KR101856808B1 - Coating solution for forming polyimide film, liquid crystal alignment agent, polyimide film, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

(식 중, Y, R₁ 및 R₂ 는 청구항 1 또는 4 에서 규정되는 기)At least one polymer selected from a polyimide precursor obtained by a polymerization reaction of a tetracarboxylic acid component and a diamine component and a polyimide obtained by imidizing the tetracarboxylic acid component and a diamine component and a polymer obtained by introducing a melamine acid structure into each of two amino groups of the diamine compound A coating liquid for forming a polyimide film containing a bifunctional compound represented by the formula [A], a liquid crystal aligning agent comprising the coating liquid, a polyimide film obtained by applying and firing the coating liquid to a substrate, A], a liquid crystal alignment film comprising the polyimide film, and a liquid crystal alignment film comprising the liquid crystal alignment film.

(Wherein Y, R ₁ and R ₂ are groups defined in claim 1 or 4)

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating liquid for forming a polyimide film, a liquid crystal aligning agent, a polyimide film, a liquid crystal alignment film, and a liquid crystal display device,

The present invention relates to a novel coating liquid for forming a polyimide film and a liquid crystal aligning agent, a polyimide film and a liquid crystal alignment film formed using the same, and a liquid crystal display element.

In the liquid crystal display element, the liquid crystal alignment film plays a role of orienting the liquid crystal in a certain direction. The main liquid crystal alignment film currently used industrially is formed by applying a polyimide-based liquid crystal aligning agent composed of polyamic acid (also referred to as polyamic acid), polyamic acid ester, or polyimide solution, which is a polyimide precursor, . When the liquid crystal is oriented parallel or obliquely with respect to the substrate surface, the film is further subjected to surface stretching treatment by rubbing. A method of using an anisotropic photochemical reaction by polarized ultraviolet irradiation or the like has been proposed as an alternative to the rubbing treatment, and studies for industrialization have been conducted recently.

In order to improve the display characteristics of such a liquid crystal display device, a method of changing the structure of a polyamic acid, a polyamic acid ester or a polyimide, a blend of a polyamic acid, a polyamic acid ester or a polyimide having different characteristics, , Improvements in liquid crystal alignment properties and electrical characteristics, control of the pretilt angle, and the like are performed.

Among techniques for controlling the pretilt angle by the polyimide structure, a method of using a diamine having a side chain as a part of the polyimide raw material can control the pretilt angle according to the use ratio of the diamine, It is relatively easy to make angles and is useful as means for increasing the pretilt angle. Examples of the side chain structure of a diamine that increases the pretilt angle of a liquid crystal include a long chain alkyl group or a fluoroalkyl group (see, for example, Patent Document 1), a cyclic group or a combination of a cyclic group and an alkyl group , A steroid skeleton (see, for example, Patent Document 3), and the like.

The diamine for increasing the pretilt angle of liquid crystals as described above has also been studied to improve the stability of the pretilt angle and the process dependency. The side chain structure used here includes a ring such as a phenyl group or a cyclohexyl group Structure (see, for example, Patent Documents 4 and 5). Further, diamines having such a ring structure in three to four side chains have been proposed (see, for example, Patent Document 6).

2. Description of the Related Art In recent years, liquid crystal display devices have been widely used for liquid crystal televisions and fixed mobile applications (display portions of digital cameras and cellular phones) on a large screen. As a result, have. Even in such a situation, it has been demanded that a liquid crystal alignment film is uniformly applied to a large substrate or a step in terms of display characteristics.

When a solution of a polyamic acid or a solution of a solvent-soluble polyimide is applied to a substrate in a production process of a liquid crystal alignment film, it is generally industrially carried out by flexography or the like. The solvent of the coating liquid may be, for example, N-methyl-2-pyrrolidone or? -Butyrolactone, which is a solvent excellent in solubility of the resin (hereinafter also referred to as good solvent) Butyl cellosolve, which is a low-solubility solvent for the resin (hereinafter, also referred to as a poor solvent), and the like are mixed. However, since the poor solvent has a poor ability to dissolve polyamic acid or polyimide, precipitation occurs when mixed in a large amount (see, for example, Patent Document 7). Particularly, this problem is conspicuous in a solution of a solvent-soluble polyimide. In addition, the polyimide obtained by using the diamine having side chains described above tends to lower the coating uniformity of the solution. Therefore, it is necessary to increase the mixing amount of the poor solvent. It becomes an important characteristic.

In addition, the performance of the liquid crystal display device has been improved, the size of the liquid crystal display device has been increased, the power consumption of the display device has been reduced, and furthermore, the liquid crystal display has been required to be used under various environments. Particularly, problems such as baking due to accumulation charge (RDC) and printing failure due to precipitation and separation due to prolongation of the tact time when the liquid crystal aligning agent is applied to the substrate are a problem. It is difficult to solve both of them at the same time.

As described above, in the polyimide-based liquid crystal alignment film, various diamine components are used as a part of raw materials in order to improve the desired properties, but there are cases where the desired diamine components can not be freely used in relation to other properties .

In addition, polyimide is widely used as a protective material and an insulating material in electric and electronic fields in addition to a liquid crystal alignment film for its high mechanical strength, heat resistance and solvent resistance, and even when used as such a material , The diamine component to be a raw material of the polyimide is modified, but the same is also true that the desired diamine component can not be used freely. It is desired that improvements of these desired characteristics can be easily carried out.

Japanese Patent Application Laid-Open No. 2-282726 Japanese Unexamined Patent Application Publication No. 3-179323 Japanese Patent Application Laid-Open No. 4-281427 Japanese Patent Application Laid-Open No. 9-278724 International Publication No. 2004/52962 pamphlet Japanese Patent Application Laid-Open No. 2004-67589 Japanese Unexamined Patent Application Publication No. 2-37324

The object of the present invention is to solve the above-mentioned problems of the prior art described above, and it is an object of the present invention to provide a coating liquid for forming a polyimide film and a liquid crystal aligning agent capable of easily obtaining various polyimide films, A polyimide film, a liquid crystal alignment film, and a liquid crystal display element.

The coating liquid for forming a polyimide film of the present invention which solves the above problems is a polyimide precursor obtained by polymerizing at least one tetracarboxylic acid component selected from a tetracarboxylic acid and a derivative thereof and a diamine component, At least one polymer selected from a polyimide obtained by imidizing a polyimide precursor and a bifunctional compound represented by the following formula [A] wherein a melamine acid structure is introduced into each of two amino groups of the diamine compound do.

[Chemical Formula 1]

(Wherein Y represents a divalent organic group derived from the diamine compound, R ₁ and R ₂ are each -H, or a benzene ring, a cyclohexane ring, a heterocycle, a fluorine, an ether bond, an ester bond, May be connected to a part of Y to form a ring, and R ₁ and R ₂ may be the same or different and may be the same or different)

The liquid crystal aligning agent of the present invention is characterized by comprising the coating liquid for forming the polyimide film.

The polyimide film of the present invention is obtained by applying the coating liquid for forming a polyimide film to a substrate and firing the coating liquid.

The polyimide film of the present invention is a polyimide precursor obtained by polymerizing at least one tetracarboxylic acid component selected from a tetracarboxylic acid and a derivative thereof and a diamine component and a polyimide precursor obtained by imidizing the polyimide precursor Wherein at least one polymer selected from the group consisting of polyamides crosslinked with a bifunctional compound represented by the following formula [A] introducing a meldrum acid structure into each of two amino groups of the diamine compound.

(2)

(Wherein Y represents a divalent organic group derived from the diamine compound, R ₁ and R ₂ are each -H, or a benzene ring, a cyclohexane ring, a heterocycle, a fluorine, an ether bond, an ester bond, May be connected to a part of Y to form a ring, and R ₁ and R ₂ may be the same or different and may be the same or different)

The liquid crystal alignment film of the present invention is characterized by being formed of the polyimide film.

Further, the liquid crystal display element of the present invention is characterized by comprising the liquid crystal alignment film.

According to the present invention, by forming a coating liquid for forming a polyimide film such as a liquid crystal aligning agent containing a bifunctional compound represented by the above formula [A] and introducing a melamine acid structure into each of two amino groups of the diamine compound, It is possible to obtain a polyimide film such as a liquid crystal alignment film in which branch characteristics are improved freely. The bifunctional compound represented by the above formula [A] is obtained by introducing a marmer acid structure into each of the two amino groups of the diamine compound, and a diamine component for obtaining desired properties which have been conventionally studied as the diamine compound , It is possible to easily improve various characteristics of the obtained polyimide film. The polyimide precursor or polyimide contained in the coating solution for forming a polyimide film of the present invention is crosslinked with the bifunctional compound represented by the above formula [A] by heating, so that the obtained polyimide film is resistant to the organic solvent There is also an effect of becoming a hard film.

Hereinafter, the present invention will be described in detail.

The coating liquid for forming a polyimide film of the present invention contains a bifunctional compound represented by the following formula [A] into which a melamine acid structure is introduced into each of two amino groups of a diamine compound.

(3)

(Wherein Y represents a divalent organic group derived from the diamine compound, R ₁ and R ₂ are each -H, or a benzene ring, a cyclohexane ring, a heterocycle, a fluorine, an ether bond, an ester bond, May be connected to a part of Y to form a ring, and R ₁ and R ₂ may be the same or different and may be the same or different)

In the above formula [A], Y is a divalent organic group derived from a diamine compound which is a raw material of the bifunctional compound represented by the above formula [A] and its structure is not particularly limited, Examples thereof include divalent organic groups represented by the following formulas (Y-1) to (Y-120). Among them, when a polyimide film to be obtained is used as a liquid crystal alignment film, it is preferable that the film has a structure in which a diamine compound having a high linearity is used as a raw material in order to obtain a good liquid crystal alignment property. Y-22, Y-23, Y-25, Y-26, and Y- ), Y-27, Y-41, Y-42, Y-44, Y-45, (Y-67), (Y-69), (Y-64), (Y-63), Y-79, Y-80, Y-81, Y-82, Y-109, etc. . When the obtained polyimide film is used as a liquid crystal alignment film for increasing the pretilt angle of the liquid crystal, it is possible to use a long chain alkyl group (for example, an alkyl group having 10 or more carbon atoms), an aromatic ring, an aliphatic ring, a steroid skeleton, (Y-83), (Y-84), (Y-85), (Y-86) and (Y-87) , Y-88, Y-89, Y-90, Y-91, Y-93, Y-94, Y-102), (Y-103), (Y-102), (Y-103) 104), (Y-105), (Y-106), (Y-107), or (Y-108). (Y-31), (Y-40), (Y-64), (Y-65), (Y-66) , (Y-109) and (Y-110). (Y-17), (Y-18), (Y-111), (Y-112) (Y-115), (Y-116), (Y-117), (Y-118) and (Y-119).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

The bifunctional compound represented by the above formula [A] wherein a marmer acid structure is introduced into each of two amino groups of the diamine compound is used in, for example, trimethyl orthoformate, triethyl orthoformate, (For example, ethyl acetate, hexane, toluene, tetrahydrofuran, acetonitrile, methanol, chloroform, 1,4-dioxane, N, N-dimethylformamide, Can be produced by reacting a diamine compound represented by the following formula [B] with a melamine acid together with trimethyl orthoformate or triethyl orthoformate. As a diamine compound represented by the following formula [B], a diamine component for obtaining a desired property, that is, a tetracarboxylic acid component is polymerized to obtain a desired property as a diamine component for producing a polyimide precursor or polyimide A diamine component to be obtained can be applied. The reaction temperature and the reaction time are not particularly limited. For example, the reaction may be carried out at 60 to 120 ° C for 30 minutes to 2 hours.

