TWI782997B - Method for producing liquid display cell, and liquid 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 liquid crystal unit cell and liquid crystal display element

The present invention relates to a method of manufacturing a zero-surface anchoring film using a polymer stabilization technology that can be manufactured inexpensively and without complicated steps, and a liquid crystal display element driven by a lower voltage using the manufacturing method and its Production method.

In recent years, liquid crystal display elements have been widely used in monitors of mobile phones, computers, and televisions. Liquid crystal display elements have the characteristics of thinness, lightness, and low power consumption. In the future, they are expected to be used in 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. Both modes use a film (liquid crystal alignment film) that induces liquid crystals into a desired alignment state.

Especially products with touch panels such as tablet PCs, smart phones, and smart TVs prefer to use even touch screens. The IPS mode, which is not easy to disturb the display when touched, has gradually begun to use FFS (Fringe Field Switching, Frindge Field Switching) liquid crystal display elements, and optical alignment. Technology of contact technology.

However, compared with IPS, FFS has a larger manufacturing cost of the substrate, and a problem of display defects unique to the FFS mode called Vcom shift occurs. Also, with regard to photo-alignment, compared with the rubbing method, there are advantages that the size of the device that can be manufactured is increased and the display characteristics are greatly improved, but there is a problem in the principle of photo-alignment (if it is a decomposed type, there will be decomposition products. If it is heterosexual type, there will be branding caused by insufficient alignment, etc.). In order to solve these problems, manufacturers of liquid crystal display elements and liquid crystal alignment films have made various efforts.

On the other hand, in recent years, someone has proposed the IPS mode using zero-plane anchoring. By using this method, it is reported that compared with the conventional IPS mode, the contrast ratio can be improved and the voltage can be greatly reduced (see Patent Document 1). .

Specifically, a liquid crystal alignment film with strong anchoring energy is used on one side of the substrate, and the substrate side with electrodes that generate a transverse electric field is treated to completely eliminate the alignment constraint of the liquid crystal to produce an IPS mode liquid crystal. Method for displaying components.

In recent years, some people have used thick polymer brushes to create a zero-surface state, and proposed a technical proposal for zero-surface anchoring IPS mode (Reference 2). Through this technology, the contrast ratio is greatly improved and the driving voltage is greatly reduced.

[Prior Art Literature]

[Patent Document]

[Patent Document 1] Japanese Patent No. 4053530

[Patent Document 2] Japanese Unexamined Patent Publication No. 2013-231757

On the other hand, this technology has problems that will occur in principle. First, for example, in order to stably generate polymer brushes on the substrate, it needs to be carried out under very delicate conditions, and it is not practical for mass production. The second point is that, for example, the alignment film is responsible for important functions such as suppressing burn-in, but when using a polymer brush or the like, it is not easy to control the necessary electrical and physical properties. The third point, for example, as far as the driving principle is concerned, the response speed when the voltage is off will become very slow. When the alignment constraint force is zero, the resistance applied to the liquid crystal during driving is eliminated, and the brightness can be expected to increase due to a large drop in the threshold voltage and a reduction in the poor alignment area during driving. However, for the recovery of the liquid crystal, due to the The power depends on the elastic force of the liquid crystal, and it is considered that the speed will be greatly reduced compared with the case with an alignment film.

If such a technical problem can be solved, it is considered to be advantageous in terms of cost, battery consumption reduction, image quality improvement, etc. for panel manufacturers.

The present invention aims to solve the above-mentioned problems, and aims to provide a production method using a polymer stabilization technology capable of producing a zero-surface anchor film, and to simultaneously achieve non-contact alignment and low drive at room temperature in a simple and inexpensive method. Transverse electric field liquid crystal display element with voltageization and faster response speed when off and methods of manufacture thereof.

As a result, the inventors of the present invention have diligently studied to solve the above-mentioned problems, found that the above-mentioned problems can be solved, and completed the present invention having the following gist.

That is, the present invention includes the following.

[1] A method for producing a zero-surface anchoring film, comprising the step of: 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, and given to polymerize the radical polymerizable compound sufficient energy for the reaction.

[2] The method for producing a zero-surface anchoring film according to [1], wherein the radical generating film on the first substrate is a radical generating film subjected to uniaxial alignment treatment.

[3] The manufacturing method of the zero-surface 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-surface anchoring film according to any one of [1] to [3], wherein the radical generating film is a film formed by immobilizing an organic radical that induces radical polymerization.

[5] The method for producing a zero-surface anchoring film according to any one of [1] to [3], wherein the free radical generating film is composed of a compound having a free radical-generating radical and a polymer. It is obtained by applying, curing, forming a film, and being fixed in the film.

[6] The method for producing a zero-surface 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-surface anchoring film according to [6], wherein the organic radical that induces free radical polymerization The polymer is obtained by using a diamine component containing a diamine containing an organic group that induces free radical polymerization, and is obtained by at least one polymerization selected from polyimide precursors, polyimides, polyureas, and polyamides. thing.

[8] The method for producing a zero-surface anchoring film according to any one of [4], [6], and [7], wherein the organic group that induces free radical polymerization has the following structures [X-1]~[X Organic groups represented by -18], [W], [Y], [Z];

In the formulas [X-1]~[X-18], * represents the bonding site with a part 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 with 1 to 10 carbons, and an alkoxy group with 1 to 10 carbons, R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or an alkyl group with 1 to 4 carbons the alkyl group;

In the formulas [W], [Y], [Z], * represents a bonding site with a part other than the polymerizable reactive group of the compound molecule, and Ar represents a free group that may have an organic group and/or a halogen atom as a substituent. An aromatic hydrocarbon group in the group consisting of phenylene, naphthylene, and biphenylene, R ⁹ and R ¹⁰ each independently represent an alkyl group with 1 to 10 carbons or an alkoxy group with 1 to 10 carbons , when R ⁹ and R ¹⁰ are alkyl groups, they can also 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 with 1 to 4 carbon atoms, and * represents the difference between the compound molecule and the part other than Q. Bonding site; ^R12 represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbons, or an alkoxy group with 1 to 10 carbons.

[9] The method for producing a zero-surface anchoring film according to [7], wherein the diamine containing an organic group that induces free 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 atom-substituted C1-20 alkylene group, the alkene group Any one or more of -CH ₂ - or -CF ₂ - in the alkyl group can also be independently replaced by a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and then Alternatively, any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- may be replaced by these groups on the condition that they are not adjacent to each other ; R ⁸ represents a free radical polymerization reactive group selected from the following formula; [Chemical 5]

In the formulas [X-1]~[X-18], * represents the bonding site with the part 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 with 1 to 10 carbons, and an alkoxy group with 1 to 10 carbons, R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a carbon number 1 ~4 alkyl groups;

In ^formula ( ⁷ ), T1 and T2 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 alkane with carbon numbers of 1 to 20 One or more of any -CH ₂ - or -CF ₂ - of the alkylene group can also be independently replaced by one selected from the group consisting of -CH=CH-, divalent carbocycle, and divalent heterocycle 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 on the condition that Replaced by such groups, J is an organic group represented by the following formula, [Chemical 7]

^In the formulas [W], [Y], [Z], * represents the bonding position with T2, and Ar represents the group selected from phenylene, naphthyl, and and the aromatic hydrocarbon group in the group consisting of biphenyl, ^R9 and R10 each independently represent an alkyl group with 1 to ¹⁰ carbons or an alkoxy group with 1 to 10 carbons, and 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 with 1 to 4 carbon atoms, and * represents the difference between the compound molecule and the part other than Q. Bonding site; ^R12 represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbons, or an alkoxy group with 1 to 10 carbons.

[10] The method for producing a zero-surface anchoring film according to any one of [1] to [9], wherein at least one of the radically polymerizable compounds is compatible with liquid crystals in one molecule. A compound having one polymerizable reactive group.

[11] The method for producing a zero-surface anchoring film according to [10], wherein the polymerizable reactive group of the radically polymerizable compound is selected from the following structures, [Chemical 9]

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

[12] The method for producing a zero-surface anchoring film according to any one of [1] to [11], wherein in the liquid crystal composition containing liquid crystal and a radical polymerizable compound, a compound containing the radical polymerizable A liquid crystal composition of a radically polymerizable compound whose Tg of the polymer obtained by polymerizing the compound is 100° C. or lower.

[13] A method of manufacturing a liquid crystal cell, using the method of manufacturing a zero-surface anchoring film according to any one of [1] to [12], comprising the following steps: preparing a first substrate with a free radical generating film and also There may be a second substrate with a free radical generating film; making a unit cell with the free radical generating film on the first substrate facing the second substrate; and filling the space between the first substrate and the second substrate containing liquid crystal and free radical polymerization Liquid crystal composition of sexual compounds.

[14] The method for producing a liquid crystal cell according to [13], wherein the second substrate is a second substrate without a radical generating film.

[15] The method for producing 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 Liquid crystal alignment film for horizontal alignment.

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

[18] A liquid crystal composition comprising a liquid crystal and a radically polymerizable compound, wherein at least one of the radically polymerizable compounds is a compound having one polymerizable reactive group in a molecule compatible with the liquid crystal, The polymerizable reactive group is selected from the following structures;

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

[19] A method of manufacturing a liquid crystal display element using a film having a zero-surface anchored state obtained by the method of any one of [1] to [17].

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

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

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

According to the present invention, a zero-surface anchor film can be produced industrially with good yield. Using the method of the present invention, a liquid crystal display element similar to the zero-surface anchored IPS mode liquid crystal display element described in Patent Documents 1 and 2 can be easily manufactured with cheap raw materials and existing manufacturing methods. Moreover, the liquid crystal display element obtained by the manufacturing method of the present invention can provide such excellent advantages as compared with the prior art, that the response speed of the liquid crystal is faster when it is off, and it is low driving voltage, has no bright spots, and Vcom offset is not easy to occur. Characteristic liquid crystal display elements.

