol monomethyl ether 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 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, pentyl acetate, butyl butyrate, butyl ether, diisobutanone, methyl Hexene, 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, Methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- 1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate Ester, 2-ethyl-1-hexanol and the like. These solvents may be used in combination. When using these solvents, it is preferable that the total amount of the solvent contained in the liquid crystal alignment agent is 5 to 80% by mass, and more preferably 20 to 60% by mass.

The radical-generating film-forming composition may contain components other than the above. Examples thereof include compounds which make the film thickness uniformity and surface smoothness when coating the radical-generating film-forming composition, compounds which make the radical-generating film-forming composition and the substrate more adhesive, and Compounds having better film strength of the radical-generating film-forming composition.

Examples of the compound that improves the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a polysiloxane-based surfactant, and a nonionic surfactant. More specifically, for example: EFTOP EF301, EF303, EF352 (made by Tohkem Products)), MegafacF171, F173, R-30 (made by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (made by Sumitomo 3M), AsahiGuard AG710 , SurflonS-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.), etc. When using these surfactants, the use ratio is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, relative to the total amount of the polymer contained in the radical-generating film-forming composition.

Specific examples of the compound that improves the adhesion between the radical-generating film-forming composition and the substrate include a compound containing a functional silane, a compound containing an epoxy group, and the like. For example: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropane Trimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrisilane Ethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 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-aminopropyltriethoxy Silyl, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethyl) -3-amino Propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethyl Oxysilane, ethylene glycol dipropylene oxide, polyethylene glycol dipropylene oxide, propylene glycol dipropylene oxide, tripropylene glycol dipropylene oxide, polypropylene glycol dipropylene oxide, neopentyl glycol Diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentadiol diglycidyl ether, 1,3,5,6 -Tetraglycidyl-2,4-hexanediol, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-glycidylamine Methyl) cyclohexane, N, N, N ', N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-epoxy Propyl) aminopropyltrimethoxysilane, 3- (N, N-diepoxypropyl) aminopropyltrimethoxysilane, and the like.

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

In addition, in addition to the above, in the radical-generating film-forming composition, a dielectric may be added in order to change the electrical properties such as the dielectric constant and the conductivity of the radical-generating film within a range that does not impair the effects of the present invention. Body, conductive material.

[Radical-Generating Film] The radical-generating film of the present invention can be obtained using the above-mentioned radical-generating film-forming composition. For example, the radical-generating film-forming composition used in the present invention can be applied to a substrate, and then dried and calcined to obtain a cured film, which can be directly used as a radical-generating film. In addition, the cured film may be rubbed, polarized, or irradiated with light of a specific wavelength, etc., or subjected to an ion beam or the like, or UV may be applied to the liquid crystal display element filled with the liquid crystal as a PSA alignment film.

The substrate to which the radical-generating film-forming composition is applied is not particularly limited as long as it is a substrate having high transparency, and a substrate having a transparent electrode for driving liquid crystal on the substrate is preferred. Specific examples include glass plates, polycarbonate, poly (meth) acrylate, polyether fluorene, polyarylate, polyurethane, polyfluorene, polyether, polyetherketone, and trimethyl. Transparent electrodes such as pentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triethyl cellulose, diethyl cellulose, and cellulose acetate butyrate form transparent electrodes The substrate.

For substrates that can be used for IPS-type liquid crystal display elements, standard IPS comb-tooth electrodes, electrode patterns such as PSA fish bone electrodes, and protrusion patterns such as MVA can also be used. In addition, in a high-performance element such as a TFT element, an element in which a transistor is formed between an electrode for driving liquid crystal and a substrate is used. When manufacturing a transmissive liquid crystal display element, a substrate such as the above is generally used, but when manufacturing a reflective liquid crystal display element, if the substrate is only one side, an opaque substrate such as a silicon wafer can also be used. At this time, the electrode formed on the substrate may also be made of a material such as aluminum that reflects light.

Examples of the coating method of the radical-generating film-forming composition include a spin coating method, a printing method, an inkjet method, a spray method, and a roll coating method. However, in terms of productivity, the transfer printing method is widely used in industry. The present invention is also ideally used.

The drying step after applying the radical-generating film-forming composition is not necessarily necessary, but when the time from the coating of each substrate to the calcination is not fixed, or when the calcination is not immediately after coating, it is preferable to include a drying step. . This drying may be performed so long as the solvent is removed to such an extent that the shape of the coating film is not deformed by the substrate transportation or the like, and there is no particular limitation on the drying means. 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.

The coating film formed by coating the radical-generating film-forming composition by the above method can be calcined and made into a cured film. At this time, the calcination temperature can usually be performed at any temperature of 100 ° C to 350 ° C, preferably 140 ° C to 300 ° C, more preferably 150 ° C to 230 ° C, and still more preferably 160 ° C to 220 ° C. The calcination time can usually be calcined at any time from 5 minutes to 240 minutes. It is preferably 10 to 90 minutes, and more preferably 20 to 90 minutes. For heating, generally known methods such as a hot plate, a hot air circulation oven, an IR oven, a belt furnace, and the like can be used.

The thickness of this cured film can be selected according to need, and it is preferably 5 nm or more, and more preferably 10 nm or more, since it is easy to obtain the reliability of the liquid crystal display element, so it is ideal. When the thickness of the cured film is preferably 300 nm or less, and more preferably 150 nm or less, the power consumption of the liquid crystal display element does not become extremely large, which is desirable.