[Chemical Formula 19]

(Y, R ₁ and R ₂ are the same as Y, R ₁ and R ₂ in the formula [A])

Of course, one bifunctional compound represented by the above formula [A] may be used, or two or more types may be used in combination.

The coating liquid for forming a polyimide film of the present invention is a polyimide precursor obtained by polymerizing at least one tetracarboxylic acid component selected from a tetracarboxylic acid and a derivative thereof and a diamine component, And at least one polymer selected from polyimides obtained by imidization. Of course, the polyimide precursor and the polyimide may be of one type, or two or more types may be used in combination. The polyimide precursor refers to polyamic acid and polyamic acid ester.

The polyimide precursor contained in the coating solution for forming a polyimide film of the present invention is obtained by polymerizing at least one tetracarboxylic acid component and a diamine component selected from the tetracarboxylic acids and derivatives thereof as described above .

The diamine component includes, for example, a diamine compound represented by the above formula [B]. In addition, a diamine component that is used when a polyimide precursor is obtained by reacting a conventional diamine component with a tetracarboxylic acid component can be used. The diamine component which is the raw material of the polyimide precursor may be the same as the diamine compound which is a raw material of the bifunctional compound represented by the above formula [A], and the diamine component and the diamine component represented by the above formula [A] The diamine compound as a raw material of the bifunctional compound may be a different compound.

As the at least one tetracarboxylic acid component selected from a tetracarboxylic acid and a derivative thereof, a tetracarboxylic acid component used when a polyimide precursor is obtained by reacting a diamine component with a tetracarboxylic acid component is used . Examples of the tetracarboxylic acid derivative include tetracarboxylic acid dihalide, tetracarboxylic acid dianhydride represented by the following formula [C], tetracarboxylic acid diester dichloride, tetracarboxylic acid diester and the like. For example, a polyamic acid can be obtained by reacting a tetracarboxylic acid or a derivative thereof with a diamine component such as a tetracarboxylic acid dihalide or a tetracarboxylic acid dianhydride. The polyamic acid ester can be obtained by reacting the tetracarboxylic acid diester dichloride with the diamine component or by reacting the tetracarboxylic acid diester and the diamine component in the presence of a suitable condensing agent or a base.

[Chemical Formula 20]

(X is a 4-valent organic group)

Specific examples of X in the formula [C] include quaternary organic groups represented by the following formulas (X-1) to (X-46). (X-1), (X-2), (X-3), (X-4) , X-16, X-17, X-19, X-21, X-25, X-26, X- X-32) or (X-46). (X-1), (X-2), and (X-2) are preferably used as the X, and it is preferable to use tetracarboxylic acid dianhydride having an alicyclic or aliphatic cyclic structure in order to improve the transparency of the obtained polyimide film. 25) is more preferable, and (X-1) is more preferable from the viewpoint of reactivity with the diamine component.

[Chemical Formula 21]

Specific examples of the tetracarboxylic acid diester include 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester , 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl Ester, 1,2,3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid Dicarboxy-1-cyclohexylsuccinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dialkyl ester, 1,2, Butanetetracarboxylic acid dialkyl ester, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3 ', 4,4'-dicyclo Hexyltetracarboxylic acid dialkyl ester, 2,3, Tricarboxycyclopentyl acetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 ^{2 5]} nonane -3,4,7,8- tetracarboxylic acid -3,4: 7,8-di-alkyl ester, cyclo hexa [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- di-alkyl ester, 4- (2,5-dioxo-tetrahydrofuran-3-yl) 1,2,3,4-tetrahydronaphthalene-1,2-dicarbondi-alkyl ester, and aliphatic tetracarboxylic acid diesters such as pyromellitic acid dialkyl ester, 3,3 ', 4,4'- Biphenyltetracarboxylic acid dialkyl ester, 3,3'-biphenyltetracarboxylic acid dialkyl ester, 2,3,3 ', 4-biphenyltetracarboxylic acid dialkyl ester, 3,3'4,4'-benzophenonetetracarboxylic acid dialkyl ester, 2,3,3 ', 4-benzophenonetetracarboxylic acid dialkyl ester, bis (3,4-dicarbox Bis (3,4-dicarboxyphenyl) sulfonyldialkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalenetetracarboxylic acid And an aromatic tetracarboxylic acid dialkyl ester such as a dialkyldicarboxylate.

Of course, each of the diamine component and the tetracarboxylic acid component may be used alone or two or more of them may be used in combination.

A method of synthesizing a polyimide precursor by polymerization reaction of a tetracarboxylic acid component and a diamine component is not particularly limited, and a known synthetic method can be used.

For example, the reaction of the diamine component and the tetracarboxylic acid dianhydride may be performed by reacting the diamine component and the tetracarboxylic acid dianhydride in an organic solvent. The organic solvent to be used at this time is not particularly limited as long as the resulting polyimide precursor dissolves. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, , Hexamethyl sulfoxide,? -Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, Ethyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, Glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol mono Diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, N-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene, diethylene glycol, propylene Carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid pro Methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, Propyl propionate, butyl 3-methoxypropionate, diglyme or 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination. The solvent may be a solvent that does not dissolve the polyimide precursor, or may be mixed with the solvent to the extent that the resulting polyimide precursor does not precipitate. In addition, water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the resulting polyimide precursor, and therefore, the organic solvent is preferably dehydrated and dried.

When the diamine component and the tetracarboxylic acid dianhydride are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid dianhydride is dispersed or dissolved in the organic solvent A method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic acid dianhydride and a diamine component, and the like, Either method may be used. When a plurality of diamine components or tetracarboxylic acid dianhydrides are used to carry out the reaction, they may be reacted in a preliminarily mixed state, or they may be sequentially reacted individually, and the low molecular weight compounds reacted individually are mixed and reacted, . The polymerization temperature at that time may be any temperature between -20 DEG C and 150 DEG C, preferably between -5 DEG C and 100 DEG C. The reaction can be carried out at an arbitrary concentration. However, if the concentration is too low, a polymer having a high molecular weight is not easily obtained. If the concentration is too high, the viscosity of the reaction liquid becomes too high, and uniform stirring becomes difficult. Therefore, the content is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction is carried out at a high concentration in the initial stage, and then an organic solvent can be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total molar number of the diamine component to the total molar number of the tetracarboxylic acid dianhydride is preferably 0.8 to 1.2. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

The polyamic acid ester can be obtained by reacting the tetracarboxylic acid diester dichloride with the diamine component or by reacting the tetracarboxylic acid diester and the diamine component in the presence of a suitable condensing agent and a base. Alternatively, it is also possible to synthesize a polyamic acid in advance by the above-mentioned method and esterify the carboxyl group of the polyamic acid by using a polymer reaction.

Specifically, for example, the tetracarboxylic acid diester dichloride and the diamine component are reacted in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, , It is possible to synthesize a polyamic acid ester by reacting it for 1 hour to 4 hours.

As the base, pyridine, triethylamine, and 4-dimethylaminopyridine can be used, but pyridine is preferable for the reaction to proceed mildly. The addition amount of the base is an amount that is easy to remove and is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easily obtaining a high molecular weight material.

When the tetracarboxylic acid diester and the diamine component are polycondensed in the presence of a condensing agent, it is possible to use, as the base, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide N, N ', N ', N ' -tetrahydrofuran, -Tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphite, (2,3-dihydro- 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) 4-methoxymorpholinium chloride n-hydrate Etc. may be used.

Further, in the method using the condensing agent, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0.1 to 1.0 times the molar amount of the diamine or tetracarboxylic acid diester to be reacted.

The solvent used in the above reaction may be the same solvent as the solvent used in the synthesis of the polyamic acid shown above. However, the solubility of the monomer and the polymer may vary depending on the solvent used for the synthesis of the polyamic acid, such as N-methyl-2-pyrrolidone, And they may be used alone or in combination of two or more. From the viewpoint that the precipitation of the polymer does not occur well and the high molecular weight substance can be easily obtained, the concentration at the time of the synthesis is preferably in the range of from 0.1 to 10% by weight, more preferably from 0.1 to 10% by weight, in the reaction solution of the tetracarboxylic acid derivative such as tetracarboxylic acid diester dichloride or tetracarboxylic acid diester and diamine component Is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass%. In order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent the introduction of outside air in a nitrogen atmosphere.

The polyimide contained in the coating liquid for forming a polyimide film of the present invention is obtained by subjecting the polyimide precursor to dehydration ring closure. In the polyimide, the dehydration / removal rate (imidization rate) of the amidic acid group does not necessarily have to be 100%, and can be arbitrarily adjusted depending on the application and purpose.

Examples of the method for imidizing the polyimide precursor include a heat imidization for directly heating the solution of the polyimide precursor or a catalyst imidization for adding a catalyst to a solution of the polyimide precursor.

When the polyimide precursor is thermally imidized in a solution, the temperature is preferably 100 to 400 ° C, more preferably 120 to 250 ° C. It is preferable to carry out the removal while removing water generated by the imidization reaction out of the system.

The catalyst imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, pyridine is preferable since it has a basicity suitable for proceeding the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Of these, use of acetic anhydride is preferred because purification after completion of the reaction is facilitated. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

When the polyimide precursor or polyimide produced from the polyimide precursor or polyimide reaction solution is recovered, the reaction solution may be put into a solvent and precipitated. Examples of the solvent used in the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by charging into the solvent can be recovered by filtration and then dried under normal pressure or reduced pressure at room temperature or by heating. In addition, when the polymer precipitated and recovered is redissolved in an organic solvent, and the operation of re-precipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. As the solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be exemplified, and when three or more kinds of solvents selected from these solvents are used, the purification efficiency is further improved, which is preferable.

The polyimide precursor or polyimide contained in the coating liquid for forming a polyimide film of the present invention is preferably a polyimide precursor having a gel permeation rate (GPC) The weight average molecular weight measured by a Chromatography method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

The coating liquid for forming a polyimide film of the present invention may contain a polymer other than the polyimide precursor and polyimide as a polymer component. Examples of the polymer other than the polyimide precursor and the polyimide include acrylic polymer, methacrylic polymer, polystyrene, polysiloxane and polyamide.