The present invention is a method for producing a zero-surface anchoring film, which is characterized in that the free 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 is a method for manufacturing a zero-surface anchoring film, which includes the following steps: preparing a substrate containing liquid crystal and free radicals between a first substrate with a free radical generating film and a second substrate that may also have a free radical generating film. a unit cell of a liquid crystal composition of a radically polymerizable compound; and giving sufficient energy to the unit cell to cause the polymerization reaction of the radically polymerizable compound to proceed. Preferably, it is a method for manufacturing a liquid crystal cell, comprising the following steps: preparing a first substrate with a free radical generating film and a second substrate without a free radical generating film; making the crystal in such a way that the free radical generating film faces the second substrate and, filling the liquid crystal composition containing liquid crystal and radical polymerizable compound between the first substrate and the second substrate. For example, a low-voltage driving IPS liquid crystal display element manufacturing method, the second substrate does not have a free radical generating film, and is a substrate with a liquid crystal alignment film that has been uniaxially aligned, and the first substrate is a substrate with comb electrodes.

In the present invention, "zero-surface 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, it is weaker than the intermolecular force between liquid crystals, and this film alone cannot make the liquid crystal molecules toward appoint A film with uniaxial alignment in one direction. Also, the zero-surface anchoring film is not limited to a solid film, but also includes a liquid film covering a solid surface. Usually, in a liquid crystal display element, a liquid crystal alignment film, which is a film that constrains the alignment of liquid crystal molecules, is used in pairs to align the liquid crystals, but the paired use of the zero-plane anchoring film and the liquid crystal alignment film can also align the liquid crystals. . The reason is that the alignment constraint force of the liquid crystal alignment film is also transmitted to the thickness direction of the liquid crystal layer through the intermolecular force between the liquid crystal molecules, and as a result, the liquid crystal molecules close to the zero-plane anchoring film are also aligned. Therefore, when the liquid crystal alignment film is used for horizontal alignment, the entire liquid crystal cell can be in a horizontal alignment state. Horizontal alignment refers to the state in which the long axes of liquid crystal molecules are roughly aligned parallel to the surface of the liquid crystal alignment film. Even if there is a tilt alignment of about several degrees, it is also included in the category of horizontal alignment.

[Free radical generating film-forming composition]

The radical-generating membrane-forming composition for forming the radical-generating membrane used in the present invention contains a polymer and radical-generating radicals as components. In this case, the composition may contain a polymer to which a radical-generating radical is bonded, or may be a composition having a compound having a radical-generating radical and a polymer serving as a base resin. By applying such a composition and forming a film by curing, a radical generating film capable of generating radicals based on immobilization in the film can be obtained. The radical capable of generating free radicals is preferably an organic radical that induces free radical polymerization.

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

【chemical 11】

In the formulas [X-1]~[X-18], * represents the bonding site with a part 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 with 1 to 10 carbons, and an alkoxy group with 1 to 10 carbons, R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or an alkyl group with 1 to 4 carbons the alkyl group;

In the formulas [W], [Y], [Z], * represents a bonding site with a part other than the polymerizable reactive group of the compound molecule, and Ar represents a group that may have an organic group and/or a halogen atom as a substituent. An aromatic hydrocarbon group in the group consisting of phenylene, naphthylene, and biphenylene, R ⁹ and R ¹⁰ each independently represent an alkyl group with 1 to 10 carbons or an alkoxy group with 1 to 10 carbons , when R ⁹ and R ¹⁰ are alkyl groups, the terminals may be bonded to each other to form a ring structure. Q represents the following structures.

In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-, R represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and * represents any part of the compound molecule other than Q. bonding site.

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

Polymers, for example, at least one polymer selected from the group consisting of polyimide precursors, polyimides, polyureas, polyamides, polyacrylates, polymethacrylates, etc. is preferred .

In order to obtain the free radical generating film used in the present invention, when using the aforementioned polymer having an organic group that induces free radical polymerization, in order to obtain a polymer having a radical capable of generating free radicals, in terms of monomer components, it is preferable to use a compound containing Monomers with photoreactive side chains selected from at least one of methacrylic, acrylic, vinyl, allyl, coumarin, styryl, and cinnamonyl, and the side chains can be decomposed by ultraviolet radiation It is better to manufacture monomers that generate free radicals. On the other hand, considering the problem that the free radical-generating monomer itself will spontaneously polymerize, etc., it will become an unstable compound. Therefore, in view of the ease of synthesis, it is preferable to use a polymer derived from a diamine having a free radical generating site. Ideally, polyimide precursors such as polyamide acid and polyamide ester, polyimide, polyurea, polyamide, and the like are more preferable.

Such a diamine containing a free radical generating site is specifically, for example, a diamine having a side chain capable of generating free radicals and polymerizing, such as a diamine represented by the following general formula (6), but not limited thereto.

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 atom-substituted C1-20 alkylene group, the alkene group Any one or more of -CH ₂ - or -CF ₂ - in the alkyl group may also be independently substituted with a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, Furthermore, any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- can also be provided on the condition that these groups are not adjacent to each other. to replace; R ⁸ represents a free radical polymerization reactive group selected from the following formula:

In the formulas [X-1]~[X-18], * represents the bonding site with the part 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 with 1 to 10 carbons, and an alkoxy group with 1 to 10 carbons, R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a carbon number 1 ~4 alkyl groups.

In formula (6), the bonding positions of the two amine groups (—NH ₂ ) are not limited. Specifically, the bonding groups relative to the side chains are 2,3 positions, 2,4 positions, 2,5 positions, 2,6 positions, 3,4 positions, 3 , the position of 5. Among them, the 2,4 position, the 2,5 position, or the 3,5 position are preferable from the viewpoint of reactivity when synthesizing polyamic acid. Considering the ease of synthesizing diamines, the 2,4 positions or the 3,5 positions are more ideal.

As a diamine having a photoreactive group containing at least one photoreactive group 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, Specifically, the following compounds are listed, but not limited thereto.

In the formula, J1 represents ^a bonding group selected from a single bond, -O-, -COO-, -NHCO-, or -NH-, J2 represents a single bond, or a carbon number ¹ that is unsubstituted or substituted by a fluorine atom ~20 alkylene groups.

As the diamine having a side chain that is decomposed by ultraviolet irradiation to generate radicals, diamines represented by the following general formula (7) may be mentioned, but not limited thereto.

In ^formula ( ⁷ ), T1 and T2 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 alkane with 1 to 20 carbons that is unsubstituted or substituted by a fluorine atom Any one or more of -CH ₂ - or -CF ₂ - in the alkylene group can also be independently substituted with one selected from -CH=CH-, divalent carbocycle, and divalent heterocycle Moreover, any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH-, can also be provided on the condition that they are not adjacent to each other. Substituted by a group, J is an organic group represented by the following formula,

^In the formulas [W], [Y], [Z], * represents the bonding position with T2, and Ar represents the group selected from phenylene, naphthyl, and and the aromatic hydrocarbon group in the group consisting of extended biphenyl, R ⁹ and R ¹⁰ each independently represent an alkyl group with 1 to 10 carbons or an alkoxy group with 1 to 10 carbons, and 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 with 1 to 4 carbon atoms, and * represents the difference between the compound molecule and the part other than Q. bonding site.

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

The bonding positions of the two amine groups (—NH ₂ ) in the above formula (7) are not limited. Specifically, the bonding groups relative to the side chains are 2,3 positions, 2,4 positions, 2,5 positions, 2,6 positions, 3,4 positions, 3 , the position of 5. Among them, the 2,4 position, the 2,5 position, or the 3,5 position are preferable from the viewpoint of reactivity when synthesizing polyamic acid. If the ease of synthesizing diamine is also taken into consideration, the positions of 2,4 or 3,5 are more preferable.

In particular, the structure represented by the following formula is ideal, but not limited thereto, from the viewpoints of easiness of synthesis, high degree of versatility, and characteristics.

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

The above-mentioned diamines can be used alone or in combination of two or more according to properties such as liquid crystal alignment when forming a radical generating film, sensitivity during polymerization, voltage retention characteristics, and charge accumulation.

Such a diamine having a site for free radical polymerization is preferably used as a free radical-generating film-forming component. The amount of the diamine component used for the synthesis of the polymer contained in the finished product is preferably 5-50 mol%, more preferably 10-40 mol%, and most preferably 15-30 mol%.

Also, when the polymer used in the radical generating membrane of the present invention is obtained from a diamine, diamines other than the above-mentioned diamine having a site for generating radicals can be used as the diamine as long as the effects of the present invention are not hindered. Ingredients come and go. 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-diaminotoluene 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'-trifluoromethane Base-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'-diaminodiphenyl ether, 4,4'-sulfonyl diphenylamine, 3,3'-sulfonyl Diphenylamine, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-amine phenyl)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'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine phenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3, 4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminobenzophenone Naphthalene, 1,6-diamino Naphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8 -Diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl) ) propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis (3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis (4-aminophenoxy)benzene, 4,4'-[1,4-phenylene bis(methylene)]diphenylamine, 4,4'-[1,3-phenylene bis(methylene) Methyl)]diphenylamine, 3,4'-[1,4-phenylene bis(methylene)]diphenylamine, 3,4'-[1,3-phenylene bis(methylene)] Diphenylamine, 3,3'-[1,4-Phenylbis(methylene)]diphenylamine, 3,3'-[1,3-Phenylbis(methylene)]diphenylamine, 1 ,4-Phenylbis[(4-aminophenyl)methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1,3-phenylenebis[ (4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylene bis(4-aminobenzoate ), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene bis(3-aminobenzoate) -aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl) Isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N ,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide) , N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N, N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)isophthalamide, N,N'-bis(3-amine phenyl) m-phthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenyl anthracene, 2,2' -Bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis (4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane Fluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane alkanes, 2,2'-bis(3-amino-4-methylphenyl)propane, transformer-1,4-bis(4-aminophenyl)cyclohexane, 3,5-diaminobenzene Formic acid, 2,5-diaminobenzoic acid, Bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis (3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis (4-aminophenoxy)pentane, 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)decane Aromatic diamines such as dioxane, 1,12-bis(3-aminophenoxy)dodecane; bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl) ) methane and other alicyclic diamines; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1, 7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1 ,12-diaminododecane and other aliphatic diamines; 1,3-bis[2-(p-aminophenyl)ethyl]urea, 1,3-bis[2-(p-aminophenyl) Ethyl]-1-tertiary butoxycarbonyl urea and other diamines with urea structure; N-p-aminophenyl-4-p-aminophenyl (tertiary butoxycarbonyl)aminomethylpiperidine Diamines with nitrogen-containing unsaturated heterocyclic structures; N-tertiary butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine and other diamines with N-Boc groups, etc.