The first substrate having a radical generating film can be obtained as described above, but the radical generating film can be subjected to a uniaxial alignment process. Examples of the method for performing the uniaxial alignment process include a photo-alignment method, an oblique vapor deposition method, friction, and a uniaxial alignment process using a magnetic field.

When performing the alignment processing by performing the rubbing treatment in one direction, for example, the substrate is moved while the rubbing roller wound with the rubbing cloth is rotated while the rubbing cloth is brought into contact with the film. In the case of the first substrate of the present invention in which comb-shaped electrodes have been formed, the direction of the liquid crystal is used to select the direction. However, when a liquid crystal with positive dielectric anisotropy is used, the rubbing direction should be set to the direction of the comb electrode. It is preferable that the extending directions are substantially the same.

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

<Liquid crystal cell> The liquid crystal cell of the present invention is formed by the above-mentioned method to form a radical generating film on a substrate, and then the substrate having the radical generating film (the first substrate) and the substrate having the known liquid crystal alignment film (the first (2 substrates) are arranged so that the radical generating film and the liquid crystal alignment film face each other, the spacer is held therebetween and fixed with a sealant, and the liquid crystal composition containing the liquid crystal and the radical polymerizable compound is injected and sealed. The size of the spacer used at this time is usually 1 to 30 μm, preferably 2 to 10 μm. In addition, the rubbing direction of the first substrate and the rubbing direction of the second substrate can be used in parallel in the IPS mode and the FFS mode. If the rubbing direction is perpendicularly intersected, the rubbing nematic mode can be used. The method for injecting a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is not particularly limited. Examples include a vacuum method of injecting a mixture containing liquid crystal and a polymerizable compound into a liquid crystal cell after the pressure is reduced, After the mixture of the liquid crystal and the polymerizable compound is sealed, a dropping method such as sealing is performed.

<Liquid crystal composition containing liquid crystal and radical polymerizable compound> The polymerizable compound used with the liquid crystal during the production of the liquid crystal display device of the present invention is not particularly limited as long as it is a radical polymerizable compound. For example, one molecule has A compound having one or more polymerizable reactive groups. A compound having one polymerizable reactive group in one molecule (hereinafter sometimes referred to as a "monofunctional polymerizable group compound", a "monofunctional polymerizable group compound", etc.) is preferred. The polymerizable reactive group is preferably a radical polymerizable reactive group such as a vinyl bond.

At least one of the aforementioned radical polymerizable compounds is preferably a compound having one polymerizable reactive group in one molecule having compatibility with liquid crystal. That is, a compound having a monofunctional radical polymerizable group is preferred.

The polymerizable group of the radical polymerizable compound is preferably a polymerizable group selected from the following structures. [Chemical 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 linear alkyl group having 2 to 8 carbon atoms, and E represents a bonding group selected from the group consisting of a single bond, -O-, -NR ^c- , -S-, an ester bond, and an amidine bond. R ^c represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.

The liquid crystal composition containing a liquid crystal and a radically polymerizable compound preferably contains a radically polymerizable compound having a Tg of 100 ° C. or lower for a polymer obtained by polymerizing the radically polymerizable compound.

Monofunctional radically polymerizable compounds have reactive groups that can undergo radical polymerization in the presence of organic radicals, such as: third butyl methacrylate, hexyl methacrylate, 2-ethyl methacrylate Methacrylate monomers such as hexyl ester, nonyl methacrylate, lauryl methacrylate, n-octyl methacrylate; third butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, acrylic acid Nonyl, benzyl acrylate, lauryl acrylate, n-octyl acrylate and other acrylate monomers; styrene, styrene derivatives (for example: o, m, p-methoxystyrene, o, m, p Butoxystyrene, o-, m-, p-chloromethylstyrene, etc.), vinyl esters (e.g. vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate, etc.), ketenes (e.g. : Vinylmethanone, vinylhexanone, methylisopropenone, etc.), N-vinyl compounds (for example: N-vinylpyrrolidone, N-vinylpyrrole, N-vinylcarbazole, N-vinyl Indole, etc.), (meth) acrylic acid derivatives (e.g., acrylic Acrylonitrile, methacrylonitrile, acrylamide, isopropylacrylamide, methacrylamide, etc.), halogenated vinyls (e.g. vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachlorobutadiene , Fluorinated vinyl, etc.), but are not limited to these. These various radical polymerizable monomers may be used alone or in combination of two or more. In addition, they are preferably compatible with liquid crystals.

The radical polymerizable compound is also preferably a compound represented by the following formula (1). [Chemical 23] In formula (1), R ^a and R ^b each independently represent a linear alkyl group having 2 to 8 carbon atoms, and E represents a member selected from a single bond, -O-, -NR ^c- , -S-, an ester bond, and 醯Bonding group in amine bond. Herein, R ^c represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.

At least one of the aforementioned radically polymerizable compounds is preferably a compound having one polymerizable reactive group in one molecule that is compatible with liquid crystal, that is, a compound having a monofunctional radical polymerizable group is more suitable good.

In the radically polymerizable compound represented by the formula (1), in the synthetic formula, E is an ester bond (a bond represented by -C (= O) -O- or -OC (= O)-). From the standpoint of easiness, compatibility with liquid crystal, and polymerization reactivity, compounds having the following structures are preferred, but are not particularly limited.