At least one selected from polyimide precursors obtained by polymerization reaction of at least one tetracarboxylic acid component selected from tetracarboxylic acid and derivatives thereof with a diamine component and polyimide obtained by imidizing the polyimide precursor, And a bifunctional compound represented by the above formula [A] in which a melamine acid structure is introduced into each of the two amino groups of the diamine compound, that is, a polyimide for forming a conventional liquid crystal alignment film, The coating liquid for forming a polyimide film is obtained by adding a bifunctional compound represented by the above formula [A] to the coating liquid for film formation so as to obtain a polyimide film improved in various properties comparatively freely.

More specifically, the bifunctional compound represented by the above formula [A] has two structures at both ends of a structure having a meldrum acid structure, that is, a structure derived from meldrum acid. The meldrum acid structure is heated (for example, (I.e., a carbonyl compound having a bivalent group > C = C = O) accompanied by the elimination of carbon dioxide and acetone, and the ketone is singly dimerized or the polyimide precursor or polyimide (For example, a carbon-carbon double bond, a carbon-carbon triple bond, an imine (carbon-nitrogen double bond), a carbodiimide, a sulfurylid, a phosphoryl group, a carboxyl group, an amino group, a thiol group, an aldehyde, Lead), an amide bond or an ester bond, a carbonyl group of an imide bond, an active methylene group or the like. Therefore, the bifunctional compound represented by the above formula [A] does not react with the polyimide precursor or polyimide in the coating liquid for forming a polyimide film which is not heated to a high temperature (for example, 100 ° C or less) Is introduced into the polyimide precursor or polyimide through the meldrum acid structure. Further, since the bifunctional compound represented by the above formula [A] has two meldrum structures, it is presumed that after heating, the polyimide is a structure crosslinked by the bifunctional compound represented by the above formula [A].

Therefore, the polyimide film obtained by applying the coating liquid for forming a polyimide film of the present invention to a substrate and firing can be obtained by the structure of Y of the bifunctional compound represented by the formula [A], that is, the bifunctional compound represented by the formula [A] The structure of the Y derived from the diamine compound as the raw material of the polyimide is introduced into the polyimide.

Here, the conventional polyimide film is widely used as a liquid crystal alignment film, a protective material and an insulating material in the electric and electronic fields for its high mechanical strength, heat resistance and solvent resistance. In order to improve desired characteristics, The diamine component is used as a part of the raw material, but the desired diamine component may not be used freely. For example, in a liquid crystal alignment film, various diamine components are used as a part of raw materials in order to improve desired properties such as liquid crystal alignment property and enhancement of pretilt angle. However, a diamine component Depending on the kind, combination, and amount of the diamine component and the tetracarboxylic acid component, the polymerization reactivity of the diamine component and the tetracarboxylic acid component deteriorates, so that the kind, combination, and amount of the diamine component for obtaining desired properties may be limited. It is also necessary to study the polymerization reaction conditions of the diamine component and the tetracarboxylic acid component for each type and combination of diamine components used to obtain desired properties. In order to form a coating liquid for forming a polyimide film capable of forming a uniform polyimide film, it is necessary to prepare a solution state in which the contained component is dissolved in a solvent. However, the kind of the diamine component used for obtaining desired properties, There is a problem that the solubility of the polyimide precursor and the polyimide contained in the coating liquid for forming a polyimide film deteriorates.

In the present invention, at the stage of the coating liquid for forming a polyimide film, a polyimide precursor or polyimide and a bifunctional compound represented by the above formula [A], which is a compound for obtaining desired characteristics, are contained as separate compounds, In the step of heating (firing) the coating liquid for forming a polyimide film, a bifunctional compound represented by the above formula [A], which is a compound for obtaining desired characteristics, is introduced into the polyimide precursor or polyimide. Therefore, the polyimide precursor or polyimide contained in the coating liquid for forming a polyimide film does not need to have a diamine component as a raw material for obtaining desired characteristics, and therefore, the problem that the polymerization reactivity of the diamine component and the tetracarboxylic acid component is deteriorated , It is necessary to examine the polymerization reaction conditions of the diamine component and the tetracarboxylic acid component for each type and combination of diamine components used for obtaining the desired properties and the problems that the polyimide precursor contained in the coating liquid for forming a polyimide film There is no problem that the solubility of the polyimide is deteriorated. Therefore, the coating liquid for forming a polyimide film of the present invention is excellent in the polymerization reactivity of the diamine component and the tetracarboxylic acid component, the necessity of examination of the polymerization reaction conditions, the necessity of examination of the polyimide precursor and the polyimide solubility, , It is possible to comparatively freely improve various properties of the obtained polyimide film as compared with the conventional coating liquid for forming a polyimide film.

The bifunctional compound represented by the above formula [A] is obtained by introducing a melamine acid structure into each of the two amino groups of the diamine compound. The diamine component for obtaining the desired characteristics, which has been conventionally studied as the diamine compound, A diamine component for obtaining desired properties as a diamine component for producing a polyimide precursor or polyimide by polymerization reaction with a carboxylic acid component can be applied. Therefore, various properties of the obtained polyimide film can be easily improved.

Further, since the polyimide precursor and polyimide contained in the coating liquid for forming a polyimide film of the present invention are crosslinked with the bifunctional compound represented by the above formula [A] by heating, the obtained polyimide film is resistant to the organic solvent And it becomes a hard film.

The method for producing the coating liquid for forming a polyimide film of the present invention is not particularly limited and includes a polyimide precursor obtained by polymerizing at least one tetracarboxylic acid component selected from a tetracarboxylic acid and a derivative thereof and a diamine component, And at least one polymer selected from polyimides obtained by imidizing the polyimide precursor and a bifunctional compound represented by the above formula [A] in which a melamine acid structure is introduced into each of the two amino groups of the diamine compound into a solvent And dissolve it.

The solvent of the coating liquid for forming a polyimide film of the present invention is a polyimide precursor obtained by polymerizing at least one tetracarboxylic acid component selected from the above tetracarboxylic acids and derivatives thereof and a diamine component, At least one polymer selected from polyimides obtained by imidizing a diamine compound and a bifunctional compound represented by the above formula [A] having a melamine acid structure introduced into each of two amino groups of the diamine compound, Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2- But are not limited to, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, gamma -butyrolactone, 1,3-dimethyl- imidazolidinone, Ketones, Organic solvents such as methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme and 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination.

The coating liquid for forming a polyimide film of the present invention preferably has an organic solvent content of 70 to 97 mass% from the viewpoint of forming a uniform polyimide film by coating. This content can be appropriately changed depending on the intended thickness of the polyimide film such as the liquid crystal alignment film.

The content of the polyimide precursor and the polyimide in the coating liquid for forming a polyimide film of the present invention is preferably 3 to 30% by mass. This content can also be appropriately changed depending on the intended thickness of the polyimide film such as the liquid crystal alignment film.

The content of the bifunctional compound represented by the above formula [A] in the coating liquid for forming a polyimide film of the present invention is preferably 1 to 200 parts by mass based on 100 parts by mass of the total amount of the polyimide precursor and the polyimide, More preferably 1 to 100 parts by mass, and particularly preferably 1 to 50 parts by mass, in order that the crosslinking reaction proceeds to exhibit desired film curability and does not lower the alignment property of the liquid crystal.

The coating liquid for forming a polyimide film of the present invention is not particularly limited as long as the effect of the present invention is not impaired, A solvent (also referred to as a poor solvent) or a compound may be used. Further, a compound or the like which improves the adhesion between the polyimide film and the substrate may be used.

Specific examples of the poor solvent for improving the uniformity of the film thickness or the surface smoothness include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve, Propylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoacetate, , Propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, dipropyl ether Propylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol N-pentane, n-pentane, n-pentane, n-butane, n-pentane, n-pentane, n-pentane, n-pentane, Methyl propionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, Ethyl, 3-methoxypropionate, 3-methoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol- Acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n (2-ethoxypropoxy) -Propyl ester, n-butyl lactate or lactic acid iso-ethyl ester, and the like. These poor solvents may be used alone or in combination. When such a poor solvent is used, it is preferably 1 to 50 mass%, more preferably 5 to 30 mass%, of the total amount of the organic solvent contained in the coating liquid for forming a polyimide film.

Examples of the compound that improves film thickness uniformity and surface smoothness include fluorinated surfactants, silicone surfactants, and nonionic surfactants. Specific examples thereof include F-top EF301, EF303, EF352 ( SC101, SC102, SC103, SC104, SC102, SC104, SC102, SC104, SC102, SC104, SC104, SC104, SC104, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total amount of the polymer components contained in the coating liquid for forming a polyimide film.

Specific examples of the compound that improves the adhesion between the polyimide film and the substrate include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- Aminopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylene Trimethoxysilylpropyl triethylenetriamine, 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- Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) (Oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether , Tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2 -Dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl- (N, N-diglycidylaminomethyl) cyclohexane or N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and the like Sensuality Silane-containing compounds, there may be mentioned epoxy group-containing compound.

When a compound that adheres to these substrates is used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the polymer components contained in the coating liquid for forming a polyimide film of the present invention. Mass part. If it is less than 0.1 part by mass, the effect of improving the adhesion can not be expected, and if it exceeds 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

In the coating liquid for forming a polyimide film of the present invention, a dielectric material or a conductive material may be added for the purpose of changing electrical characteristics such as dielectric constant and conductivity of the polyimide film provided that the effect of the present invention is not impaired.

In the coating liquid for forming a polyimide film of the present invention, a crosslinking compound having an epoxy group, an isocyanate group, or an oxetane group, and further, a hydroxyl group or an alkoxyl group is preferable as long as the effect of the present invention is not impaired A crosslinkable compound having at least one substituent, or a crosslinkable compound having a polymerizable unsaturated bond may be mixed.

Such a coating liquid for forming a polyimide film of the present invention can be used as a liquid crystal aligning agent for forming a liquid crystal alignment film. The liquid crystal alignment film is a film for aligning the liquid crystal in a predetermined direction.

The polyimide film can be formed by applying the coating liquid for forming a polyimide film of the present invention to a substrate and firing it. When the coating liquid for forming a polyimide film of the present invention is used as a liquid crystal aligning agent, it is preferably coated on a substrate and subjected to an orientation treatment by rubbing treatment, light irradiation, or the like after being baked, The liquid crystal alignment film can be formed without alignment treatment.

The substrate is not particularly limited as long as it is capable of applying a coating solution for forming a polyimide film. However, when a liquid crystal alignment film is formed, it is preferable that the substrate has high transparency. Specific examples thereof include glass substrates, plastic substrates such as acrylic substrates and polycarbonate substrates, and the like. It is preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed from the viewpoint of process simplification. In the reflection type liquid crystal display device, if only one side substrate is used, it can be used for an opaque material such as a silicon wafer. In this case, a material for reflecting light such as aluminum can also be used. In a high-performance device such as a TFT-type device, a device such as a transistor is formed between an electrode for liquid crystal driving and a substrate.