The above-mentioned other diamines can be used alone or in combination of two or more according to properties such as liquid crystal alignment when forming a radical generating film, sensitivity during polymerization, voltage retention characteristics, and charge accumulation.

In the synthesis when the polymer is polyamic acid, the tetracarboxylic dianhydride reacted with the diamine component is not particularly limited. Specifically, pyromellitic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 2,3,6,7-Anthracene tetracarboxylic acid, 1,2,5,6-Anthracene tetracarboxylic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3',4 '- Biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl) ether, 3,3',4,4'-benzophenone tetracarboxylic acid, bis(3,4-dicarboxyphenyl)pyridine, 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'-diphenylpyridine tetracarboxylic acid, 3,4,9,10-perylene Tetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid, oxydiphthalyl tetracarboxylic acid, 1,2,3,4-cyclobutane tetracarboxylic acid , 1,2,3,4-cyclopentane tetracarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4 -Cyclobutane tetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic acid, 1,2,3,4-cycloheptane tetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid, 2,3, 5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo[3,3,0]octane-2,4,6, 8-tetracarboxylic acid, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]decane-2,4,7,9-tetracarboxylic Acid, bicyclo[4,4,0]decane-2,4,8,10-tetracarboxylic acid, tricyclo[6.3.0.0<2,6>]undecane-3,5,9,11-tetra Carboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2 -Dicarboxylic acid, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5-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-tricarboxynorbornane-2:3,5:6 dicarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid and other tetracarboxylic dianhydrides.

Of course, tetracarboxylic dianhydrides can also be used alone or in combination according to properties such as liquid crystal alignment when forming a radical generating film, sensitivity during polymerization, voltage retention characteristics, and charge accumulation.

In the synthesis when the polymer is polyamide ester, the structure of the dialkyl tetracarboxylate reacted with the diamine component is not particularly limited, and specific examples thereof are given below.

Specific examples of aliphatic tetracarboxylic acid diesters include dialkyl 1,2,3,4-cyclobutane tetracarboxylate, 1,2- Dimethyl-1,2,3,4-cyclobutane tetracarboxylate dialkyl, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylate dialkyl, 1, 2,3,4-Tetramethyl-1,2,3,4-cyclobutane tetracarboxylate dialkyl, 1,2,3,4-cyclopentane tetracarboxylate dialkyl, 2,3, Dialkyl 4,5-tetrahydrofuran tetracarboxylate, Dialkyl 1,2,4,5-cyclohexane tetracarboxylate, Dialkyl 3,4-dicarboxy-1-cyclohexyl succinate, 3,4 -Dicarboxy-1,2,3,4-tetrahydro-1-naphthalene dialkyl succinate, 1,2,3,4-butane tetracarboxylic acid dialkyl ester, bicyclo[3,3,0]octane Dialkyl-2,4,6,8-tetracarboxylate, dialkyl 3,3',4,4'-dicyclohexyltetracarboxylate, dialkyl 2,3,5-tricarboxycyclopentyl acetic acid Alkyl esters, Dialkyl cis-3,7-dibutylcyclooct-1,5-diene-1,2,5,6-tetracarboxylate, Tricyclo[4.2.1.0<2,5>] Nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dialkyl ester, hexacyclo[6.6.0.1<2,7>.0<3,6>.1<9, 14>.0<10,13>]hexadecane-4,5,11,12-tetracarboxylic acid-4,5: 11,12-dialkyl ester, 4-(2,5-dioxo-tetrahydrofuran -3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dialkyl ester, etc.

Dialkyl aromatic tetracarboxylates include dialkyl pyromellitate, dialkyl 3,3',4,4'-biphenyl tetracarboxylate, 2,2',3,3'-biphenyl tetracarboxylate Dialkyl carboxylate, 2,3,3',4-diphenyl tetracarboxylate, 3,3',4,4'-benzophenone tetracarboxylate, 2,3,3' ,4'-Benzophenone tetracarboxylic acid dialkyl ester, bis(3,4-dicarboxyphenyl) ether dialkyl ester, bis(3,4-dicarboxyphenyl) dialkyl ester, 1,2, Dialkyl 5,6-naphthalene tetracarboxylate, dialkyl 2,3,6,7-naphthalene tetracarboxylate, etc.

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

【Chemical 21】

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

The aliphatic diisocyanate shown in K-1~K-5 has poor reactivity but has the advantage of better solvent solubility, and the aromatic diisocyanate shown in K-6~K-7 is highly reactive and has heat resistance It has the effect of improving the performance, but has the disadvantage of low solvent solubility. In terms of versatility and characteristics, K-1, K-7, K-8, K-9, and K-10 are the best. Considering electrical characteristics, K-12 is more ideal. From the perspective of liquid crystal alignment, K -13 is preferred. One or more diisocyanates can be used in combination, and it is better to use them according to the characteristics to be obtained.

Also, a part of the diisocyanate can be replaced by the above-mentioned tetracarboxylic dianhydride, which can be used in the form of a copolymer of polyamic acid and polyurea, and can also be converted into polyimide and polyurea by chemical imidization. Copolymers of polyurea are used in this form.

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

Alicyclic dicarboxylic acids include 1,1-cyclopropane dicarboxylic acid, 1,2-cyclopropane dicarboxylic acid, 1,1-cyclobutane dicarboxylic acid, 1,2-cyclobutane dicarboxylic 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-cyclopentane dicarboxylic acid, 1,2-cyclopentane dicarboxylic acid , 1,3-cyclopentane dicarboxylic acid, 1,1-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid Hexanedicarboxylic acid, 1,4-(2-norcamphene)dicarboxylic acid, norcamphene-2,3-dicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, Bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-dioxo-1,4-bicyclo[2.2.2]octanedicarboxylic acid, 1,3-adamantanedicarboxylate acid, 4,8-dioxo-1,3-adamantanedicarboxylic acid, 2,6-spiro[3.3]heptanedicarboxylic acid, 1,3-adamantanediacetic acid, camphoric acid, etc.

Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, and 5-aminoisophthalic acid. , 5-hydroxyisophthalic acid, 2,5-dimethyl terephthalic acid, tetramethyl terephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6 -naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-anthracene dicarboxylic acid, 1,4-anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4'-biphenyl Benzene dicarboxylic acid, 1,5-extended biphenyl dicarboxylic acid, 4,4"-terphenyl dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl Ethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4' -bibenzyl dicarboxylic acid, 4,4' - stilbene dicarboxylic acid, 4,4'-ethynyl dibenzoic acid, 4,4'-carbonyl dibenzoic acid, 4,4'- Sulfonyl dibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylenediacetic acid, 3,3'-p-phenylenedipropionic acid, 4-carboxycinnamic acid, p-phenylenediacrylate , 3,3'-[4,4'-(methylene bis-p-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxygenylylene)]di Propionic acid, 4,4'-[4,4'-(oxybis-p-phenylene)]dibutyric acid, (isopropylidene bis-p-phenylenedioxy)dibutyric acid, bis(p-carboxy Dicarboxylic acids such as phenyl)dimethylsilane.

二唑-3,4-二羧酸、2,3-吡啶二羧酸、2,4-吡啶二羧酸、2,5-吡啶二羧酸、2,6-吡啶二羧酸、3,4-吡啶二羧酸、3,5-吡啶二羧酸等。 Examples of dicarboxylic acids containing heterocyclic rings include 1,5-(9-oxofluorene)dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4, 5-thiazoledicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-

Oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4 - dipicolinic acid, 3,5-pyridinedicarboxylic acid, etc.

The various dicarboxylic acids mentioned above can also be acyl dihalides or anhydride structures. If these dicarboxylic acids are dicarboxylic acids capable of imparting a linear structure to polyamide, they are ideal for 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 ) propane dicarboxylic acid, 4,4-terphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,5-pyridine dicarboxylic acid, or their acyl dihalides are preferred. These compounds may have isomers, and mixtures thereof may be included. In addition, two or more compounds may be used in combination. In addition, the dicarboxylic acids used in the present invention are not limited to the above-mentioned exemplified compounds.

Diamine (also described as "diamine component") as a raw material, and tetracarboxylic dianhydride (also described as "tetracarboxylic dianhydride component"), tetracarboxylic acid diester, and diisocyanate selected from raw materials To obtain polyamic acid, polyamic acid ester, polyurea, and polyamide by reacting components in dicarboxylic acid, known synthesis methods can be used. Generally, there is a method of making a diamine component and one or more components selected from tetracarboxylic dianhydride components, tetracarboxylic diesters, diisocyanates, and dicarboxylic acids react in an organic solvent.

The reaction between the diamine component and the tetracarboxylic dianhydride component is relatively easy in an organic solvent and is advantageous from the viewpoint of not generating by-products.

The organic solvent used in the above reaction is not particularly limited as long as it can dissolve the formed polymer. Furthermore, even if it is an organic solvent that does not dissolve the polymer, it can be used in admixture with the above-mentioned solvent within the range where the produced polymer does not precipitate. In addition, the moisture in the organic solvent will hinder the polymerization reaction, and then cause the hydrolysis of the generated polymer, so the organic solvent should be dehydrated and dried.