[Chemical 24]

In the formulae (1-1) and (1-2), R ^a and R ^b each independently represent a linear alkyl group having 2 to 8 carbon atoms.

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

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

In addition, liquid crystal generally refers to a substance that exhibits properties of both solids and liquids. Representative liquid crystal phases are nematic liquid crystal and smectic liquid crystal. The liquid crystal usable in the present invention is not particularly limited. For example, it is 4-pentyl-4'-cyanobiphenyl.

Then, a sufficient amount of energy is introduced into the liquid crystal cell into which the mixture (liquid crystal composition) containing the liquid crystal and the radical polymerizable compound is subjected to a polymerization reaction. This can be carried out by, for example, heating or UV irradiation, and the desired properties can be exhibited by polymerizing the radical polymerizable compound in situ. Among them, the use of UV can make the alignment patternable, and the polymerization reaction can be performed in a short time. From this viewpoint, UV irradiation is better. In the case of using the twisted nematic mode, a chiral dopant may be introduced into the liquid crystal cell in addition to the liquid crystal composition as described above.

In addition, heating may be performed during UV irradiation. The heating temperature during UV irradiation is preferably a temperature range in which the introduced liquid crystal exhibits liquid crystallinity, which is usually above 40 ° C, and is preferably heated at a temperature before the liquid crystal changes to an isotropic phase.

Here, the UV irradiation wavelength when UV irradiation is performed, it is better to select the optimal wavelength for the reaction quantum yield of the polymerizable compound to be reacted. The UV irradiation amount is usually 0.01 ~ 30J, preferably 10J or less. The UV irradiation amount The smaller the number, the more it is possible to suppress the decrease in reliability caused by the damage of the components constituting the liquid crystal display, and it is possible to improve the tact in manufacturing by reducing the UV irradiation time, which is ideal.

In addition, when the polymerization is performed only by heating without UV irradiation, the temperature is preferably within a temperature range where the polymerizable compound reacts and does not reach the decomposition temperature of the liquid crystal. Specifically, it is, for example, 100 ° C or higher and 150 ° C or lower.

When sufficient energy is given to cause the radically polymerizable compound to undergo a polymerization reaction, it is preferable to be in an electric field-free state without applying a voltage.

<Liquid crystal display element> The liquid crystal cell obtained in this way can be used to produce a liquid crystal display element. For example, a reflective electrode, a transparent electrode, a λ / 4 plate, a polarizing film, a color filter layer, etc. may be provided in the liquid crystal cell according to a conventional method as required, and a reflective liquid crystal display element may be manufactured. In addition, the liquid crystal cell is provided with a backlight, a polarizing plate, a λ / 4 plate, a transparent electrode, a polarizing film, a color filter layer, and the like according to a conventional method as required, and can be made into a transmissive liquid crystal display element. [Example]

The present invention is described more specifically with examples, but the present invention is not limited to these examples. The abbreviations of the compounds used in the polymerization of the polymer and the preparation of the film-forming composition, and the methods of characteristic evaluation are as follows.

[Chemical 25]

NMP: N-methyl-2-pyrrolidone, GBL: γ-butyl lactone, BCS: butyl cyperidine

<Viscosity measurement> For a polyamic acid solution, an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) was used, and a sample volume of 1.1 mL and Cone Rotor TE-1 (1 ° 34 ', R24) was measured at 25 ° C. Of viscosity.

<Measurement of hydrazone imidization ratio> 20 mg of polyfluorene imine powder was placed in an NMR sample tube (NMR standard sampling tube φ5 manufactured by Kusano Science Co., Ltd.), and deuterated dimethylsulfine (DMSO-d6, 0.05% by mass TMS) was added. (Tetramethylsilane) mixed product) 0.53 ml, completely dissolved by applying ultrasonic waves. A 500 MHz proton NMR of this solution was measured with a measuring device (manufactured by Japan Electronics Data Corporation, JNW-ECA500). The rate of imidization is determined based on protons from structures that do not change before and after imidization. The peaks of this proton are used to accumulate ammonium and protons from ammonium NH in the vicinity of 9.5 to 10.0 ppm. Peaks accumulate 値 and are calculated by the following formula.醯 Imination ratio (%) = (1-α · x / y) × 100 In the formula, x is the accumulation of proton peaks of NH derived from hydrazone, y is the accumulation of peaks of reference protons, y is α It is the ratio of the number of reference protons to the NH protons of the amido group at the time of polyamidic acid (the ammonium imidization rate is 0%).

<Polymerization of Polymer and Preparation of Free Radical Generation Film Forming Composition> Synthesis Example 1 Polymerization of TC-1, TC-2 (50) / DA-1 (50), and DA-2 (50) polyimide In a 100 ml 4-neck flask equipped with a nitrogen introduction tube, an air cooling tube, and a mechanical stirrer, measure 1.62 g of DA-1 (15.00 mmol) and 3.96 g of DA-2 (15.00 mmol), add 48.2 g of NMP, and Stir under nitrogen to completely dissolve. After confirming dissolution, 3.75 g of TC-2 (15.00 mmol) was added and reacted at 60 ° C for 3 hours under a nitrogen atmosphere. After returning to room temperature, 2.71 g of TC-1 (13.80 mmol) was added, and the mixture was reacted at 40 ° C for 12 hours under a nitrogen atmosphere. The polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity became 1000 mPa · s to obtain a polymerization solution having a polyamic acid concentration of 20% by mass. In a 200 ml conical flask equipped with a magnetic stir bar, measure 60 g of the polyamic acid solution obtained above, add 111.4 g of NMP to prepare a 7% by mass solution, and add 9.10 g (88.52 mmol) of acetic anhydride while stirring, 3.76 g (47.53 mmol) of pyridine was stirred at room temperature for 30 minutes, and then stirred at 55 ° C for 3 hours to react. After the reaction was completed, the solution was returned to room temperature, and the reaction solution was poured into 500 ml of methanol while stirring to precipitate a solid. The solid was recovered by filtration, and then the solid was poured into 300 ml of methanol and stirred for 30 minutes for washing, for a total of 2 times to filter and recover the solid. After air-drying, it was dried in a vacuum oven at 60 ° C to obtain a number average molecular weight of 11,300, Polyfluorene imine (PI-1) having a weight average molecular weight of 32900 and a fluorene imidization rate of 53%.