The method of applying the coating liquid for forming a polyimide film to the substrate is not particularly limited, but is generally industrially carried out by screen printing, offset printing, flexographic printing, inkjet or the like. Examples of other application methods include dip, roll coater, slit coater, and spinner, and these may be used depending on the purpose.

A coating liquid for forming a polyimide film is coated on a substrate, and if necessary, a part or all of the solvent is dried and then fired. The firing may be carried out by heating the melamine acid structure of the bifunctional compound represented by the above formula [A] to ketene or the like and reacting with the carboxyl group of the polyimide precursor or polyimide. For example, by a heating means such as a hot plate, a hot air circulation path or an infrared ray at 180 to 250 ° C to evaporate the solvent and react the melamine acid structure with the polyimide precursor or polyimide to form a polyimide precursor Or a bifunctional compound represented by the above formula [A] is introduced into the polyimide to form the polyimide film of the present invention. The polyimide film thus obtained has a structure in which the polyimide is crosslinked by the bifunctional compound represented by the above formula [A], so that it becomes a hard film and excellent in cutting resistance.

The thickness of the polyimide film formed after firing is disadvantageous in view of power consumption of the liquid crystal display element if it is made of a liquid crystal alignment film and if it is too thick. If it is too thin, the reliability of the liquid crystal display element may deteriorate. To 300 nm, and more preferably from 10 to 200 nm. When the liquid crystal is horizontally oriented or tilted, the coated film after firing is treated by rubbing, polarized ultraviolet irradiation, or the like.

The liquid crystal display element of the present invention is obtained by obtaining a substrate having a liquid crystal alignment film attached thereto by the above-described technique, and then a liquid crystal cell is produced by a known method to form a liquid crystal display element. For example, the liquid crystal display device includes two substrates arranged to face each other, a liquid crystal layer formed between the substrates, and a liquid crystal alignment layer formed between the substrate and the liquid crystal layer and formed by a liquid crystal aligning agent comprising the coating liquid for forming a polyimide film of the present invention. A liquid crystal display device comprising a liquid crystal cell having a liquid crystal alignment film. As the liquid crystal display of the present invention, various kinds of liquid crystal display devices such as a twisted nematic (TN) type, a vertical alignment (VA) type, and an in-plane switching (IPS) .

The substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a substrate having high transparency, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed. Specific examples include the same substrates as those described in the polyimide film.

The liquid crystal alignment film is formed by applying the liquid crystal aligning agent of the present invention on the substrate and then baking, and the details are the same as described above.

The liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited, and conventional liquid crystal materials such as MLC-2003, MLC-6608 and MLC-6609 manufactured by Merck can be used.

One example of a method of manufacturing a liquid crystal cell is to prepare a pair of substrates on which a liquid crystal alignment film is formed and spread the spacer such as beads on the liquid crystal alignment film of one of the substrates to make the liquid crystal alignment film face inward, A method in which a substrate is bonded and a liquid crystal is injected under reduced pressure to seal the substrate or a method in which a liquid crystal is dropped on a surface of a liquid crystal alignment film on which a spacer is dispersed and sealing is performed by bonding the substrate. The thickness of the spacer at this time is preferably 1 to 30 占 퐉, more preferably 2 to 10 占 퐉.

Since the liquid crystal display device manufactured as described above is manufactured by using a liquid crystal aligning agent having at least one of a bifunctional compound represented by the above formula [A] and a polyimide precursor and a polyimide capable of introducing desired characteristics , And various characteristics can be improved.

Example

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the interpretation of the present invention is not limited to these examples.

[Synthesis of bifunctional compound represented by the above formula [A]

≪ Synthesis Example 1 &

Bis (2,2-dimethyl-1,3-dioxane-4 (4-phenylenebis (azanediyl) bis , 6-dione)

[Chemical Formula 22]

Meldrum acid [1] (14.7 g, 102 mmol) and trimethyl orthoformate [2] (147 g) were added to a 300 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, paraphenylenediamine [3] (5.0 g, 46 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 15.8 g (yield: 82%) of compound [4].

≪ Synthesis Example 2 &

Bis (2,2-dimethyl-1, 3-dioxane-4) bis (methane-1-yl) , 6-dione)

(23)

Meldrum acid [1] (14.7 g, 102 mmol) and trimethyl orthoformate [2] (147 g) were added to a 300 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, metaphenylenediamine [5] (5.0 g, 46 mmol) was added, and further refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 14.1 g (yield: 72%) of compound [6].

≪ Synthesis Example 3 &

The compound 5,5 '- (pyridine-2,6-diylbis (azanediyl)) bis (methan-1-yl-1-ylidene) bis (2,2- dimethyl-1,3-dioxane -4,6-dione)

≪ EMI ID =

Meldrum acid [1] (16.0 g, 111 mmol) and trimethyl orthoformate (160 g) were added to a 300 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, 2,6-diaminopyridine [7] (5.5 g, 50 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 16.7 g (yield: 80%) of the compound [8].

≪ Synthesis Example 4 &

(4,4'-methylenebis (4,1-phenylene) bis (azanediyl)) bis (methan-1-yl- 1- ylidene) bis (2,2- dimethyl-1,3-dioxane-4,6-dione)

(25)

Meldrum acid [1] (14.7 g, 102 mmol) and trimethyl orthoformate [2] (147 g) were added to a 300 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, 4,4'-diaminodiphenylmethane [9] (5.0 g, 46 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 14.1 g (yield: 72%) of the compound [10].

≪ Synthesis Example 5 &

Bis (2,2-dimethylbenzene) bis (methan-1-yl-1-ylidene) bis (2,2- dimethyl-1,3-dioxane-4,6-dione)

(26)

Meldrum acid [1] (7.92 g, 54.9 mmol) and trimethyl orthoformate [2] (78 g) were added to a 200 ml four-necked flask and refluxed for 1 hour. Then, 4,4'-diaminodiphenyl ether [11] (5.0 g, 25.0 mmol) was added, and further refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane. Thereafter, the solid was dried to obtain 11.7 g (yield: 92%) of the compound [12].

≪ Synthesis Example 6 &

(4,4'-azanediylbis (4,1-phenyl ene) bis (azanediyl)) bis (methan-1-yl- 1- ylidene) bis -dimethyl-1,3-dioxane-4,6-dione)

(27)

Meldrum acid [1] (7.96 g, 55.2 mmol) and trimethyl orthoformate [2] (79 g) were added to a 200 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, 4,4'-diaminodiphenylamine [13] (5.0 g, 25.1 mmol) was further added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 10.1 g (yield: 79%) of the compound [14].

≪ Synthesis Example 7 &

Bis (4,1-phenylene) bis (azanediyl) bis (methan-1-yl-1-ylidene) bis (2, 5 ' , 2-dimethyl-1,3-dioxane-4,6-dione)

(28)

Meldrum acid [1] (14.9 g, 103 mmol) and trimethyl orthoformate [2] (100 g) were added to a 500 ml four-necked flask and refluxed for 1 hour. Thereafter, 4,4'-diaminodiphenylmethylamine [15] (10.0 g, 46.9 mmol) was further added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 21.7 g (yield: 86%) of the compound [16].

≪ Synthesis Example 8 &

Bis (4,1-phenylene)) bis (azanediyl) bis (methan-1-yl) benzene represented by the following formula [18] yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

[Chemical Formula 29]

Meldrum acid [1] (16.6 g, 115 mmol) and trimethyl orthoformate [2] (111 g) were added to a 300 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [17] (15.0 g, 52.4 mmol) was added, and the mixture was further refluxed for 2 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane. Thereafter, the solid was dried to obtain 20.8 g (yield: 67%) of compound [18].

≪ Synthesis Example 9 &

Synthesis of 1,3-bis (4 - ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) phenethyl) urea represented by the following formula [20]

(30)

Meldrum acid [1] (28.6 g, 147 mmol) and trimethyl orthoformate [2] (200 g) were added to a 200 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Then, Compound [19] (20.0 g, 67.0 mmol) was added, and further refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 40.3 g (yield: 99%) of compound [20].

≪ Synthesis Example 10 &

The compound 5,5 '- (6,7,9,10,17,18,20,21-octahydro dibenzo [b, k] [1,4,7,10,13,16] Synthesis of bis (azanediyl) bis (methan-1-yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

(31)

Meldrum acid [1] (7.38 g, 51.2 mmol) and trimethyl orthoformate [2] (100 g) were added to a 200 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [21] (10.0 g, 25.6 mmol) was added, and further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 17.9 g (yield: 96%) of the compound [22].

≪ Synthesis Example 11 &

The compound 5 - ((3 - ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) benzylamino) methylene) -2,2-dimethyl -1,3-dioxane-4,6-dione

(32)

Meldrum acid [1] (23.6 g, 164 mmol) and trimethyl orthoformate (2 g) (100 g) were added to a 300 ml four-necked flask and refluxed for 1 hour. Then, 3-aminobenzylamine [23] (10.0 g, 81.9 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 36.2 g (yield: 100%) of the compound [24].

≪ Synthesis Example 12 &

Bis (piperidin-4,1-diyl) bis (methan-1-yl-1-ylidene) benzene represented by the following formula [26] ) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

(33)

Meldrum acid [1] (11.7 g, 81.0 mmol) and trimethyl orthoformate [2] (128 g) were added to a 200 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, 1,3-di-4-piperidyl propane [25] (8.52 g, 40.5 mmol) was added, and further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 20.2 g (yield: 99%) of the compound [26].

≪ Synthesis Example 13 &

Bis (2,2-dimethyl-1,3-dioxane) bis (methane-1-yl-1-ylidene) bis -4,6-dione)

(34)

Meldrum acid [1] (42.8 g, 297 mmol) and trimethyl orthoformate [2] (150 g) were added to a 500 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, 1,3-diaminopropane [27] (10.0 g, 135 mmol) was added, and further refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 24.8 g (yield: 48%) of compound [28].

≪ Synthesis Example 14 &

Bis (2,2-dimethyl-1) - bis (methylene-1-yl-1-ylidene) bis , 3-dioxane-4,6-dione)

(35)

Meldrum acid [1] (44.6 g, 309 mmol) and trimethyl orthoformate [2] (200 g) were added to a 500 ml four-necked flask and refluxed for 1 hour. Thereafter, 1,3-bisaminomethylcyclohexane (cis- / trans-mixture) [29] (20.0 g, 141 mmol) was added and the mixture was further refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 58.3 g (yield 92%) of a compound [30] (cis- / trans- mixture) .

≪ Synthesis Example 15 &

Synthesis of 3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) benzoic acid represented by the following formula [32]

(36)

Meldrum acid [1] (10.4 g, 72.3 mmol) and trimethyl orthoformate [2] (105 g) were added to a 200 ml four-necked flask and refluxed for 1 hour. Thereafter, 3,5-diaminobenzoic acid [31] (5.0 g, 32.9 mmol) was further added, and further refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 9.0 g (yield: 59%) of the compound [32].