烷、正己烷、正戊烷、正辛烷、二乙醚、環己酮、碳酸伸乙酯、丙烯碳酸酯、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸丙二醇單乙醚、丙酮 酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、二甘二甲醚、4-羥基-4-甲基-2-戊酮、2-乙基-1-己醇等。該等有機溶劑可單獨使用也可混用。 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-dimethylpropanamide, N - Methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfoxide, hexamethylsulfoxide, γ-butyrolactone, isopropanol, methoxymethylpentanol, Dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellothreon, ethyl cellothreonate, methyl cellothreoacetate, butyl Base cellothracetate, ethyl cellothracetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethyl carbitol Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tertiary butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, Diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetic acid Ester monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxy Butyl alcohol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, di

alkanes, 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 monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethyl Oxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2- Pentanone, 2-ethyl-1-hexanol, etc. These organic solvents may be used alone or in combination.

When reacting the diamine component and the tetracarboxylic dianhydride component in an organic solvent, the following method is exemplified: the solution obtained by dispersing or dissolving the diamine component in the organic solvent is stirred, and the tetracarboxylic dianhydride component, Or the method of adding after dispersing or dissolving it in an organic solvent, the method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride component in an organic solvent in reverse, mixing the tetracarboxylic dianhydride component and As for the method of adding the diamine component alternately, any of these methods can be used. In addition, when the diamine component or the tetracarboxylic dianhydride component is composed of a plurality of compounds, they can be reacted in a premixed state, or they can be individually reacted sequentially, and the individually reacted low-molecular-weight substances can also be mixed. React and make high molecular weight body.

The temperature when the diamine component reacts with the tetracarboxylic dianhydride component can be selected at any temperature, for example: -20~100°C, preferably in the range of -5~80°C. Moreover, reaction can be performed at arbitrary concentration, For example, the total amount of a diamine component and a tetracarboxylic dianhydride component is 1-50 mass % with respect to a reaction liquid, Preferably it is 5-30 mass %.

In the above polymerization reaction, the ratio of the total moles of the tetracarboxylic dianhydride components to the total moles of the diamine components can be selected in accordance with the molecular weight of the polyamic acid to be obtained. Like the usual polycondensation reaction, the closer the molar ratio is to 1.0, the greater the molecular weight of the polyamic 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 above-mentioned method. When synthesizing polyamic acid, it can be the same as the general polyamic acid synthesis method, replacing the above-mentioned tetracarboxylic dianhydride with the corresponding structure of four Tetracarboxylic acid derivatives such as carboxylic acid or tetracarboxylic acid dihalide are reacted by a known method to obtain the corresponding polyamic acid. Moreover, when synthesizing polyurea, what is necessary is just to make diamine and diisocyanate react. When producing polyamide esters or polyamides, diamines and components selected from tetracarboxylic acid diesters and dicarboxylic acids can be derivatized into acyl halides in the presence of known condensing agents or by known methods. , to react it with a diamine.

The method of imidating the above-mentioned polyamic acid to produce polyimide includes the following methods: heat imidization by directly heating a solution of polyamic acid; Catalyst imidization of media. Also, the imidization rate from polyamic acid to polyimide is preferably 30% or more, more preferably 30-99%, in consideration of the high voltage retention rate. On the other hand, 70% or less is preferable from the viewpoint of the whitening characteristic, that is, the polymer precipitation suppression varnish. Considering the characteristics of both parties, 40~80% is more ideal.

The temperature for thermal imidization of polyamic acid in the solution is usually 100~400°C, preferably 120~250°C. good.

Catalyzed imidization of polyamic acid can be implemented by adding alkaline catalyst and acid anhydride to the solution of polyamic acid, usually at -20~250°C, preferably at 0~180°C and stirring. The amount of alkaline catalyst is usually 0.5~30 mole times of amide acid group, preferably 2~20 mole times, and the amount of acid anhydride is usually 1~50 mole times of amide acid group, preferably 3~30 mole times. Basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, Trioctylamine and the like, among them, pyridine is preferable because it has a moderate basicity for the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, use of acetic anhydride is preferable because it facilitates purification after the reaction. The imidization rate obtained by catalytic imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

When recovering the produced polymer from the reaction solution of the polymer, the reaction solution can be poured into a poor solvent and allowed to precipitate. Examples of poor solvents used for precipitation formation include methanol, acetone, hexane, butylcellosulfate, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer that has been thrown into a poor solvent and precipitated can be dried under normal pressure or reduced pressure at room temperature or by heating after filtration and recovery. In addition, if the polymer recovered by precipitation is dissolved in an organic solvent and then re-precipitated and recovered, and this operation is repeated 2 to 10 times, the impurities in the polymer can be reduced. Poor solvents at this time are, for example, alcohols, ketones, hydrocarbons, etc. If more than three kinds of poor solvents selected from them are used, the refining efficiency will be better, so it is more ideal.

In addition, 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 also contain a polymer other than the polymer containing an organic group that induces radical polymerization. other polymers. In this case, the content of other polymers in the total polymer composition is preferably 5 to 95% by mass, more preferably 30 to 70% by mass.

The molecular weight of the polymer contained in the radical-generating film-forming composition is determined as The weight average molecular weight determined by GPC (Gel Permeation Chromatography) method is 5,000~1,000,000 is ideal, more preferably 10,000~150,000.

When the free radical generating film used in the present invention is obtained by applying a composition of a compound having a radical generating radical and a polymer, hardening it into a film, and immobilizing it in the film, the polymer is selected from those produced by the above-mentioned production method. The polyimide precursor, and the polymers in the group consisting of polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, etc., can be used to produce free radical polymerization The diamine is at least one kind of polymer obtained from 0 mol % of the diamine component used in the synthesis of the polymer contained in the radical generating film forming composition. Compounds having radical-generating radicals to be added at this time are listed below.

A compound that generates free radicals thermally is a compound that generates free radicals by heating above the decomposition temperature. Such radical thermal polymerization initiators, for example: ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.) etc.), hydrogen peroxides (hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tertiary butyl peroxide, dicumyl base peroxides, diperoxylauryl, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxide Trimethylacetic acid-tert-butyl ester, 2-ethylcyclohexane peroxy-tert-pentyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (Azobisisobutyronitrile, and 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.

啉代丙-1-酮、2-苄基-2-二甲胺基-1-(4-

啉代苯基)-丁酮-1,4-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸異戊酯、4,4’-二(第三丁基過氧羰基)二苯酮、3,4,4’-三(第三丁基過氧羰基)二苯酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、2-(4’-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三

、2-(3’,4’-二甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三

、2-(2’,4’-二甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三

、2-(2’-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三

、2-(4’-戊氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三

、4-[對N,N-二(乙氧基羰基甲基)]-2,6-二(三氯甲基)-s-三

、1,3-雙(三氯甲基)-5-(2’-氯苯基)-s-三

、1,3-雙(三氯甲基)-5-(4’-甲氧基苯基)-s-三

、2-(對二甲胺基苯乙烯基)苯并

唑、2-(對二甲胺基苯乙烯基)苯并噻唑、2-巰基苯并噻唑、3,3’-羰基雙(7-二乙胺基香豆素)、2-(鄰氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-肆(4-乙氧基羰基苯基)-1,2’-聯咪唑、2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’雙(2,4-二溴苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2,4,6-三氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、3-(2-甲基-2-二甲胺基丙醯基)咔唑、3,6-雙(2-甲基-2-

啉代丙醯基)-9-正十二基咔唑、1-羥基環己基苯酮、雙(5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦、3,3’,4,4’-四(第三丁基過氧羰基)二苯酮、3,3’,4,4’-四(第三己基過氧羰基)二苯酮、3,3’-二(甲氧基羰基)-4,4’-二(第三丁基過氧羰基)二苯酮、3,4’-二(甲氧基羰基)-4,3’-二(第三丁基過 氧羰基)二苯酮、4,4’-二(甲氧基羰基)-3,3’-二(第三丁基過氧羰基)二苯酮、2-(3-甲基-3H-苯并噻唑-2-亞基)-1-萘-2-基-乙酮、或2-(3-甲基-1,3-苯并噻唑-2(3H)-亞基)-1-(2-苯甲醯基)乙酮等。該等化合物可單獨使用，也可混用2種以上。 The compound that generates radicals with light is not particularly limited as long as it is a compound that initiates radical polymerization by exposure to light. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone , 1-hydroxycyclohexyl benzophenone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl Acetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-

Linopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-

Phinophenyl)-butanone-1,4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4,4'-di(tert-butylperoxycarbonyl) di Benzophenone, 3,4,4'-tris(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine 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'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-tri

, 4-[p-N,N-bis(ethoxycarbonylmethyl)]-2,6-bis(trichloromethyl)-s-three

, 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 base)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl (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 Acryl) carbazole, 3,6-bis(2-methyl-2-

(Phenopropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro -3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4 '-Tetrakis(tertiary hexylperoxycarbonyl)benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(tertiary butylperoxycarbonyl)benzophenone, 3,4 '-bis(methoxycarbonyl)-4,3'-bis(tert-butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-bis(th Tributylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, or 2-(3-methyl -1,3-Benzothiazole-2(3H)-ylidene)-1-(2-benzoyl)ethanone, etc. These compounds may be used alone or in combination of two or more.

Also, even when the radical generating film is composed of a polymer having an organic group that induces radical polymerization, it may contain a compound having the above radical generating group in order to promote radical polymerization when energy is supplied.

The composition for forming a radical generating film may contain an organic solvent for dissolving or dispersing components other than the polymer component and optionally the radical generating agent. Such an organic solvent is not particularly limited, for example, the organic solvents exemplified in the above-mentioned synthesis of polyamic acid. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N- Dimethylpropanamide and the like are ideal from the point of view of solubility. In particular, N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is preferable, but a mixed solvent of two or more kinds can also be used.