Synthesis Example 2 Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-3 (50) polyimide on 100ml of 4 equipped with nitrogen introduction tube, air cooling tube, mechanical stirrer In a mouth flask, 1.62 g of DA-1 (15.00 mmol) and 4.96 g of DA-3 (15.00 mmol) were weighed, and NMP51.90 g was added, and the mixture was stirred and completely dissolved in a nitrogen environment. After confirming the dissolution, 3.75 g of TC-2 (15.00 mmol) was added and reacted at 60 ° C for 3 hours under a nitrogen atmosphere. After returning to room temperature, 2.64 g of TC-1 (13.5 mmol) was added, and the reaction was performed at 40 ° C for 12 hours under a nitrogen atmosphere. The polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity became 1000 mPa · s to obtain a polymerization solution having a polyamic acid concentration of 20% by mass. In a 200 ml conical flask equipped with a magnetic stir bar, measure 60 g of the polyamic acid solution obtained above, add NMP111.4 g to prepare a 7% by mass solution, and add 8.38 g (81.4 mmol) of acetic anhydride while stirring. 3.62 g (45.8 mmol) of pyridine was stirred at room temperature for 30 minutes, and then stirred at 55 ° C for 3 hours for reaction. After the reaction was completed, the solution was returned to room temperature, and the reaction solution was injected while stirring in 500 ml of methanol to precipitate a solid. The solid was recovered by filtration, and the solid was added to 300 ml of methanol and stirred and washed for a total of 2 times for 30 minutes. The solid was recovered by filtration, dried in a vacuum oven at 60 ° C to obtain a number average molecular weight Mn of 13,100 Polyimide (PI-2) having a weight average molecular weight Mw of 34,000 and a fluorene imidization rate of 55%.

Synthesis Example 3 Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-4 (50) polyimide on 100ml of 4 equipped with nitrogen introduction tube, air cooling tube, mechanical stirrer In a mouth flask, 1.62 g of DA-1 (15.00 mmol) and 5.65 g of DA-4 (15.00 mmol) were weighed. 55.4 g of NMP was added and stirred under a nitrogen environment to completely dissolve. After confirming the dissolution, 3.75 g of TC-2 (15.00 mmol) was added, and reacted at 60 ° C for 3 hours under a nitrogen atmosphere. After returning to room temperature, 2.82 g of TC-1 (14.40 mmol) was added, and the reaction was performed at 40 ° C for 12 hours under a nitrogen atmosphere. The polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity became 1000 mPa · s to obtain a polymerization solution having a polyamic acid concentration of 20% by mass. In a 200 ml conical flask equipped with a magnetic stir bar, measure 60 g of the polyamic acid solution obtained above, add NMP111.4 g to prepare a 7% by mass solution, and add 8.36 g (81.2 mmol) of acetic anhydride while stirring. 3.65 g (46.1 mmol) of pyridine was stirred at room temperature for 30 minutes, and then stirred at 55 ° C. for 3 hours to react. After the reaction was completed, the solution was returned to room temperature, and the reaction solution was poured into 500 ml of methanol while stirring to precipitate a solid. The solid was recovered by filtration, and then the solid was poured into 300 ml of methanol and stirred and washed for a total of 2 times. The solid was recovered by filtration, air-dried, and then dried in a vacuum oven at 60 ° C. to obtain the number average molecular weight Mn. Polyimide (PI-3) of 12,900, a weight average molecular weight Mw of 31,000, and a fluorene imidization rate of 51%.

Free radical generating film-forming composition: Preparation of AL1 In a 50 ml Erlenmeyer flask equipped with a magnetic stirrer, 2.0 g of polyimide powder (PI-1) obtained in Synthesis Example 1 was weighed, and 18.0 g of NMP was added, and the temperature was 50 ° C. Stir to completely dissolve. 6.7 g of NMP and 6.7 g of BCS were further added, and the mixture was further stirred for 3 hours to obtain the radical-generating film-forming composition of the present invention: AL1 (solid content: 6.0% by mass, NMP: 66% by mass, BCS: 30% by mass).

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

Non-radical-generating film-forming composition: AL3 was prepared in a 50-ml Erlenmeyer flask equipped with a magnetic stirrer. 2.0 g of polyimide powder (PI-3) obtained in Synthesis Example 3 was measured, and 18.0 g of NMP was added. Stir at 50 ° C to completely dissolve. Then, NMP6.7g and BCS6.7g were added, and the mixture was further stirred for 3 hours to obtain a non-radical-generating film-forming composition for comparison: AL3 (solid content: 6.0% by mass, NMP: 66% by mass, BCS: 30% by mass). ).