≪ Synthesis Example 16 &

(3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) -N- (pyridin-3-ylmethyl) benzamide Synthesis of

(37)

Meldrum acid [1] (6.5 g, 45.4 mmol) and trimethyl orthoformate [2] (66 g) were added to a 200 ml four-necked flask and refluxed for 1 hour. Thereafter, Compound [33] (5.0 g, 20.6 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 11.3 g (yield: 98%) of the compound [34].

≪ Synthesis Example 17 &

(2,2-dimethyl-4,6-dioxo-1,3-dioxan-3-yl) propyl) -3,5- 5-ylidene) methylamino) benzamide

(38)

Meldrum acid [1] (10.1 g, 52.1 mmol) and trimethyl orthoformate [2] (50 g) were added to a 200 ml four-necked flask and refluxed for 1 hour. Thereafter, Compound [35] (5.0 g, 23.7 mmol) was added, and further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 13.4 g (yield: 100%) of the compound [36].

≪ Synthesis Example 18 &

Synthesis of 3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) benzyl furan-2-carboxylate represented by the following formula [38]

[Chemical Formula 39]

Meldrum acid [1] (13.7 g, 94.7 mmol) and trimethyl orthoformate [2] (100 g) were added to a 200 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, Compound [37] (10.0 g, 43.1 mmol) was added, and further refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 21.1 g (yield: 90%) of the compound [38].

≪ Synthesis Example 19 &

1-ylidene) bis (2,2-dimethyl-1,3-phenylene) bis (azanediyl) bis (methan- 1,3-dioxane-4,6-dione)

(40)

Meldrum acid [1] (10.8 g, 75.2 mmol) and trimethyl orthoformate [2] (100 g) were added to a 300 ml four-necked flask and refluxed for 1 hour. Thereafter, Compound [39] (10.0 g, 34.2 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 29.7 g (yield: 99%) of the compound [40].

≪ Synthesis Example 20 &

Bis (2,2-dimethyl-1,3-phenylene) bis (azanediyl) bis (methan-1-yl- 1,3-dioxane-4,6-dione)

(41)

Meldrum acid [1] (4.2 g, 29.2 mmol) and trimethyl orthoformate [2] (42 g) were added to a 100 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Then, Compound [41] (5.0 g, 13.3 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 6.4 g (yield: 71%) of the compound [42].

≪ Synthesis Example 21 &

4-heptylcyclohexyl) phenoxy) -1,3-phenylene) bis (azanediyl) bis (methan-1-yl) -1-ylidene ) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

(42)

Meldrum acid [1] (4.2 g, 28.9 mmol) and trimethyl orthoformate [2] (41 g) were added to a 100 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [43] (5.0 g, 13.1 mmol) was added, and further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 9.0 g (yield: 98%) of the compound [44].

≪ Synthesis Example 22 >

(Cyclohexan) -4-yl) phenoxy) -1,3-phenylene) bis (azanediyl) bis (trans-4- Synthesis of (methan-1-yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

(43)

Meldrum acid [1] (9.0 g, 62.1 mmol) and trimethyl orthoformate [2] (120 g) were added to a 300 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [45] (12.3 g, 28.2 mmol) was added, and further refluxed for 2 hours. After the completion of the reaction, the solvent was removed with a separator and dried to obtain 20.68 g (yield: 98%) of the compound [46].

≪ Synthesis Example 23 >

4-yl) phenoxy) methyl) -1,3-phenylene) bis ((trans-4- azanediyl) bis (methan-1-yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

(44)

Meldrum acid [1] (19.0 g, 98.6 mmol) and trimethyl orthoformate [2] (200 g) were added to a 500 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [47] (20.0 g, 44.6 mmol) was added, and further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 33.4 g (yield: 99%) of the compound [48].

≪ Synthesis Example 24 &

The compound 4'-pentylbi (trans-cyclohexan) -4-yl 3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan- methylamino) benzoate

[Chemical Formula 45]

Meldrum acid [1] (13.3 g, 92.0 mmol) and trimethyl orthoformate [2] (150 g) were added to a 500 ml four-necked flask and refluxed for 1 hour. Thereafter, Compound [49] (15.0 g, 41.8 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 28.8 g (yield: 99%) of the compound [50].

≪ Synthesis Example 25 >

(2,4-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) phenyl) -4- (trans- 4-pentylcyclohexyl) benzamide

(46)

Meldrum acid [1] (8.2 g, 56.7 mmol) and trimethyl orthoformate [2] (80 g) were added to a 300 ml four-necked flask and refluxed for 1 hour. Thereafter, Compound [51] (10.0 g, 25.8 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature. The precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 16.0 g (yield: 92%) of the compound [52].

≪ Synthesis Example 26 &

(2,4-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) phenyl) -4- 4-Heptylcyclohexyl) benzamide

(47)

Meldrum acid [1] (11.7 g, 81.0 mmol) and trimethyl orthoformate [2] (150 g) were added to a 300 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Then, Compound [53] (15.0 g, 36.8 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane. Thereafter, the solid was dried to obtain 26.1 g (yield: 99%) of the compound [54].

≪ Synthesis Example 27 >

The compound represented by the following formula [56]: 5,5 '- (4 - ((3S, 8S, 9S, 10R, 13R, 14S, 17R) -10,13- 2-yl) -2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta [a] phenanthren-3- Synthesis of bis (methan-1-yl-1-ylidene) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

(48)

Meldrum acid [1] (4.1 g, 29 mmol) and trimethyl orthoformate [2] (50 g) were added to a 100 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Then, Compound [55] (10.0 g, 13 mmol) was added, and further refluxed for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 9.9 g (yield: 99%) of compound [56].

≪ Synthesis Example 28 >

(E) -2,4-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) phenethyl 3- (4- decyloxy) phenyl) acrylate

(49)

Meldrum acid [1] (7.3 g, 37 mmol) and trimethyl orthoformate [2] (75 g) were added to a 200 ml four-necked flask and refluxed for 1 hour. Thereafter, the compound [57] (7.46 g, 17 mmol) was added, and further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 12.5 g (yield: 99%) of the compound [58].

≪ Synthesis Example 29 &

(E) -3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methylamino) benzyl 3- (4- decyloxy) phenyl) acrylate

(50)

Meldrum acid [1] (6.3 g, 33 mmol) and trimethyl orthoformate [2] (63 g) were added to a 200 ml four-necked flask and refluxed for 1 hour. Thereafter, Compound [59] (6.3 g, 15 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 10.7 g (yield: 99%) of compound [60].

≪ Synthesis Example 30 &

5, 5 '- (((6,7,9,10,17,18,20,21-octahydrodiben zo [b, k] [1,4,7,10,13,16 ] hexaoxacyclooctadecine-2,14-diyl) bis (azanediyl) bis (methanylidene)) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

(51)

Meldrum acid [1] (4.87 g, 33.8 mmol) and trimethyl orthoformate [2] (60 g) were added to a 200 ml four-necked flask and refluxed for 1 hour. Then, Compound [61] (6.00 g, 15.4 mmol) was added, and further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 10.4 g of a compound [62] (yield: 97%).

≪ Synthesis Example 31 &

Diazacyclooctadecane-7,16-diyl) bis (methanyllidene) bis (2,2-dimethyl-1,3,4,5- 1,3-dioxane-4,6-dione)

(52)

Meldrum acid [1] (24.17 g, 167.7 mmol) and trimethyl orthoformate [2] (200 g) were added to a 500 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, Compound [63] (20.00 g, 76.2 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 43.2 g (yield: 100%) of the compound [64].

≪ Synthesis Example 32 >

Bis (4,1-phenylene)) bis (azanediyl) bis (methanelylidene) oxybenzene represented by the following formula [66] )) bis (2,2-dimethyl-1,3-dioxane-4,6-dione)

(53)

Meldrum acid [1] (22.00 g, 153 mmol) and trimethyl orthoformate [2] (200 g) were added to a 500 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [65] (20.00 g, 69.4 mmol) was added, and further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 40.2 g of a compound [66] (yield: 97%).

≪ Synthesis Example 33 >

Synthesis of 2- (methacryloyloxy) ethyl 3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) benzoate represented by the following formula [68]

(54)

Meldrum acid [1] (24.18 g, 168 mmol) and trimethyl orthoformate [2] (300 g) were added to a 500-mL four-necked flask and refluxed for 1 hour. Thereafter, Compound [67] (20.00 g, 76.3 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, hexane was added, filtered, and dried to obtain 43.7 g (yield: 100%) of the compound [68].

≪ Synthesis Example 34 &

(E) -2,4-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- '-butoxy- [1,1'-biphenyl] -4-yl) acrylate

(55)

Meldrum acid [1] (4.00 g, 20.4 mmol) and trimethyl orthoformate [2] (40 g) were added to a 100 mL four-necked flask, and the mixture was heated under reflux for 1 hour. Then, Compound [69] (4.00 g, 9.3 mmol) was added, and the mixture was further refluxed for 2 hours. After the completion of the reaction, the solvent was removed with a separator and dried to obtain 6.8 g (yield: 99%) of compound [70].

≪ Synthesis Example 35 >

(E) -2,4-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- -cyclohexylphenyl) acrylate

(56)

Meldrum acid [1] (4.35 g, 30 mmol) and trimethyl orthoformate [2] (50 g) were added to a 200 ml four-necked flask and refluxed for 1 hour. Then, Compound [71] (5.00 g, 14 mmol) was added, and further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 9.63 g (yield: 99%) of the compound [72].

≪ Synthesis Example 36 >

(E) -2,4-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- - (Synthesis of [trans-1,1'-bi (cyclohexan)] -4-yl) phenyl) acrylate

(57)

Meldrum acid [1] (2.84 g, 20 mmol) and trimethyl orthoformate [2] (40 g) were added to a 200 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [73] (4.00 g, 9.0 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 6.6 g (yield: 99%) of the compound [74].

≪ Synthesis Example 37 &

(E) -2,4-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- - (trans-4-pentylcyclohexyl) phenyl) acrylate Synthesis of

(58)

Meldrum acid [1] (13.55 g, 69.8 mmol) and trimethyl orthoformate [2] (140 g) were added to a 300 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Then, the compound [75] (13.79 g, 31.7 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 22.4 g (yield: 95%) of the compound [76].

≪ Synthesis Example 38 &

(E) -2,4-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) phenethyl 3- - (trans-4-heptylcyclohexyl) phenyl) acrylate Synthesis of

[Chemical Formula 59]

Meldrum acid [1] (3.43 g, 23.8 mmol) and trimethyl orthoformate [2] (50 g) were added to a 100 ml four-necked flask, and the mixture was heated under reflux for 1 hour. Then, Compound [77] (5.00 g, 10.8 mmol) was added, and further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 8.3 g of a compound [78] (yield: 100%).