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

Solvents to improve the uniformity and smoothness of the coating film, such as: isopropanol, methoxymethylpentanol, methyl cellol, ethyl cellol, butyl cellol, methyl cellol Threo acetate, butyl cellothreoacetate, ethyl cellothreoacetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol Alcohol Monoacetate, Ethylene Glycol Monoisopropyl Ether, Ethylene Glycol Monobutyl Ether, Propylene Glycol, Propylene Glycol Monoethyl Ether Ester, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol Glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, Propylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl Isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether , methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-ethyl Methyl ethyl oxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate, 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxy Butyl propionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol Monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropane oxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isopentyl lactate, 2-ethyl-1-hexanol, and the like. These solvents may also be used in combination of multiple types. When these solvents are used, it is preferably 5-80% by mass of the total solvent contained in the liquid crystal alignment agent, more preferably 20-60% by mass.

The composition for forming a radical generating film may contain components other than those described above. Examples thereof include compounds that improve the film thickness uniformity and surface smoothness when coating a radical-generating film-forming composition, compounds that improve the adhesion between a radical-generating film-forming composition and a substrate, A compound with better film strength of a radical-generating film-forming composition, etc.

Examples of compounds that improve the uniformity of film thickness and surface smoothness include fluorine-based surfactants, Polysiloxane-based surfactants, non-ionic surfactants, etc. More specifically, for example: EFTOP EF301, EF303, EF352 (manufactured by Tohkem Products Co., Ltd.), MegafacF171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), AsahiGuard AG710 , surflonS-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), etc. When using these surfactants, the proportion thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total amount of polymers contained in the radical generating film forming composition.

As a specific example of the compound which improves the adhesiveness of a radical generating film forming composition and a board|substrate, the compound containing a functional silane, the compound containing an epoxy group, etc. are mentioned. For example: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyl Trimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane 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 N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylenyl)-3-amino Propyltrimethoxysilane, N-bis(oxyethylenyl)-3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol di Glycidyl Ether, Tripropylene Glycol Diglycidyl Ether, Polypropylene Glycol Diglycidyl Ether, Neopentyl Glycol Diglycidyl Ether, 1,6-Hexanediol Diglycidyl Ether, Glycerin Diglycidyl Ether ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diecidylaminomethyl)cyclohexane, N,N,N',N '-tetraepoxypropyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-epoxypropyl)aminopropyltrimethoxysilane, 3-(N , N-diepoxypropyl) aminopropyl trimethoxysilane and so on.

In addition, in order to further increase the film strength of the radical generating film, 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, tetrakis(methoxymethyl)bis Phenol compounds such as phenol. When using these compounds, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of the polymer contained in a radical generating film forming composition, and it is more preferable that it is 1-20 mass parts.

Furthermore, in addition to the above, in the composition for forming a radical generating film, a dielectric material for changing the electrical properties such as the dielectric constant and conductivity of the radical generating film may be added within the range not impairing the effect of the present invention. bodies, conductive substances.

[Free radical generating film]

The radical generating film of the present invention can be obtained using the above-mentioned composition for forming a radical generating film. For example, the composition for forming a radical generating film used in the present invention can be coated on a substrate, dried and calcined to obtain a cured film, which can be directly used as a radical generating film. In addition, it is also possible to rub the cured film, polarize it, irradiate it with light of a specific wavelength, etc., or perform ion beam treatment, or irradiate UV to the liquid crystal display element filled with liquid crystal as an alignment film for PSA.

The substrate on which the composition for forming a radical generating film is applied is not particularly limited as long as it is highly transparent, and a substrate on which transparent electrodes for driving liquid crystals are formed is preferred.

Specific examples include glass plates, polycarbonates, poly(meth)acrylates, polyether resins, polyarylates, polyurethanes, polyester resins, polyethers, polyether ketones, trimethyl Pentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, diacetyl cellulose, cellulose acetate butyrate and other plastic plates form transparent electrodes the substrate.

The substrates that can be used in IPS liquid crystal display elements can also use standard IPS comb electrodes, electrode patterns such as PSA herringbone electrodes, and protrusion patterns such as MVA.

Also, among high-performance devices such as TFT devices, devices such as transistors are used between electrodes for driving liquid crystals and a substrate.

When manufacturing transmissive liquid crystal display elements, the above-mentioned substrates are generally used, but when manufacturing reflective liquid crystal display elements, if it is a substrate with only one side, opaque substrates such as silicon wafers can also be used. In this case, a material such as aluminum that reflects light may also be used for the electrodes formed on the substrate.

As the coating method of the radical generating film forming composition, spin coating method, printing method, inkjet method, spray coating method, roll coating method, etc. are mentioned, but in terms of productivity, transfer printing method is widely used in industry, and in The present invention is also ideally used.

The drying step after coating the radical generating film-forming composition is not necessarily necessary, but it is preferable to include a drying step when the time from coating to firing of each substrate is not fixed, or when firing is not immediately after coating. . The drying method is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed due to substrate transportation or the like. For example, 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 applying the composition for forming a radical generating film by the above-mentioned method can be calcined to form a cured film. At this time, the calcination temperature can generally be carried out at any temperature from 100°C to 350°C, preferably from 140°C to 300°C, more preferably from 150°C to 230°C, and more preferably from 160°C to 220°C. The calcination time can usually be calcination at any time from 5 minutes to 240 minutes. Preferably it is 10 to 90 minutes, more preferably 20 to 90 minutes. Commonly known methods can be used for heating, for example: hot plate, hot air circulation oven, IR oven, belt furnace, etc.

The thickness of the cured film can be selected according to needs, preferably at least 5nm, more preferably at least 10nm, because it is easy to obtain the reliability of the liquid crystal display element, so it is ideal. In addition, when the thickness of the cured film is preferably at most 300 nm, more preferably at most 150 nm, it is preferable because the power consumption of the liquid crystal display element does not become extremely large.

The first substrate having the radical generating film can be obtained in the above manner, but the radical generating film can be subjected to uniaxial alignment treatment. The method for uniaxial alignment treatment includes photo-alignment method, oblique vapor deposition method, rubbing, uniaxial alignment treatment using a magnetic field, and the like.

When the alignment process is performed by rubbing in one direction, for example, the substrate is moved so that the rubbing cloth comes into contact with the film while rotating a rubbing drum around which the rubbing cloth is wound. In the case of the first substrate of the present invention on which the comb-toothed electrodes have been formed, the direction is selected by utilizing the electrical and physical properties of the liquid crystal, but when using liquid crystals with positive dielectric anisotropy, the rubbing direction should be set to be opposite to the comb-toothed electrodes. The extension directions are preferably substantially the same direction.

The second substrate of the present invention is the same as the above-mentioned first substrate except that it does not have the radical generating film. It is preferably a substrate with a conventionally known liquid crystal alignment film.

<Liquid Crystal Cell>

In the liquid crystal cell of the present invention, after the free radical generating film is formed on the substrate by the above method, the substrate with the free radical generating film (the first substrate) and the substrate with the known liquid crystal alignment film (the second substrate) are freely separated. The radical generating film and the liquid crystal alignment film are disposed so as to face each other, the spacer is sandwiched and fixed with a sealant, and a liquid crystal composition containing a liquid crystal and a radical polymerizable compound is injected and sealed. The size of the spacer used at this time is usually 1-30 μm, preferably 2-10 μm. Also, by making the rubbing direction of the first substrate parallel to the rubbing direction of the second substrate, it can be used in IPS mode and FFS mode, and it can be used in twisted nematic mode if the rubbing directions are arranged so that the rubbing directions are perpendicular to each other.

The method of injecting the liquid crystal composition containing the liquid crystal and the radical polymerizable compound is not particularly limited, and examples include the vacuum method of injecting a mixture containing the liquid crystal and the polymerizable compound after the prepared liquid crystal cell is brought into a depressurized state, dropwise adding a liquid crystal composition containing The liquid crystal and the polymer compound mixture are then sealed by drop method, etc.

<Liquid Crystal Composition Containing Liquid Crystal and Radical Polymerization Compound>

When making the liquid crystal display element of the present invention, the polymerizable compound used together with the liquid crystal is not particularly limited as long as it is a radically polymerizable compound, for example: a compound having one or more polymerizable reactive groups in one molecule. Preferably, it is a compound having one polymerizable reactive group in one molecule (hereinafter sometimes referred to as "a compound with a single functional polymerizable group", "a compound with a monofunctional polymerizable group", etc.). The polymerizable reactive group is preferably a radical polymerizable reactive group, such as a vinyl bond.

At least one of the aforementioned radically polymerizable compounds is preferably one molecule compatible with liquid crystals A compound with one polymerizable reactive group in it. That is, a compound having a monofunctional radical polymerizable group is preferable.

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

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

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

Compounds with monofunctional free radical polymerizable groups have reactive groups that can undergo free radical polymerization in the presence of organic free radicals, such as: tertiary butyl methacrylate, hexyl methacrylate, 2-ethyl methacrylate Methacrylate monomers such as hexyl methacrylate, nonyl methacrylate, lauryl methacrylate, and n-octyl methacrylate; tertiary 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 third butoxystyrene, o-, m-, p-chloromethylstyrene, etc.), vinyl esters (e.g. vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate, etc.), ketenes (e.g. : Vinyl ketone, vinyl hexanone, methyl isopropenyl ketone, etc.), N-vinyl compounds (for example: N-vinylpyrrolidone, N-vinylpyrrole, N-vinylcarbazole, N-vinyl Indole, etc.), (meth)acrylic acid derivatives (such as acrylonitrile, methacrylonitrile, acrylamide, isopropylacrylamide, methacrylamide, etc.), vinyl halides (such as: vinyl chloride , vinylidene chloride, tetrachloroethylene, hexachlorobutadiene, vinyl fluoride, etc.), but are not limited to these. These various radically polymerizable monomers may be used alone or in combination of two or more. Also, they are preferably compatible with liquid crystals.