[Table 1] Table 1 Composition of polyimide

[Table 2] Table 2 Composition of film-forming composition

<Production of liquid crystal display element> The liquid crystal display element SE-6414 (manufactured by Nissan Chemical Industries, Ltd.) used in the above-mentioned AL1 to AL3 and horizontal alignment liquid crystal alignment agent was used to produce a liquid crystal display element with the configuration shown in Table 3.

[Table 3] Table 3 Composition of the unit cell

(First substrate) The first substrate (hereinafter also referred to as an IPS substrate) is an alkali-free glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. An ITO (Indium-Tin-Oxide) electrode with a comb-shaped pattern having an electrode width of 10 μm and an electrode-to-electrode spacing of 10 μm is formed on a substrate, and pixels are formed. The size of each pixel is 10 mm in length and about 5 mm in width. AL1 ~ AL3 or SE-6414 are filtered by a 1.0 μm filter, and then coated on the electrode formation surface of the IPS substrate by spin coating, and dried on a hot plate at 80 ° C. for 1 minute. Then, AL1 to AL3 were calcined at 150 ° C for 20 minutes, and SE-6414 was calcined at 220 ° C for 20 minutes to form coating films each having a thickness of 100 nm. When the rubbing treatment is "yes", rubbing is performed so that the rubbing direction becomes parallel to the comb electrode. The rubbing cloth made by Yoshikawa Chemical Co., Ltd .: YA-20R was performed 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 pushing amount of 0.4 mm. However, only the film coated with SE-6414 set the above rotation speed to 1000 rpm. After the rubbing treatment, ultrasonic irradiation was performed in pure water for 1 minute, and drying was performed at 80 ° C for 10 minutes.

(Second substrate) The second substrate (also referred to as the back ITO substrate) is an alkali-free glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. An ITO film is formed on the back (the surface facing the outside of the cell). Furthermore, a columnar spacer having a height of 4 μm was formed on the surface (the surface facing the inside of the unit cell). AL1, AL2, or SE-6414 was filtered through a 1.0 μm filter, and then applied to the electrode formation surface of the IPS substrate by a spin coating method, and dried on a hot plate at 80 ° C. for 1 minute. Then, AL1 and AL2 were calcined at 150 ° C for 20 minutes, and SE-6414 was calcined at 220 ° C for 20 minutes to obtain a coating film having a thickness of 100 nm, followed by rubbing treatment. The rubbing treatment was carried out using a cloth made by Yoshikawa Chemical Co., Ltd .: YA-20R, and rubbing was performed under conditions of a roll diameter of 120 mm, a rotation speed of 1000 rpm, a moving speed of 50 mm / sec, and a pushing amount of 0.4 mm. However, a film coated with AL1 or AL2 was set at 300 rpm. After the rubbing treatment, it was irradiated with ultrasonic waves in pure water for 1 minute, and dried at 80 ° C for 10 minutes.

(Manufacturing of liquid crystal cell) The above two types of substrates (first substrate and second substrate) with a liquid crystal alignment film were used, leaving the liquid crystal injection port and sealing the surroundings, to produce an empty cell with a cell gap of about 4 μm. At this time, if the first substrate is not subjected to rubbing treatment, the comb electrode electrodes of the first substrate and the rubbing direction of the second substrate are combined in parallel. When the rubbing treatment is performed on the first substrate, the first substrate is used. It is combined so that the rubbing direction of the second substrate becomes antiparallel. In this empty cell, liquid crystal (in which 10 wt% HMA is added to MLC-3019 manufactured by Merck) is vacuum-injected at room temperature, and then the injection port is sealed to obtain a liquid crystal cell. The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was heat-treated at 120 ° C for 20 minutes. When UV treatment is used, a high-pressure mercury lamp is used to irradiate a liquid crystal cell with a bandpass filter with a wavelength of 313 nm to irradiate ultraviolet rays so that the exposure amount becomes 1000 mJ.

<Evaluation of Liquid Crystal Alignment> The alignment of a liquid crystal cell was confirmed using a polarizing plate mounted on a cross nicol. Those with no defects and alignment are rated as ○, those with slight alignment defects are rated as △, those without alignment are rated as ×.

<Measurement of VT curve and evaluation of driving threshold voltage and brightness maximum voltage> A white LED backlight and a brightness meter are installed in a manner consistent with the optical axis, and a liquid crystal cell with a polarizing plate is installed in a manner so that the brightness is minimized. (Liquid crystal display element) The voltage was applied at 1V intervals up to 8V, and the brightness of the voltage was measured to measure the VT curve. From the obtained V-T curve, the driving threshold voltage and the voltage at which the brightness becomes the maximum are estimated.

＜ Evaluation of the response speed of the liquid crystal display ＞ Using the device used for the measurement of the VT curve described above, connect the luminance meter to the oscilloscope, and measure the response speed (Ton) when the voltage to the maximum brightness is applied and the response speed when the voltage is 0 (Toff).