≪ Synthesis Example 39 &

(E) -3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) benzyl 3- - (trans-4-pentylcyclohexyl) phenyl) acrylate Synthesis of

(60)

Meldrum acid [1] (11.31 g, 78.5 mmol) and trimethyl orthoformate [2] (150 g) were added to a 300 ml four-necked flask and refluxed for 1 hour. Then, Compound [79] (15.00 g, 35.7 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 25.3 g (yield: 99%) of the compound [80].

≪ Synthesis Example 40 &

(E) -3,5-bis ((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) amino) benzyl 3- - (trans-4'-pentyl- [1,1'-bi (cyclohexan)] -4-yl) phenoxy) acrylate

(61)

Meldrum acid [1] (1.83 g, 12.7 mmol) and trimethyl orthoformate [2] (45 g) were added to a 200 ml four-necked flask and refluxed for 1 hour. Thereafter, Compound [81] (3.00 g, 5.8 mmol) was added, and the mixture was further refluxed for 2 hours. After completion of the reaction, the solvent was removed with a separator and dried to obtain 4.8 g (yield: 100%) of the compound [82].

[Synthesis of polyamic acid or polyimide and preparation of solution thereof]

The abbreviations used in the following are as follows.

(Tetracarboxylic acid dianhydride)

CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride

(62)

(Diamine)

p-PDA: p-phenylenediamine

DDM: 4,4'-diaminodiphenylmethane

PCH7AB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

(63)

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

(Measurement of molecular weight)

The molecular weight of the polymer (polyamic acid, polyimide) in the present example was measured using a gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Corporation, a column (KD-803, KD-805 ) Was used, and measurement was carried out as follows.

Column temperature: 50 ° C

Eluent: N, N-dimethylformamide (30 m mol / l of lithium bromide-hydrate (LiBr.H ₂ O) as additive, 30 mmol / l of phosphoric acid anhydrous crystal (o-phosphoric acid) (THF) of 10 ml / l)

Flow rate: 1.0 ml / min

Standard for the production of calibration curve Sample: TSK standard polyethylene oxide (molecular weight about 900,000, 150,000, 100,000, 30,000) manufactured by Toso Corporation and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.

(Measurement of imidization rate)

In this example, the imidization rate of polyimide was measured as follows.

About 20 mg of the polyimide powder was placed in an NMR sample tube, and about 0.53 ml of deuterated dimethylsulfoxide (DMSO-d ₆ , 0.05% TMS mixture) was added and completely dissolved by ultrasonic wave. This solution was measured for proton NMR at 500 MHz using an NMR measuring device. The proton derived from the structure in which the imidization rate does not change before and after imidization is defined as a reference proton and the proton peak value of this proton and the proton peak cumulative value derived from the NH group of amic acid appearing around 10.0 ppm . In the following formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and? Is the amount of the amic acid in the case where the polyamic acid (imidation rate is 0% Is the number of reference protons for one NH group proton.

Imidization ratio (%) = (1 -? X / y) x 100

<Synthesis of polyamic acid (PAA-1) and preparation of the solution>

7.93 g (40 mmol) of DDM and 20 g of NMP were added to a 100 ml four-necked flask and dissolved. After cooling to about 10 캜, 7.46 g (38 mmol) of CBDA in NMP (67 g) And the mixture was returned to room temperature and reacted under a nitrogen atmosphere for 6 hours to obtain a solution having a concentration of polyamic acid (PAA-1) of 15 mass%.

88 g of a solution having a concentration of 15 mass% of the polyamic acid (PAA-1) was transferred to a 200 ml Erlenmeyer flask, and 87.6 g of NMP and 43.8 g of BCS were added to dilute the polyamic acid (PAA-1) %, A polyamic acid (PAA-1) solution having 74 mass% of NMP and 20 mass% of BCS. This polyamic acid (PAA-1) had a number average molecular weight of 12,081 and a weight average molecular weight of 30,449.

<Synthesis of polyamic acid (PAA-2) and preparation of its solution>

8.65 g (80 mmol) of p-PDA and 49 g of NMP were added and dissolved in a 200 ml four-necked flask, followed by cooling to about 10 ° C. NMP (80 g) of CBDA 14.1 g (72 mmol) The slurry solution was added, and the mixture was returned to room temperature and reacted under a nitrogen atmosphere for 6 hours to obtain a solution having a concentration of polyamic acid (PAA-2) of 15 mass%.

125 g of a solution having a concentration of 15 mass% of the polyamic acid (PAA-2) was transferred to a 300 ml Erlenmeyer flask, and 118.5 g of NMP and 60.9 g of BCS were added to dilute the polyamic acid (PAA-2) %, A polyamic acid (PAA-2) solution having 74 mass% of NMP and 20 mass% of BCS. This polyamic acid (PAA-2) had a number average molecular weight of 7,609 and a weight average molecular weight of 15,837.

<Synthesis of polyamic acid (PAA-3) and preparation of its solution>

After adding 8.05 g (74 mmol) of p-PDA, 2.13 g (5.6 mmol) of PCH7AB and 118 g of NMP to the 200-ml four-necked flask, the solution was cooled to about 10 DEG C and 14.1 g (100 g) in NMP (100 g) was added, and the mixture was returned to room temperature and reacted under nitrogen atmosphere for 6 hours to obtain a solution having a concentration of 10 mass% of polyamic acid (PAA-3).

234 g of the solution having a concentration of 10 mass% of the polyamic acid (PAA-3) was transferred to a 300 ml Erlenmeyer flask, and 70.8 g of NMP and 76.2 g of BCS were added to dilute the solution to obtain 6 mass of polyamic acid (PAA-3) %, A polyamic acid (PAA-3) solution having 74 mass% of NMP and 20 mass% of BCS. This polyamic acid (PAA-3) had a number average molecular weight of 6,092 and a weight average molecular weight of 12,002.

<Synthesis of Soluble Polyimide (SPI-1) and Preparation of Its Solution>

BODA (16.9 g, 68 mmol), p-PDA (6.8 g, 63 mmol) and PCH7AB (10.3 g, 27 mmol) were mixed in NMP (100 g) After reacting for 3 hours, CBDA (4.1 g, 21 mmol) and NMP (52 g) were added and reacted at 40 ° C for 3 hours to obtain a polyamic acid solution. NMP was added to the polyamic acid solution (130 g) to dilute it to 6 mass%, acetic anhydride (16 g) and pyridine (12 g) were added as an imidation catalyst and reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (1.6 L), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (SPI-1). The imidization ratio of the polyimide was 54%, the number average molecular weight was 18,300, and the weight average molecular weight was 45,300. The amount of the carboxyl group in the polyimide is 0.92 relative to the repeating unit.

NMP (98 g) and BCS (90 g) were added to the obtained polyimide powder (SPI-1) (12.0 g) and dissolved by stirring at 80 ° C for 40 hours to prepare a soluble polyimide (SPI- .

[Preparation of coating liquid (liquid crystal aligning agent) for forming polyimide film]

&Lt; Examples 1 to 9 >

To the polyamic acid (PAA-1) solution (10.0 g) prepared above, the compound shown in the following Table 1 prepared in the above Synthesis Example as a compound represented by the above formula [A] (PAA-1)), and stirring was performed at room temperature (25 캜) until a homogeneous solution was obtained. As a result, the polyimide film formation of Examples 1 to 9 To prepare a coating liquid for application (coating liquid for forming a functional polymer film).

[Table 1]

&Lt; Examples 10 to 34 >

To the polyamic acid (PAA-1) solution (10.0 g) prepared above, the compound shown in the following Table 2, which was prepared in the above synthesis example, as the compound represented by the above formula [A] (Polyamic acid (PAA-1)) was added so that the ratio was as shown in Table 2 below, and the mixture was stirred at room temperature until a homogeneous solution was obtained. As a result, the polyimide film formation To prepare a coating liquid for application.

[Table 2]

&Lt; Examples 35 to 45 >

(PAA-2) solution (10.0 g) as the polyamic acid (PAA-2) solution prepared in the above Synthesis Example as a compound represented by the above formula [A] (I.e., polyamic acid (PAA-2)), and the mixture was stirred at room temperature until a homogeneous solution was obtained. The coating liquid for forming a polyimide film of Examples 35 to 45 Lt; / RTI &gt;

[Table 3]

&Lt; Examples 46 to 59 >

To the polyamic acid (PAA-3) solution (40.0 g) prepared above was added the compound shown in the following Table 4 as the compound represented by the above formula [A] as the polyamic acid (PAA-3) solution (PAA-3)) as shown in Table 4, and the mixture was stirred at room temperature until a homogeneous solution was obtained. As a result, the polyimide film formation of Examples 46 to 59 To prepare a coating liquid for application.

[Table 4]

&Lt; Examples 60 to 62 >

(PAA-2) solution (70.0 g) as the polyamic acid (PAA-2) solution prepared above as the compound represented by the above formula [A] (PAA-2)) was added so as to have the ratios shown in Table 5 below, and stirring was performed at room temperature until a homogeneous solution was obtained. As a result, the polyimide film formation of Examples 60 to 62 To prepare a coating liquid for application.

[Table 5]

&Lt; Examples 63 to 76 >

To the soluble polyimide (SPI-1) solution (10.0 g) prepared above, the compound shown in the following Table 6, which was prepared in the above Synthesis Example as a compound represented by the above formula [A], was dissolved in a soluble polyimide (SPI- ) Was added to the solid content of the solution (i.e., soluble polyimide (SPI-1)) so as to be the ratio shown in Table 6 below, and stirring was performed at room temperature until a homogeneous solution was obtained. To prepare a coating liquid for forming a mid film.

[Table 6]

&Lt; Examples 77 to 86 and Comparative Example 1 > [Confirmation test of crosslinking effect (stripping test)] [

The coating liquid for forming a polyimide film of Examples 63 to 72 was spin-coated on a silicon wafer (2500 rpm / 30 seconds) and fired on a hot plate at 230 캜 for 30 minutes to form a coating film [a1] . The film thickness of the obtained coating film [a1] was measured using a Surfcoder ET4000M manufactured by Kosaka Laboratory Co., Ltd. Next, the silicon wafer on which the coating film [a1] was formed was set again on the spin coater, and NMP was dropped until the entire surface of the silicon wafer was covered. After 60 seconds of stoppage, the NMP was spin-dried (1500 rpm / ) And baked on a hot plate at 100 캜 for 30 seconds, and the remaining film was used as a coating film [a2]. The film thickness of the coating film [a2] was measured again, and the residual film ratio was calculated based on the following calculation formula. As a comparative example 1, the same operation was also performed on the soluble polyimide solution (SPI-1) prepared as described above, that is, the soluble polyimide solution not containing the compound represented by the above formula [A] Respectively. The results are shown in Table 7.