Moreover, the above-mentioned radically polymerizable compound is also preferably a compound represented by the following formula (1).

In formula (1), R ^a and R ^b each independently represent a straight-chain alkyl group with 2 to 8 carbon atoms, and E represents a group selected from single bond, -O-, -NR ^c -, -S-, ester bond, acyl The bonding group in the amine bond. Herein, R ^c represents a hydrogen atom or 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 crystals, that is, a compound having a monofunctional radically polymerizable group is more good.

In addition, for the radically polymerizable compound represented by the aforementioned formula (1), E in the synthetic formula is an ester bond (a bond represented by -C(=O)-O- or -O-C(=O)-) The viewpoints of ease of use, compatibility with liquid crystals, and polymerization reactivity are preferable, and specifically, compounds having the following structures are preferable, but not particularly limited.

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

The content of the radically polymerizable compound in the liquid crystal composition is preferably at least 3% by mass, more preferably at least 5% by mass, more preferably at most 50% by mass, and more preferably at least 5% by mass relative to the total mass of the liquid crystal and the radically polymerizable compound. Preferably, it is 20% by mass or less.

The Tg of the polymer obtained by polymerizing the aforementioned radically polymerizable compound is preferably not higher than 100°C.

In addition, liquid crystals generally refer to substances in a state that exhibits both solid and liquid properties. Representative liquid crystal phases include nematic liquid crystals and smectic liquid crystals. The liquid crystals that can be used in the present invention are not particularly limited. As an example, it is 4-pentyl-4'-cyanobiphenyl.

Then, sufficient energy for polymerizing the radical polymerizable compound is introduced into the liquid crystal cell into which the mixture (liquid crystal composition) containing the liquid crystal and the radical polymerizable compound is introduced. It can be implemented by, for example, heating or irradiating UV, and exhibits desired characteristics by in-situ polymerization of the radically polymerizable compound. Among them, the use of UV can make the alignment patternable, and can also carry out the polymerization reaction in a short time. From this point of view, UV irradiation is better. Also, when using the twisted nematic mode, in addition to the above-mentioned liquid crystal composition, a chiral dopant may be introduced into the liquid crystal cell if necessary.

In addition, heating may be performed during UV irradiation. The heating temperature during UV irradiation should be within the temperature range where the introduced liquid crystal exhibits liquid crystallinity, usually above 40°C, and it is better to heat at a temperature that does not reach the temperature at which the liquid crystal changes to an isotropic phase.

Here, the wavelength of UV irradiation during UV irradiation should be selected to be the optimal wavelength of the reaction quantum yield of the polymerizable compound to be reacted. The amount of UV irradiation is usually 0.01~30J, preferably below 10J. The amount of UV irradiation The less it is, the more it can suppress the reliability drop caused by the damage of the components constituting the liquid crystal display, and the tact in manufacturing can be improved by reducing the UV irradiation time, which is more ideal.

In addition, when the polymerization is performed only by heating without UV irradiation, it is preferable to perform the polymerization at a temperature at which the polymerizable compound reacts and within a temperature range that does not reach the decomposition temperature of liquid crystals. Specifically, for example, it is 100°C or more and 150°C or less.

When giving sufficient energy for the polymerization reaction of the radically polymerizable compound, it is preferable not to It is better to apply a voltage without an electric field.

<Liquid crystal display element>

The liquid crystal cells obtained in this way can be used to produce liquid crystal display elements.

For example, reflective electrodes, transparent electrodes, λ/4 plates, polarizing films, color filter layers, etc. are arranged in the liquid crystal cell according to the usual method, and can be made into reflective liquid crystal display elements.

In addition, the liquid crystal cell can be equipped with backlight, polarizing plate, λ/4 plate, transparent electrode, polarizing film, color filter layer, etc. according to the usual method, and can be made into a transmissive liquid crystal display element.

[Example]

The present invention is described in more detail by 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 method of property evaluation are as follows.

【Chemical 25】

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

<Viscosity measurement>

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

<Determination of imidization rate>

Put 20 mg of polyimide powder into an NMR sample tube (NMR standard sampling tube φ5 manufactured by Kusano Scientific Co., Ltd.), and add deuterated dimethyl sulfide (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) mixture) 0.53ml, apply ultrasound to dissolve it completely. The 500 MHz proton NMR of this solution was measured with the measuring apparatus (JNW-ECA500 manufactured by JEOL Data Corporation).

The imidization rate is determined based on the protons from the structure that does not change before and after imidization as the standard proton, using the peak cumulative value of this proton and the protons from the NH of the amido group appearing around 9.5~10.0ppm The cumulative value of the peak is calculated according to the following formula.

Imidization rate (%)=(1-α‧x/y)×100

In the formula, x is the cumulative value of the proton peak of NH derived from the amido group, y is the cumulative value of the peak of the reference proton, and α is the amido group when the polyamide acid (imidization rate is 0%) The ratio of the number of reference protons targeted by one NH proton.

<Polymerization of Polymer and Preparation of Free Radical Generating Film Forming Composition>

Synthesis Example 1

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

Measure 1.62g of DA-1 (15.00mmol) and 3.96g of DA-2 (15.00mmol) in a 100ml 4-neck flask equipped with a nitrogen inlet tube, an air-cooled tube, and a mechanical stirrer, and add 48.2g of NMP, Stir under nitrogen atmosphere to dissolve completely. 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. Returning to room temperature, 2.71 g of TC-1 (13.80 mmol) was added, and reacted at 40° C. for 12 hours under a nitrogen atmosphere. After confirming the polymerization viscosity, TC-1 was added so that the polymerization viscosity became 1000 mPa‧s to obtain a polymerization solution with a polyamic acid concentration of 20% by mass.

Measure the polyamic acid solution obtained above in a 200ml Erlenmeyer flask equipped with a magnetic stirrer 60g, add 111.4g of NMP to prepare a 7 mass% solution, add 9.10g (88.52mmol) of acetic anhydride and 3.76g (47.53mmol) of pyridine while stirring, stir at room temperature for 30 minutes, then stir at 55°C for 3 hours to allow it to react. After the reaction was completed, the solution was returned to room temperature, and the reaction solution was injected into 500 ml of methanol while stirring to precipitate a solid. Use filtration to recover the solid, then pour the solid into 300ml of methanol and stir for 30 minutes to wash it, carry out a total of 2 times to recover the solid by filtration, air dry and then dry it in a vacuum oven at 60°C to obtain a number average molecular weight of 11300, Polyimide (PI-1) with a weight average molecular weight of 32,900 and an imidization rate of 53%.

Synthesis example 2

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

Measure 1.62g of DA-1 (15.00mmol) and 4.96g of DA-3 (15.00mmol) in a 100ml 4-necked flask equipped with a nitrogen inlet tube, an air-cooled tube, and a mechanical stirrer, add 51.90g of NMP, and Stir under nitrogen and allow to dissolve completely. 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. Returning to room temperature, 2.64 g of TC-1 (13.5 mmol) was added, and the reaction was carried out at 40° C. for 12 hours under a nitrogen atmosphere. After confirming the polymerization viscosity, TC-1 was added so that the polymerization viscosity became 1000 mPa‧s to obtain a polymerization solution with a polyamic acid concentration of 20% by mass.

Measure 60 g of the polyamic acid solution obtained above in a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, add 111.4 g of NMP 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 to react. After the reaction was completed, the solution was returned to room temperature, and the reaction solution was injected into 500 ml of methanol while stirring to precipitate a solid. Use filtration to recover the solid, then put the solid into 300ml of methanol and stir and wash it for 30 minutes for a total of 2 times, then filter to recover the solid, air-dry it and put it in a vacuum oven at 60°C Dried to obtain polyimide (PI-2) with number average molecular weight Mn of 13100, weight average molecular weight Mw of 34000 and imidization rate of 55%.

Synthesis example 3

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

Measure 1.62g of DA-1 (15.00mmol) and 5.65g of DA-4 (15.00mmol) in a 100ml 4-neck flask equipped with a nitrogen inlet tube, an air-cooled tube, and a mechanical stirrer, add 55.4g of NMP and Stir under nitrogen atmosphere to dissolve completely. 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. Returning to room temperature, 2.82 g of TC-1 (14.40 mmol) was added, and the reaction was carried out at 40° C. for 12 hours under a nitrogen atmosphere. After confirming the polymerization viscosity, TC-1 was added so that the polymerization viscosity became 1000 mPa‧s to obtain a polymerization solution with a polyamic acid concentration of 20% by mass.

Measure 60 g of the polyamic acid solution obtained above in a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, add 111.4 g of NMP to prepare a 7% by mass solution, and add 8.36 g (81.2 mmol) of acetic anhydride while stirring, 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 injected into 500 ml of methanol while stirring to precipitate a solid. Use filtration to recover the solid, then put the solid into 300ml of methanol and stir and wash it for 30 minutes for a total of 2 times, then filter to recover the solid, air-dry it, and then dry it in a vacuum oven at 60°C to obtain the number average molecular weight Mn Polyimide (PI-3) with a weight average molecular weight Mw of 12900 and a weight average molecular weight of 31000 and an imidization rate of 51%.

Free Radical Generating Membrane Forming Composition: Preparation of AL1

Measure the polyimide powder obtained in Synthesis Example 1 in a 50ml Erlenmeyer flask equipped with a magnetic stirring bar (PI-1) 2.0g, NMP18.0g was added, stirred at 50°C, and dissolved completely. Further, 6.7 g of NMP and 6.7 g of BCS were added, and 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 Membrane Forming Composition: Preparation of AL2

In a 50ml Erlenmeyer flask equipped with a magnetic stirrer, weigh 2.0g of the polyimide powder (PI-2) obtained in Synthesis Example 2, add 18.0g of NMP, and stir at 50°C to dissolve it completely. Further, 6.7 g of NMP and 6.7 g of BCS were added, and 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, BCS: 30% by mass).