【Table 4】

In a comparison of Cell-1 to Cell-20 using horizontal alignment films that are rubbed on the back ITO substrate (second substrate) side, the IPS substrate (first substrate) side uses a free radical generating film and is UV-treated. Cell-11, Cell-12, Cell-16, and Cell-17, confirm that the alignment of the liquid crystal is good, and the driving threshold voltage and brightness maximum voltage are reduced. In addition, it was confirmed that in Cell-11 and Cell-12 in which the radical-generating film was not subjected to rubbing treatment, the Toff increase was increased. In contrast, in Cell-16 and Cell-17 in which the radical-generating film was subjected to rubbing treatment, this Toff The increase was significantly improved.

In addition to the above, in terms of supplementary facts, AL1 is used to produce a liquid crystal cell that uses both the back ITO substrate (second substrate) and the IPS substrate (first substrate), and the first substrate and the second substrate are not subjected to rubbing treatment. In this liquid crystal cell, alignment defects and bright spots (flow alignment) along the flow direction when the liquid crystal was injected were observed before UV irradiation, but the flow alignment completely disappeared after UV irradiation, and it was confirmed that the microdomains (isolation) from the liquid crystal体 (schlieren)). This suggests that when a liquid crystal containing a radical-generating film and a polymerizable compound is used in combination, by irradiating UV, the radical-generating film loses the liquid crystal alignment constraint, and a zero-plane anchoring film is formed on the radical-generating film.

In the comparison of the liquid crystal cells Cell-21 to Cell-24, Cell-21 and Cell-23 without UV irradiation showed uniaxial alignment in the rubbing direction, but Cell-22 and Cell- 24. It becomes a non-alignment state, and microdomains (isotopes) of the liquid crystal occur. This suggests that even if the radical generating film is rubbed, a zero-plane anchoring film can be formed on the radical generating film by irradiating UV.

However, if Cell-22 and Cell-24 are observed while rotating under the crossed Nicols, there will be a slight change in light and shade. This indicates that the zero-plane anchoring film is not completely without the orientation binding force, but the binding force ratio Since the intermolecular forces between the liquid crystals are weak, the binding force alone will not cause the liquid crystal molecules to be uniaxially aligned in either direction. It can be seen that the significant improvement of Toff in Cell-16 and Cell-17 is mainly due to the aforementioned weak binding effect.

Polymerizable Compound Synthesis Example 1 Synthesis of 2- (heptanoyloxymethyl) ethyl acrylate [Chem. 26] Step 1: Synthesis of 2-hydroxyethyl methacrylate In a 500 ml four-necked flask equipped with a nitrogen introduction tube, measure 10 mg of 4-methoxyphenol and DABCO (1,4-diazabicyclo [2.2. 2] Octane) 21.88 g (195.1 mmol), 50 ml of pure water was added, and 11.52 g (390.1 mmol) of paraformaldehyde was added while stirring at 10 ° C. or lower under a nitrogen atmosphere, followed by stirring for 1 hour. After confirming the change from the slurry state to the solution state, 300 ml of acetonitrile was added, and 19.53 g (195.1 mmol) of ethyl acrylate was added dropwise to the reaction at 50 ° C. for 5 hours. After the reaction, the reaction solution was transferred to a separating funnel, and 50 ml of n-hexane was added. Confirm that it has been separated into 3 layers, collect the lower 2 layers, and perform this operation 3 times. Further, hydrochloric acid was added to adjust the pH to 4 to 5, and extraction was performed using ethyl acetate. Anhydrous magnesium sulfate was added to the extracted solution, stirred, dried, and then filtered and concentrated to obtain 22.9 g (175.6 mmol, yield 90%) of a colorless and transparent oily liquid. In nuclear magnetic resonance spectroscopy confirmed the structure ⁽¹ H-NMR spectroscopy) is the desired product. The measurement data are as follows. ¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.81 (1H), 5.80 (1H), 4.31 (2H), 4.17 (1H), 1.98 (1H), 0.93 (3H)

Step 2: Synthesis of 2- (heptanoyloxymethyl) ethyl acrylate In a 500 ml 4-neck flask equipped with a nitrogen introduction tube, 19.9 g (152.9 mmol) of 2-hydroxymethacrylic acid obtained by the above method was measured. ), 300 ml of THF and 23.2 g (229.3 mmol) of triethylamine were added, and 25.0 g (168.2 mmol) of heptyl chloride was added dropwise while maintaining the temperature at 10 ° C. or lower under a nitrogen atmosphere, and reacted for 6 hours. After the reaction, the precipitated triethylamine hydrochloride was removed by filtration, and the reaction solution was concentrated to re-dissolve it in 300 ml of ethyl acetate, washed 3 times with 100 ml of a 10% potassium carbonate aqueous solution, and washed 3 times with 50 ml of pure water. After drying with anhydrous magnesium sulfate, it was filtered and concentrated to obtain a pale yellow slime. It was then purified by flash column chromatography (developing solvent: ethyl acetate: n-hexane = 20: 80), and the solvent was removed and dried under vacuum to obtain 32.2 g (133.0 mmol: 87%) of a colorless and transparent oily liquid. . In structure-based nuclear magnetic resonance spectrum ⁽¹ H-NMR spectra) confirmed to be the desired product. The measurement data are as follows. ¹ H NMR (400 MHz, 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) butyl acrylate [Chem. 27] Step 1: Synthesis of 2-hydroxybutyl methacrylate By the same operation as in the above step 1, ethyl acrylate was changed to butyl acrylate and synthesized to obtain 24.3 g of colorless and transparent oil (26.2 g: yield 85). %). In nuclear magnetic resonance spectroscopy confirmed the structure ⁽¹ H-NMR spectroscopy) is the desired product. The measurement data are as follows. ¹ H NMR (400 MHz, 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)