(%) = Film thickness of coating film [a2] / film thickness of coating film [a1] x 100

As a result, it was confirmed that the solvent resistance of the coating film (polyimide film) can be improved by using the coating liquid (liquid crystal alignment treatment agent) for forming a polyimide film to which the compound represented by the above formula [A] was added. Therefore, it is assumed that the soluble polyimide is crosslinked by the compound represented by the above formula [A]. Further, it has been confirmed that the solubility of the coating film can be relatively freely controlled by suitably selecting the bifunctional compound represented by the above formula [A] to be added.

In the same manner, coating films were formed using the coating liquids for forming polyimide films of Examples 1 to 62 and Examples 73 to 76, and subjected to a stripping test. As a result, the compound represented by the above formula [A] was not added , It was confirmed that the solvent resistance of the polyimide film can be improved by using the coating liquid for forming a polyimide film to which the compound represented by the above formula [A] is added.

[Table 7]

[Production of liquid crystal alignment film and liquid crystal cell]

Using the coating liquid (liquid crystal aligning agent) for forming a polyimide film prepared in each of the above Examples, a liquid crystal cell was produced as follows.

A coating liquid for forming a polyimide film (liquid crystal aligning agent) was spin-coated on a glass substrate or a glass substrate attached to an ITO transparent electrode, dried on a hot plate at 80 DEG C for 70 seconds, Was formed.

Thereafter, as for the liquid crystal alignment treatment by rubbing, the coated film surface was rubbed with a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under a predetermined rubbing condition to obtain a substrate having a liquid crystal alignment film adhered thereto. As for the liquid crystal alignment treatment by light, linearly polarized UV light (UV wavelength 313 nm, irradiation intensity 8.0 mW / cm ^-2 ) was changed between exposure amounts of 0 mJ and 1000 mJ on the coated film surface, 40 ° inclination. The linearly polarized UV was prepared by passing a 313 nm band-pass filter through ultraviolet light of a high-pressure mercury lamp, and then passing through a polarizer of 313 nm.

Two substrates each having a liquid crystal alignment film subjected to a liquid crystal alignment treatment were prepared, a spacer of 6 m was spread on the one liquid crystal alignment film surface, a sealant was printed thereon, and another substrate (Anti-parallel liquid crystal cell, Examples 87 to 116), or directly attached (twisted nematic liquid crystal cell, Examples 155 to 179, Examples 296 to 315, and Examples 316 to 321), or UV irradiation, the direction of the polarized light to be irradiated is parallel (anti-parallel liquid crystal cell for vertical alignment mode, Examples 180 to 182, 183 to 294) The blank was cured to prepare an empty cell. Liquid crystal MLC-2003 (manufactured by Merck) in the anti-parallel liquid crystal cell and liquid crystal MLC-2003 (manufactured by Merck Co., Ltd.) containing chiral agent in the twisted nematic liquid crystal cell were injected into this empty cell by a vacuum injection method , Liquid crystal MLC-6608 (manufactured by Merck Co.) was injected in the anti-parallel liquid crystal cell for the vertical alignment mode, and the injection port was sealed to obtain each liquid crystal cell.

[Evaluation of liquid crystal cell]

The measurement of the physical properties of each liquid crystal cell thus prepared and the evaluation method of the characteristics are as follows. The liquid crystal alignment film and the substrate of the liquid crystal cell, firing condition and rubbing condition produced in each measurement and evaluation are also shown.

&Lt; Examples 87 to 116 and Comparative Examples 2 to 4 > < Evaluation of liquid crystal alignment property &

A liquid crystal cell prepared using the coating liquid for forming a polyimide film prepared in each of the examples shown in Table 8 was sandwiched between polarizing plates and the liquid crystal cell was rotated in a state in which the backlight was irradiated from the rear portion, And whether or not the liquid crystal was aligned with or without the liquid crystal was visually observed. At that time, evaluation was made based on the following criteria. The liquid crystal cell prepared for evaluating the liquid crystal alignability had a glass substrate as a substrate and fired on a hot plate heated at 230 캜 for 30 minutes under a firing condition of a coating film of a coating solution for forming a polyimide film, At a roll revolution speed of 300 rpm, a roll advancing speed of 50 mm / sec, and an indentation amount of 0.15 mm. The coating solution (Comparative Example 3 or Comparative Example 4) to which the compound represented by the above formula [A] or the crosslinking agent was not added (Comparative Example 2) and the following commercially available crosslinking agent to which the following crosslinking agent was added (Comparative Example 3 or Comparative Example 4) Were compared. The results are shown in Table 8.

Evaluation standard

?: Alignment of liquid crystal can be confirmed, and there is no flow alignment

&Amp; cir &amp;: The liquid crystal was oriented, but the flow orientation was slightly observed

X: The liquid crystal was oriented, but the flow orientation was observed to be large

&Lt; EMI ID =

As a result, as in Comparative Example 3 and Comparative Example 4, when a commercially available crosslinking agent was used, the orientation of the liquid crystal tended to be easily inhibited in general. However, in the case of forming a polyimide film to which the compound represented by the formula [A] It has been confirmed that when the coating liquid is used, the orientation property of the liquid crystal can be improved without deteriorating the orientation property of the liquid crystal.

[Table 8]

&Lt; Examples 117 to 154 and Comparative Examples 5 to 6 > < Evaluation of rub resistance &

The surface of the liquid crystal alignment film prepared using the coating liquid for forming a polyimide film prepared in each of the examples shown in Tables 9-1 to 9-2 was observed with a confocal laser microscope and evaluated according to the following criteria. Further, using a glass substrate having an ITO transparent electrode as a substrate, the firing conditions of the coating film of the coating liquid for forming a polyimide film were fired on a hot plate heated to 230 DEG C for 30 minutes, rpm, a roll advancing speed of 50 mm / sec, and an indentation amount of 0.5 mm. In addition, the effects of the compounds represented by the above formula [A] not added (Comparative Example 5 and Comparative Example 6) were adjusted and compared. The results are shown in Tables 9-1 to 9-2.

○: No scratches or rubbing scratches were observed.

?: Cutting residue or rubbing scratches were observed.

X: The film was peeled off or rubbing scratches were visually observed.

As a result, compared with Comparative Example 5 and Comparative Example 6 in which the compound represented by the formula [A] was not added, the coating solution for forming a polyimide film to which the compound represented by the formula [A] , It was confirmed that the cutting resistance was improved by using any of the polymers.

[Table 9-1]

[Table 9-2]

&Lt; Examples 155 to 179 and Comparative Example 7 > < Pretilt angle measurement of twisted nematic liquid crystal cell &

The liquid crystal cell prepared by using the coating liquid for forming a polyimide film prepared in each of the examples shown in Table 10 was heated at 105 캜 for 5 minutes and measured for the pretilt angle. The pretilt angle was measured by the Axo Metrix Axo Scan method using the Mueller matrix method. The liquid crystal cell prepared for the measurement of the tilt angle of the twisted nematic liquid crystal cell was a glass substrate on which an ITO transparent electrode was attached as a substrate and the firing condition of the coating film of the coating liquid for forming a polyimide film was set at 230 캜 Firing was carried out on a hot plate for 30 minutes, and rubbing conditions were set at a roll revolution of 1000 rpm, a roll advancing speed of 50 mm / sec, and an indentation amount of 0.3 mm. In addition, the effect of the addition of the compound represented by the above formula [A] (Comparative Example 7) was also compared. The results are shown in Table 10.

As a result, it was confirmed that a desired pretilt angle can be arbitrarily obtained by appropriately selecting the kind and addition amount of the compound represented by the above formula [A].

[Table 10]

Examples 180 to 182 and Comparative Example 8 < Prettilt Angle Measurement of Anti-Parallel Liquid Crystal Cell >

The liquid crystal cell prepared using the coating liquid for forming a polyimide film prepared in each of the examples shown in Table 11 was heated at 120 占 폚 for 1 hour and then the pretilt angle was measured. The pretilt angle was measured by the Axo Metrix Axo Scan method using the Mueller matrix method. The liquid crystal cell prepared for the measurement of the tilt angle of the anti-parallel liquid crystal cell was obtained by using a glass substrate having an ITO transparent electrode as a substrate and heating the coating film of the coating liquid for forming a polyimide film to 200 DEG C The firing was carried out in a hot air circulating oven for 30 minutes, and the liquid crystal cell described above was subjected to no alignment treatment. In addition, the effect of comparison of the compound represented by the above formula [A] (Comparative Example 8) was also compared. The results are shown in Table 11.

As a result, compared with Comparative Example 8 in which the compound represented by the above formula [A] was not added, when a coating solution for forming a polyimide film to which the compound represented by the above formula [A] was added was used, It was confirmed that the angle can be increased. Therefore, even if the side chain component for causing liquid crystals to be introduced into the base polymer, that is, the polyimide precursor contained in the coating liquid for forming a polyimide film or the polyimide is not introduced by adding the compound represented by the above formula [A] Can be vertically oriented.

[Table 11]

&Lt; Examples 183 to 294 > < Evaluation of Liquid Crystal Alignment Properties and Measurement of Pretilt Angles of Antiparallel Liquid Crystal Cells &

The liquid crystal cell prepared using the coating liquid for forming a polyimide film prepared in each of the examples shown in Tables 12-1 to 12-4 was sandwiched between the polarizing plates and the liquid crystal cell was rotated in a state in which the backlight was irradiated from the rear part, And whether or not the liquid crystal was aligned due to the presence or absence of the flow alignment. As a result, the liquid crystal exhibited good alignment. Thereafter, an AC voltage of 3 V was applied to the liquid crystal cell, and it was visually observed whether or not the liquid crystal was aligned. At that time, evaluation was made based on the following criteria. The liquid crystal cell prepared for the evaluation of liquid crystal alignability had a glass substrate used as a substrate and fired in a hot air circulating oven heated at 200 DEG C for firing conditions of the coating film of the coating liquid for forming a polyimide film for 30 minutes, The glass substrate with the coating film thus obtained was subjected to the photo-alignment treatment described above.

Evaluation standard

Good: The alignment of the liquid crystal can be confirmed, and there is no flow alignment

Bad: The liquid crystal is oriented, but a large amount of flow orientation is observed

The liquid crystal cell prepared by using the coating liquid for forming a polyimide film prepared in each of the examples shown in Tables 12-1 to 12-4 was heated at 120 DEG C for 1 hour and then subjected to measurement of the pretilt angle Respectively. The pretilt angle was measured by the Axo Metrix Axo Scan method using the Mueller matrix method.

As a result, it has been found that by using the coating liquid (liquid crystal alignment treatment agent) for forming a polyimide film to which the compound represented by the above formula [A] having a photoreactive side chain is added, good vertical alignment property can be obtained even when the photo alignment treatment is performed . Further, it was confirmed that the application liquid (liquid crystal alignment treatment agent) for forming a polyimide film of the present invention was capable of aligning the liquid crystal in a slightly inclined state from the vertical direction by irradiating ultraviolet rays of polarized light. It was also confirmed that the control of the addition amount and the irradiation amount enabled fine adjustment of the pretilt angle. In view of this, the coating liquid (liquid crystal alignment treatment agent) for forming a polyimide film of the present invention can be used for a liquid crystal alignment film for a liquid crystal display element of a vertical alignment system and is also useful as a liquid crystal alignment film for use in a photo alignment method have.