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

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

<Production of liquid crystal display elements>

Using AL1-AL3 obtained above and SE-6414 (manufactured by Nissan Chemical Industries, Ltd.) for liquid crystal alignment for horizontal alignment, a liquid crystal display element was produced with the configuration shown in Table 3.

(1st substrate)

The first substrate (hereinafter also referred to as IPS substrate) is an alkali-free glass substrate with a size of 30 mm×35 mm and a thickness of 0.7 mm. On the substrate, ITO (Indium-Tin-Oxide) electrodes with an electrode width of 10 μm and an electrode-to-electrode interval of 10 μm are formed to form a pixel. The size of each pixel is 10mm in length and 5mm in width.

AL1~AL3 or SE-6414 are filtered through a 1.0μm filter, 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~AL3 were calcined at 150°C for 20 minutes, and SE-6414 was calcined at 220°C for 20 minutes to form a coating film with a film thickness of 100nm.

When the rubbing treatment is "Yes", rubbing is carried out so that the rubbing direction becomes parallel to the comb electrode. The rubbing is made of Yoshikawa Chemical Co., Ltd. Yarn cloth: YA-20R, under the conditions of roller diameter 120mm, rotation speed 300rpm, moving speed 50mm/sec, and pushing amount 0.4mm. But only for the film coated with SE-6414, the above-mentioned rotational speed was set to 1000rpm. After the rubbing treatment, ultrasonic irradiation was performed in pure water for 1 minute, and drying was performed at 80° C. for 10 minutes.

(2nd substrate)

The second substrate (also called back ITO substrate) is an alkali-free glass substrate with a size of 30mm×35mm and a thickness of 0.7mm, and an ITO film is formed on the back surface (the surface facing the outside of the unit cell). Also, columnar spacers with a height of 4 μm were formed on the surface (the surface facing the inner side of the unit cell).

AL1, AL2 or SE-6414, filtered through a 1.0μm filter, coated on the electrode forming surface of the IPS substrate by spin coating, 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 with a thickness of 100nm. Rub treatment. For the rubbing treatment, YA-20R yarn cloth manufactured by Yoshikawa Chemical Co., Ltd. was used. The rubbing was carried out under the conditions of a roll diameter of 120 mm, a rotational speed of 1000 rpm, a moving speed of 50 mm/sec, and a pushing amount of 0.4 mm. However, for the film coated with AL1 or AL2, the above-mentioned rotational speed is set at 300 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.

(Production of liquid crystal cells)

Using the above-mentioned two types of substrates (the first substrate and the second substrate) with the liquid crystal alignment film, leaving the liquid crystal injection port and sealing the surroundings, an empty cell with a cell gap of about 4 μm was produced. At this time, if the first substrate has not been subjected to rubbing treatment, the direction of the comb electrodes on the first substrate and the rubbing direction of the second substrate are parallel to each other; Combined so as to be antiparallel to the rubbing direction of the second substrate.

In this empty cell, liquid crystal (MLC-3019 manufactured by Merck with 10 wt% of HMA added) was vacuum-injected at room temperature, and the injection port was sealed to prepare a liquid crystal cell. The obtained liquid crystal unit cell constitutes an IPS mode liquid crystal display element. Afterwards, the obtained liquid crystal cells were heat-treated at 120° C. for 20 minutes.

When there is UV treatment, use a high-pressure mercury lamp to irradiate ultraviolet rays with a band-pass filter with a wavelength of 313 nm for the liquid crystal cell, so that the exposure amount becomes 1000 mJ.

<Evaluation of Liquid Crystal Alignment>

The alignment of the liquid crystal cell is confirmed using a polarizing plate mounted on a cross Nicol. Those aligned without defects were rated as ○, those with slight alignment defects were rated as △, and those without alignment were rated as ×.

<Determination of V-T curve and evaluation of driving threshold voltage and maximum brightness voltage>

Install a white LED backlight and a luminance meter in such a way that the optical axes are consistent, and place a liquid crystal cell (liquid crystal display element) with a polarizer installed in a way to minimize the brightness between them, and apply a voltage up to 8V at intervals of 1V to measure The brightness of the voltage is used to measure the V-T curve. From the obtained V-T curve, the driving threshold voltage and the value of the voltage at which the luminance becomes maximum were estimated.

<Evaluation of response speed of liquid crystal display>

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

【Table 4】

In the comparison of Cell-1~Cell-20 using a horizontal alignment film rubbed on the rear ITO substrate (second substrate) side, the IPS substrate (first substrate) side uses a radical generating film and undergoes UV treatment. In Cell-11, Cell-12, Cell-16, and Cell-17, it was confirmed that the alignment of the liquid crystal was good, and the driving threshold voltage and the maximum brightness voltage were lowered. Also, it was confirmed that the value of Toff increased in Cell-11 and Cell-12 in which the radical generating membrane was not rubbed, but in Cell-16 and Cell-17 in which the radical generating membrane was rubbed, the Toff The increase in value has been greatly improved.

In addition to the above, in terms of supplementary experiments, AL1 used both the ITO substrate (second substrate) and the IPS substrate (first substrate) on the back surface, and neither the first substrate nor the second substrate was subjected to rubbing treatment. In this liquid crystal cell, alignment defects and bright spots (flow alignment) along the flow direction during liquid crystal injection were observed before UV irradiation, but flow alignment completely disappeared after UV irradiation, and microdomains (isolation) from liquid crystals were confirmed. body (schlieren)). From this, it is suggested that when a liquid crystal containing a radical generating film and a polymerizable compound is used together, the free radical generating film loses the binding force of the liquid crystal alignment by irradiating UV, and forms a zero-surface anchoring film on the free radical generating film.

Also, in the comparison of the liquid crystal cells Cell-21~Cell-24, Cell-21 and Cell-23 which were not irradiated with UV showed uniaxial alignment in the rubbing direction, but Cell-22 and Cell-23 which were irradiated with UV 24. It becomes a non-aligned state, and micro-domains of liquid crystals (isoforms) occur. This suggests that even if the radical generating film is rubbed, a zero-surface anchoring film can be formed on the free radical generating film by irradiating UV.

However, if Cell-22 and Cell-24 are observed while rotating under the cross-Nicols, there will be slight changes in brightness and darkness, which shows that the zero-surface anchoring film is not completely free of alignment constraints, but the constraints are higher than Since the intermolecular force between liquid crystals is weak, the binding force alone will not cause the liquid crystal molecules to be uniaxially aligned in any direction. It can be seen from this that the Toff values in Cell-16 and Cell-17 have been greatly improved, mainly because of the above-mentioned weak binding force.

Synthesis example 1 of polymerizable compound

Synthesis of ethyl 2-(heptyloxymethyl)acrylate

Step 1: Synthesis of 2-Hydroxyethyl Methacrylate

Measure 10 mg of 4-methoxyphenol and 21.88 g (195.1 mmol) of DABCO (1,4-diazabicyclo[2.2.2] octane) in a 500 ml four-neck flask equipped with a nitrogen inlet tube, add pure Add 50 ml of water, and add 11.52 g (390.1 mmol) of paraformaldehyde while stirring below 10° C. under a nitrogen atmosphere, and stir 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, and the mixture was reacted at 50° C. for 5 hours. After the reaction was completed, the reaction solution was transferred to a separatory funnel, and 50 ml of n-hexane was added. Confirm that it has been divided into 3 layers, recycle the lower 2 layers, and do this 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, filtered and concentrated to obtain 22.9 g (175.6 mmol, 90% yield) of a colorless and transparent oily liquid. The structure was confirmed to be the object by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data are as follows.

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

Step 2: Synthesis of ethyl 2-(heptyloxymethyl)acrylate

Measure 19.9g (152.9mmol) of 2-hydroxymethacrylic acid obtained by the above method in a 500ml 4-neck flask equipped with a nitrogen inlet tube, add 300ml THF and 23.2g (229.3mmol) of triethylamine, and place in a nitrogen atmosphere 25.0 g (168.2 mmol) of heptyl chloride was added dropwise while keeping the temperature below 10° C., and reacted for 6 hours. After the reaction, remove the precipitated triethylamine hydrochloride by filtration, concentrate the reaction solution, redissolve it in 300ml of ethyl acetate, wash 3 times with 100ml of 10% potassium carbonate aqueous solution, and wash 3 times with 50ml of pure water , dried with anhydrous magnesium sulfate, filtered and concentrated to obtain light yellow viscous body. Purified by flash column chromatography (developing solvent: ethyl acetate: n-hexane = 20:80), solvent removal, and vacuum drying to obtain 32.2 g (133.0 mmol: yield 87%) of a colorless and transparent oily liquid . The structure was confirmed to be the object by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data are as follows.

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

Synthesis example 2 of polymerizable compound

Synthesis of 2-(heptyloxymethyl)butyl acrylate

Step 1: Synthesis of 2-hydroxybutyl methacrylate

By the same operation as the first step above, ethyl acrylate was changed to butyl acrylate and synthesized to obtain 24.3 g (26.2 g: 85% yield) of a colorless and transparent oil. The structure was confirmed to be the object by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data are as follows.

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

Step 2: Synthesis of 2-(heptyloxymethyl)butyl acrylate

Change the 2-hydroxymethacrylic acid in the second step above to the 2-((heptyloxy)meth)butyl acrylate obtained by the above method, and carry out the synthesis by the same operation to obtain 34.2 g of a colorless and transparent oily liquid (126.7: 82.8% yield). The structure was confirmed by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data are as follows.