Step 2: Synthesis of butyl 2- (heptanoyloxymethyl) acrylate. The 2-hydroxymethacrylic acid in the second step was changed to butyl 2-((heptanoyloxy) meth) acrylate obtained by the above method. The ester was synthesized by the same operation, and 34.2 g (126.7: yield 82.8%) of a colorless and transparent oily liquid was obtained. In nuclear magnetic resonance spectroscopy confirmed the structure ⁽¹ H-NMR spectrum) of the desired product. The measurement data are as follows. ¹ H NMR (400 MHz, 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 Itaconic Acid [Chemical 28] In a 4-neck flask equipped with a Dean Stark tube, 23.8 g (182.9 mmol) of itaconic acid and 35.5 g (347.5 mmol) of 1-hexanol were measured. 500 ml of cyclohexane and 0.9 concentrated sulfuric acid were added. g (9.1 mmol), 0.04 g (1.82 mmol) of dibutyl hydroxytoluene (BHT), a nitrogen atmosphere was used, and a dehydration condensation reaction was performed at 110 ° C for 24 hours. After the reaction was completed, 100 ml of n-hexane was added to the reaction solution, washed three times with 100 g of a 10% sodium carbonate aqueous solution, washed three times with 100 ml of pure water, and dried over anhydrous magnesium sulfate. After filtration, concentration and vacuum drying, 48.6 g (162.8 mmol: yield 89%) of a colorless transparent oily liquid was obtained. Structure Nuclear magnetic resonance spectrum ⁽¹ H-NMR spectra) confirmed the desired product. The measurement data are as follows. ¹ H NMR (400 MHz, 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 the liquid crystal cell) After preparing an empty cell in accordance with the above (production of the liquid crystal cell), the liquid crystal composition LC-1 to LC-4 (added to the MLC-3019 manufactured by Merck) are added in the empty cell. Those who have the optimum amount of the above polymerizable compound) are vacuum-injected at a vacuum of about 300 Pa at room temperature, and vacuum-injected after degassing at a vacuum of about 1 Pa for 1 hour. Liquid crystal cell. The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was heat-treated at 120 ° C for 10 minutes. Thereafter, the test was performed in the same manner as described above.

In addition, the liquid crystal compositions LC-1 to LC-4 are based on MLC-3019 and the polymerizable compounds described in the following table are added in the following introduction amounts. 【table 5】

<Evaluation result of alignment> [Table 6] ※ The free radical generating film is used without friction

The liquid crystals (LC-1, LC-2) introduced with IDBu and IDHex and the liquid crystals introduced with C2C6, C4C6 can exhibit very good alignment even when the vacuum is relatively high.

<Evaluation results of electro-optical characteristics> Then, the driving threshold voltage, the voltage at the maximum brightness, and the response speed of those who have not rubbed the radical-generating film in the unit cell of the aforementioned zero-anchored liquid crystal are summarized as follows. [Table 7] ※ Using a unit cell with a vacuum of 300 Pa during liquid crystal injection

Regardless of the presence or absence of friction treatment when using a polymerizable compound, the drive voltage was confirmed to decrease, and it was observed that the response speed tended to be improved by the friction treatment. Therefore, it can be known that the effect of increasing the response speed by zero anchoring and friction of the polymerizable compound under high vacuum can be obtained. [Industrial availability]

According to the present invention, it is possible to industrially produce a zero-face anchoring film from inexpensive raw materials with good efficiency. In addition, the liquid crystal display element obtained by the method of the present invention is useful as a liquid crystal display element of a vertical alignment system such as a PSA type liquid crystal display and an SC-PVA type liquid crystal display.

no

Claims (22)