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

Polymerizable compound synthesis example 3

Synthesis of Dihexyl Itaconate

Measure 23.8 g (182.9 mmol) of itaconic acid and 35.5 g (347.5 mmol) of 1-hexanol in a 4-neck flask equipped with a Dean Stark tube, add 500 ml of cyclohexane, 0.9 g of concentrated sulfuric acid g (9.1 mmol), 0.04 g (1.82 mmol) of dibutyl hydroxytoluene (BHT), make it into a nitrogen atmosphere, and carry out a dehydration condensation reaction at 110° C. for 24 hours. After the reaction, 100 ml of n-hexane was added to the reaction solution, washed 3 times with 100 g of 10% aqueous sodium carbonate solution, 3 times with 100 ml of pure water, and dried over anhydrous magnesium sulfate. After filtration and concentration, vacuum drying was carried out to obtain 48.6 g (162.8 mmol: 89% yield) of a colorless and transparent oily liquid. The structure of the target compound was confirmed by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data are as follows.

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

(Production of liquid crystal cells)

After making an empty unit cell according to the above (production of liquid crystal unit cell), the liquid crystal compositions LC-1~LC-4 (with MLC-3019 manufactured by Merck company respectively added an optimal amount of the above-mentioned polymerizable Compound) vacuum injection at room temperature with a vacuum of about 300 Pa, and vacuum injection at a vacuum of about 1 Pa for 1 hour after degassing, seal the injection port to make a liquid crystal cell. The obtained liquid crystal cells constitute an IPS mode liquid crystal display element. Afterwards, the obtained liquid crystal cells were heated at 120° C. for 10 minutes. Thereafter, the test was implemented in the same manner as described above.

In addition, liquid crystal compositions LC-1~LC-4 are those in which polymeric compounds listed in the following table are added to MLC-3019 in the following introduction amounts.

<Evaluation results of alignment>

【Table 6】

Liquid crystals (LC-1, LC-2) with IDBu and IDHex introduced, and liquid crystals with C2C6 and C4C6 introduced can exhibit very good alignment even in a relatively high vacuum.

<Evaluation results of electro-optical properties>

Then, the driving threshold voltage, the voltage at maximum brightness, and the response speed of the liquid crystal unit cell with zero-anchor alignment, without rubbing the free radical generating film, are summarized as follows.

Regardless of the presence or absence of rubbing treatment when using a polymeric compound, a decrease in driving voltage was confirmed, and it was observed that There is also a tendency for the response speed to improve due to friction processing.

Therefore, it can be seen that the zero anchoring of the polymeric compound under high vacuum and the effect of improving the response speed by friction can be obtained.

[Industrial Utilization]

According to the present invention, the zero-surface anchoring film can be manufactured industrially with good efficiency from cheap raw materials. Moreover, 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 method such as a PSA type liquid crystal display and an SC-PVA type liquid crystal display.

Claims (20)

A method for manufacturing a liquid crystal cell, comprising the following steps: preparing a first substrate with a free radical generating film and a second substrate without a free radical generating film; facing the second substrate with the free radical generating film on the first substrate Make a unit cell by means of the above method; and fill the liquid crystal composition containing liquid crystal and radical polymerizable compound between the first substrate and the second substrate, and make the liquid crystal composition containing liquid crystal and radical polymerizable compound contact the radical generating film state, heat or UV irradiation is used to give sufficient energy for the polymerization reaction of the radically polymerizable compound. The method for manufacturing a liquid crystal cell as claimed in claim 1, wherein the free radical generating film on the first substrate is a free radical generating film subjected to uniaxial alignment treatment. The method for manufacturing a liquid crystal cell as claimed in claim 1 or 2 of the scope of the patent application, wherein the step of giving energy is carried out without an electric field. The method for manufacturing a liquid crystal cell as claimed in claim 1 or 2 of the patent claims, wherein the free radical generating film is a film formed by immobilizing organic radicals that induce free radical polymerization. The method for manufacturing a liquid crystal cell as claimed in claim 1 or 2 of the patent claims, wherein the free radical generating film is formed by coating and hardening a composition of a compound having free radical generating radicals and a polymer Obtained by immobilization in the membrane. The method for manufacturing a liquid crystal cell as claimed in claim 1 or 2 of the patent application, wherein the free radical generating film is composed of a polymer containing an organic group that induces free radical polymerization. Such as the method of manufacturing a liquid crystal cell according to item 6 of the scope of the patent application, wherein the polymer containing an organic group that induces free radical polymerization is obtained by using a diamine component containing a diamine containing an organic group that induces free radical polymerization at least one polymer selected from polyimide precursors, polyimides, polyureas and polyamides. Such as the manufacturing method of liquid crystal cell in item 4 of the scope of the patent application, wherein the organic group that induces free radical polymerization is the following structure [X-1]~[X-18], [W], [Y], [Z ] represents the organic group;

In the formulas [X-1]~[X-18], * represents the bonding site with a part 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 with 1 to 10 carbons, and an alkoxy group with 1 to 10 carbons, R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or an alkyl group with 1 to 4 carbons Alkyl group; [Chemical 30]

In the formulas [W], [Y], [Z], * represents a bonding site with a part other than the polymerizable reactive group of the compound molecule, and Ar represents a free group that may have an organic group and/or a halogen atom as a substituent. An aromatic hydrocarbon group in the group consisting of phenylene, naphthylene, and biphenylene, R ⁹ and R ¹⁰ each independently represent an alkyl group with 1 to 10 carbons or an alkoxy group with 1 to 10 carbons , when R ⁹ and R ¹⁰ are alkyl groups, they can also 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 with 1 to 4 carbon atoms, and * represents the difference between the compound molecule and the part other than Q. Bonding site; ^R12 represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbons, or an alkoxy group with 1 to 10 carbons. Such as the manufacturing method of the liquid crystal cell of claim 7 of the patent scope, wherein, the diamine containing the organic group that induces free radical polymerization is a diamine having a structure represented by the following general formula (6) or the following general formula (7) ;

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 atom-substituted C1-20 alkylene group, the alkene group Any one or more of -CH ₂ - or -CF ₂ - in the alkyl group can also be independently replaced by a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and then Alternatively, any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- may be replaced by these groups on the condition that they are not adjacent to each other R ⁸ represents a free radical polymerization reactive group selected from the following formula;

In the formulas [X-1]~[X-18], * represents the bonding site with the part 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 with 1 to 10 carbons, and an alkoxy group with 1 to 10 carbons, R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a carbon number 1 ~4 alkyl groups;

In ^formula ( ⁷ ), T1 and T2 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 alkane with carbon numbers of 1 to 20 One or more of any -CH ₂ - or -CF ₂ - of the alkylene group can also be independently replaced by one selected from the group consisting of -CH=CH-, divalent carbocycle, and divalent heterocycle 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 on the condition that Replaced by these groups, J is an organic group represented by the following formula,

^In the formulas [W], [Y], [Z], * represents the bonding position with T2, and Ar represents the group selected from phenylene, naphthyl, and and the aromatic hydrocarbon group in the group consisting of biphenyl, ^R9 and R10 each independently represent an alkyl group with 1 to ¹⁰ carbons or an alkoxy group with 1 to 10 carbons, and 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 with 1 to 4 carbon atoms, and * represents the difference between the compound molecule and the part other than Q. Bonding site; ^R12 represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbons, or an alkoxy group with 1 to 10 carbons. The method for manufacturing a liquid crystal cell as claimed in claim 1 or 2 of the patent scope, wherein at least one of the radically polymerizable compounds is a compound having one polymerizable reactive group in one molecule that is compatible with the liquid crystal . Such as the method for manufacturing a liquid crystal cell according to item 10 of the scope of the patent application, wherein the polymerizable reactive group of the radically polymerizable compound is selected from the following structures,

In the formula, * represents the bonding site with a part other than the polymerizable reactive group of the compound molecule; R ^b represents a straight-chain alkyl group with 2 to 8 carbons, and E represents a group selected from single bonds, -O-, -NR ^c - , -S-, a bonding group in an ester bond and an amide bond; R ^c represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. The method for manufacturing a liquid crystal cell as claimed in claim 1 or 2 of the patent application, wherein, in the liquid crystal composition containing liquid crystal and a radically polymerizable compound, a polymer containing a polymer obtained by polymerizing the radically polymerizable compound is used A liquid crystal composition of a radically polymerizable compound whose Tg is 100°C or lower. The method for manufacturing a liquid crystal cell as claimed in claim 1 or 2 of the scope of the patent application, wherein the second substrate is covered with a liquid crystal alignment film having uniaxial alignment. For example, the method for manufacturing a liquid crystal cell in claim 13 of the patent application, wherein the liquid crystal alignment film with uniaxial alignment is a liquid crystal alignment film for horizontal alignment. The method for manufacturing a liquid crystal cell as claimed in claim 13 or 14, wherein the first substrate with the free radical generating film is a substrate with comb-teeth electrodes. A liquid crystal composition, containing liquid crystals and free radical polymerizable compounds, at least one of the free radical polymerizable compounds is a compound that is compatible with liquid crystals and has one polymerizable reactive group in one molecule, and the polymerizable reaction The group is selected from the following structures, and the content of the radically polymerizable compound in the liquid crystal composition is not less than 3% by mass and not more than 50% by mass relative to the total mass of the liquid crystal and the radically polymerizable compound;

In the formula, * represents the bonding site with a part other than the polymerizable reactive group of the compound molecule; R ^b represents a straight-chain alkyl group with 2 to 8 carbons, and E represents a group selected from single bonds, -O-, -NR ^c - , -S-, a bonding group in an ester bond and an amide bond; R ^c represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. A method for manufacturing a liquid crystal display element, using a liquid crystal cell obtained by using the method for manufacturing a liquid crystal cell in any one of items 1 to 15 of the scope of the patent application. A liquid crystal display element obtained by using the method for manufacturing a liquid crystal display element as claimed in item 17 of the scope of the patent application. The liquid crystal display element of claim 18, wherein the first substrate or the second substrate has electrodes. For example, the liquid crystal display element of item 18 or 19 of the scope of application is a low-voltage drive transverse electric field liquid crystal display element.