A method for manufacturing a zero-plane anchoring film includes the following steps: in a state where a liquid crystal composition containing a liquid crystal and a radical polymerizable compound is brought into contact with a radical generating film, a sufficient amount is given to cause the radical polymerizable compound to undergo a polymerization reaction; energy. For example, the method for manufacturing a zero-plane anchoring film according to item 1 of the scope of patent application, wherein the first substrate has a radical-generating film that is a radical-generating film subjected to uniaxial alignment treatment. For example, the manufacturing method of the zero-plane anchoring film according to item 1 or 2 of the patent application scope, wherein the step of applying energy is performed without an electric field. For example, the method for manufacturing a zero-plane anchoring film according to any one of claims 1 to 3, wherein the radical generating film is a film formed by immobilizing an organic group that induces radical polymerization. For example, the method for manufacturing a zero-face anchoring film according to any one of the claims 1 to 3, wherein the radical generating film is coated by applying a composition having a radical-generating compound and a polymer. Cloth is obtained by curing and forming a film. For example, the method for manufacturing a zero-face anchored film according to any one of claims 1 to 3, wherein the radical generating film is composed of a polymer containing an organic group that induces radical polymerization. For example, the method for manufacturing a zero-face anchoring film according to item 6 of the application, wherein the polymer containing an organic group that induces radical polymerization is a diamine component containing a diamine containing an organic group that induces radical polymerization. The obtained polymer is at least one polymer selected from the group consisting of a polyimide precursor, polyimide, polyurea, and polyimide. For example, a method for manufacturing a zero-plane anchoring film according to any of claims 4, 6, and 7, in which the organic group that induces radical polymerization is the following structure [X-1] ~ [X-18], Organic groups represented by [W], [Y], [Z]; [化 29] In the formulae [X-1] to [X-18], * represents a bonding site with a portion other than the polymerizable reactive group of the compound molecule, and S ¹ and S ² each independently represent -O-, -NR-,- S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, and a carbon number 1 to 4 Alkyl; 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 an organic group and / or a halogen atom as a substituent. An aromatic hydrocarbon group in the group consisting of phenylene, naphthyl, and phenylene, R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms When R ⁹ and R ¹⁰ are alkyl groups, they may be bonded to each other at the ends to form a ring structure; Q represents the following structure; [化 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 compound other than Q in a compound molecule. Bonding site; R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. For example, a method for manufacturing a zero-face anchoring film according to item 7 of the application, wherein the diamine containing an organic group that induces radical polymerization has a structure represented by the following general formula (6) or the following general formula (7) Diamine In formula (6), R ⁶ represents a single bond, -CH _2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N ( CH ₃ )-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-, R ⁷ represents a single bond, or an unsubstituted or fluorine-substituted alkylene group having 1 to 20 carbon atoms. Any one or more of -CH ₂ -or -CF ₂ -of the alkyl group may be independently replaced with a group selected from the group consisting of -CH = CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and Alternatively, any one of the following lists may be substituted, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other and are replaced with these groups. R ⁸ represents a radical polymerization reactive group selected from the following formula; In the formulae [X-1] to [X-18], * represents a bonding site with a portion other than the radical polymerization reactive group of the compound molecule, and S ¹ and S ² each independently represent -O-, -NR- , -S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, and a carbon number 1 ~ 4 alkyl group; 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 unsubstituted or fluorine-substituted alkylene having 1 to 20 carbon atoms Group, any one or more of -CH ₂ -or -CF ₂ -of the alkylene group may be independently replaced by a member selected from the group consisting of -CH = CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring In addition, any of the following groups may be used, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other. Substituted by these groups, J is an organic group represented by the following formula, [化 35] In the formulas [W], [Y], and [Z], * represents a bonding site with T ² , and Ar represents an organic group and / or a halogen atom as a substituent selected from the group consisting of phenylene, naphthyl, And an aromatic hydrocarbon group in the group consisting of biphenyl, and R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q represents the following structure; 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 compound other than Q in a compound molecule. Bonding site; R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. For example, the method for manufacturing a zero-plane anchoring film according to any one of claims 1 to 9, wherein at least one of the radical polymerizable compounds is compatible with liquid crystal and has one in one molecule. Polymerizable reactive compounds. For example, a method for manufacturing a zero-face anchoring film according to item 10 of the application, wherein the polymerizable reactive group of the radical polymerizable compound is selected from the following structure, [Chem 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 linear alkyl group having 2 to 8 carbon atoms, and E represents a single bond selected from -O-, -NR ^c- , -S-, a bonding group in an ester bond and an amidine bond; R ^c represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. For example, the method for producing a zero-plane anchoring film according to any one of claims 1 to 11, wherein the liquid crystal composition containing a liquid crystal and a radically polymerizable compound is prepared by using the liquid crystal composition containing the radically polymerizable compound. A liquid crystal composition of a radically polymerizable compound having a Tg of a polymer obtained by polymerization of 100 ° C or lower. A method for manufacturing a liquid crystal cell, using the method for manufacturing a zero-plane anchoring film according to any one of claims 1 to 12, including the following steps: preparing a first substrate with a free radical generating film and optionally The second substrate of the radical generating film; the unit cell is formed so that the radical generating film on the first substrate faces the second substrate; and the liquid crystal and the radical polymerizable compound are filled between the first substrate and the second substrate. Of liquid crystal composition. For example, the method for manufacturing a liquid crystal cell according to item 13 of the application, wherein the second substrate is a second substrate without a radical generating film. For example, the method for manufacturing a liquid crystal cell according to item 14 of the application, wherein the second substrate is coated with a liquid crystal alignment film having uniaxial alignment. For example, the method for manufacturing a liquid crystal cell of the scope of application for patent No. 15, wherein the liquid crystal alignment film with uniaxial alignment is a liquid crystal alignment film for horizontal alignment. For example, the method for manufacturing a liquid crystal cell according to any one of claims 13 to 16, wherein the first substrate having a radical generating film is a substrate having a comb-shaped electrode. A liquid crystal composition containing a liquid crystal and a radical polymerizable compound. At least one of the radical polymerizable compounds is a compound having a polymerizable reactive group in one molecule, which is compatible with the liquid crystal. Polymerizable reaction The base is selected from the following structures; In the formula, * represents a bonding site with a portion other than the polymerizable reactive group of the compound molecule; R ^b represents a linear alkyl group having 2 to 8 carbon atoms, and E represents a single bond selected from -O-, -NR ^c- , -S-, a bonding group in an ester bond and an amidine bond; R ^c represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. A method for manufacturing a liquid crystal display element using a film made of a zero-plane anchored state obtained by a method such as any one of claims 1 to 17 of the scope of patent application. A liquid crystal display element is obtained by using a method for manufacturing a liquid crystal display element such as the item 19 of the scope of patent application. For example, in the liquid crystal display element of the scope of application for a patent, the first substrate or the second substrate has an electrode. For example, the liquid crystal display element with the scope of patent application No. 20 or 21 is a liquid crystal display element driven by a low voltage transverse electric field.