[Table 12-1]

[Table 12-2]

[Table 12-3]

[Table 12-4]

&Lt; Examples 295 to 315 and Comparative Example 9 > < Measurement of voltage holding ratio (VHR)

In the liquid crystal cell produced using the coating liquid for forming a polyimide film prepared in each of the examples shown in Table 13, the initial voltage holding ratio was measured. The voltage holding ratio was measured by applying a voltage of 4 V for 60 seconds under a temperature of 90 占 폚, measuring the voltage after 16.67 ms, and calculating the voltage holding ratio to calculate the voltage holding ratio. For the measurement of the voltage holding ratio, a VHR-1 voltage maintenance rate measuring apparatus manufactured by Toyota Technica was used. The liquid crystal cell prepared for the measurement of the voltage holding ratio (VHR) was a glass substrate on which an ITO transparent electrode was adhered as a substrate, and a firing condition of the coating film of the coating liquid for forming a polyimide film was heated to 230 DEG C The plate was baked for 30 minutes, and rubbing conditions were set at a roll revolution of 1000 rpm, a roll advancing speed of 50 mm / sec, and an indentation amount of 0.3 mm. In addition, the effect of the addition of the compound represented by the above formula [A] without addition (Comparative Example 9) was compared. The results are shown in Table 13.

As a result, it was confirmed that by using the coating liquid for forming a polyimide film to which the compound represented by the above formula [A] was added, better voltage holding ratio characteristics could be obtained than in the case of using the coating liquid for forming a polyimide film.

[Table 13]

&Lt; Examples 316 to 321 and Comparative Example 10 > < Estimation of accumulated charge (RDC) >

A DC voltage was applied from 0 V to 1.0 V at 0.1 V intervals at a temperature of 23 캜 in a twisted nematic liquid crystal cell manufactured using the coating liquid for forming a polyimide film prepared in each of the examples shown in Table 14, And the calibration curve was prepared. After grounding for 5 minutes, an AC voltage of 3.0 V and a DC voltage of 5.0 V were applied. The flicker amplitude level after 1 hour was measured, and the RDC was estimated by comparing with the previously prepared calibration curve (Flicker Reference Method). The liquid crystal cell prepared for estimating the accumulated charge (RDC) was a glass substrate on which an ITO transparent electrode was attached as a substrate, and the firing conditions of the coating film of the coating liquid for forming a polyimide film were heated to 230 DEG C Firing was carried out on a hot plate for 30 minutes, and rubbing conditions were set at a roll revolution of 1000 rpm, a roll advancing speed of 50 mm / sec, and a press-in amount of 0.3 mm. In addition, the effect of comparison of the compound represented by the above formula [A] (Comparative Example 10) was also compared. The results are shown in Table 14.

As a result, it was confirmed that a liquid crystal cell with a small RDC could be obtained by using the coating liquid for forming a polyimide film to which the compound represented by the above formula [A] was added.

[Table 14]

Examples 322 to 329 and Comparative Example 11 Measurement of ion density before and after aging test

The polyamic acid (PAA-1) solution (10.0 g) was mixed with the polyamic acid (PAA-1) solution of the polyamic acid (PAA- ) Was added so as to have the ratios shown in Table 15 below, and the mixture was stirred at room temperature until a homogeneous solution was obtained to prepare a coating liquid for forming a polyimide film.

Then, the ion density of the twisted nematic liquid crystal cell prepared by using each of these polymer film forming liquids (liquid crystal aligning agent) was measured at an initial state (23 ° C), and the ion density at 60 ° C was maintained for 30 hours Aging) was carried out. In the ion density measurement, the ion density when a triangular wave of voltage ± 10 V and frequency of 0.01 Hz was applied to the liquid crystal cell was measured. The measurement temperature was 80 占 폚. As the measuring apparatus, a liquid crystal physical property evaluation apparatus of Model 6245 manufactured by Toyota Technica was used for any measurement. The results are shown in Table 15.

The twisted nematic liquid crystal cell was fabricated in the same manner as in the twisted nematic liquid crystal cell (Examples 155 to 179) except that the firing condition of the coating film of the coating liquid for forming a polyimide film was fired on a hot plate heated to 200 캜 for 30 minutes. And the same operation was carried out. In addition, the same operation was carried out for the compounds to which no compound for hydration was added to compare the effects.

As a result, it was confirmed that the ionic impurities in the liquid crystal cell were significantly reduced as compared with the case where the compound was not added, by appropriately selecting the kind and amount of the water-soluble compound.

[Table 15]

&Lt; Examples 330 to 342 >

To the polyamic acid (PAA-1) solution (10.0 g) prepared above, the compounds described in the following Table 16, which were prepared in the above Synthesis Example as a hydraulic compound, were added to the solid content of the polyamic acid (PAA- Polyamic acid (PAA-1)) was added so as to have the ratios shown in Table 16 below, and stirring was performed at room temperature until a homogeneous solution was obtained. The coating liquid for forming a polyimide film of Examples 330 to 342 was prepared Respectively.

[Table 16]

&Lt; Examples 343 to 344 >

The polyamic acid (PAA-3) solution (40.0 g) prepared above was compounded with the compound shown in the following Table 17 as the hydrating compound in the above Synthesis Example as the polyamic acid (PAA-3) (PAA-3)) as shown in Table 17, and the mixture was stirred at room temperature until a homogeneous solution was obtained. The coating liquid for forming a polyimide film of Examples 343 to 344 was prepared Respectively.

[Table 17]

&Lt; Examples 345 to 447 > < Evaluation of Liquid Crystal Alignment Property and Measurement of Pretilt Angle of Anti-parallel Liquid Crystal Cell for Vertical Alignment Mode &

[Production of liquid crystal alignment film and liquid crystal cell]

Using the coating liquid for forming a polyimide film (liquid crystal aligning agent) prepared in each of Examples 330 to 344, a liquid crystal cell was produced as follows.

The coating liquid (liquid crystal aligning agent) for forming a polyimide film was spin-coated on a glass substrate, dried on a hot plate at 80 占 폚 for 70 seconds, and then baked in a hot-air circulating oven heated at 200 占 폚 for 30 minutes, Was formed.

Thereafter, linearly polarized UV light (UV wavelength: 313 nm, irradiation intensity: 8.0 mW / cm- ² ) was changed between 0 mJ and 1000 mJ in the coating film surface and irradiated while being inclined at 40 ° with respect to the normal to the plate. The linearly polarized UV was prepared by passing a 313 nm band-pass filter through ultraviolet light of a high-pressure mercury lamp, and then passing through a polarizer of 313 nm.

Two substrates each having a liquid crystal alignment film subjected to a liquid crystal alignment treatment were prepared, a spacer of 6 m was spread on the one liquid crystal alignment film surface, a sealant was printed thereon, and another substrate The orientation of the polarizing light irradiated with the liquid crystal orientation film faced to each other was made parallel so that the sealant was cured to prepare a blank cell. A liquid crystal MLC-6608 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain an anti-parallel liquid crystal cell for each vertical alignment mode.

The produced liquid crystal cell was sandwiched between the polarizing plates, and the liquid crystal cell was rotated in a state where the backlight was irradiated from the rear portion. As a result of visually observing whether or not the liquid crystal was aligned due to the change of light or darkness or the flow alignment, Respectively. Thereafter, an AC voltage of 3 V was applied to the liquid crystal cell, and it was visually observed whether or not the liquid crystal was aligned. At that time, evaluation was made based on the following criteria. The results are shown in Tables 18-1 to 18-4.

Evaluation standard

Good: The alignment of the liquid crystal can be confirmed, and there is no flow alignment

Bad: The liquid crystal is oriented, but a large amount of flow orientation is observed

Further, the liquid crystal cell thus prepared was heated at 120 DEG C for 1 hour, and then the pretilt angle was measured. The pretilt angle was measured by the Axo Metrix Axo Scan method using the Mueller matrix method. The results are shown in Tables 18-1 to 18-4.

As a result, as shown in Tables 18-1 to 18-4, a photo-alignment treatment was carried out by using a coating liquid for forming a polyimide film (liquid crystal alignment treatment agent) to which a hydriding compound having a photoreactive side chain was added It was confirmed that a good vertical alignment property can be obtained. It was also confirmed that the coating liquid (liquid crystal alignment treatment agent) for forming a polyimide film of the present invention was capable of orienting the liquid crystal in a state of slightly tilting vertically by irradiating ultraviolet rays of polarized light. It was also confirmed that the control of the addition amount and the irradiation amount enabled fine adjustment of the pretilt angle. In view of this, the coating liquid (liquid crystal alignment treatment agent) for forming a polyimide film of the present invention can be used for a liquid crystal alignment film for a liquid crystal display element of a vertical alignment system and is also useful as a liquid crystal alignment film for use in a photo alignment method have.

[Table 18-1]

[Table 18-2]

[Table 18-3]

[Table 18-4]

&Lt; Examples 448 to 471 >

To the polyamic acid (PAA-1) solution (10.0 g) prepared above was added the compound shown in the following Table 19 as the hydrating compound in the above Synthesis Example to the solid component of the polyamic acid (PAA-1) Polyamic acid (PAA-1)) was added so as to have the ratios shown in Table 19 below, and the mixture was stirred at room temperature until a homogeneous solution was obtained. The coating liquid for forming a polyimide film of Examples 448 to 471 was prepared Respectively.

[Table 19]

&Lt; Examples 472 to 495 > < Evaluation of liquid crystal alignability of anti-parallel cell for horizontal alignment mode &

[Production of liquid crystal alignment film and liquid crystal cell]

Using the coating liquid for forming a polyimide film (liquid crystal aligning agent) prepared in each of Examples 448 to 471, a liquid crystal cell was produced as follows.

The coating liquid (liquid crystal aligning agent) for forming a polyimide film was spin-coated on a glass substrate and dried on a hot plate at 80 DEG C for 70 seconds and then baked in a hot air circulating oven heated to 200 DEG C for 30 minutes to obtain a film thickness of 100 Nm thick coating film was formed.

Thereafter, linearly polarized UV light (UV wavelength: 313 nm, irradiation intensity: 8.0 mW / cm- ² ) was changed between exposure amounts of 0 mJ and 1000 mJ on the coated film surface, and the substrate was irradiated immediately above. The linearly polarized UV was prepared by passing a 313 nm band-pass filter through ultraviolet light of a high-pressure mercury lamp, and then passing through a polarizer of 313 nm.

Two substrates each having a liquid crystal alignment film subjected to a liquid crystal alignment treatment were prepared, a spacer of 6 m was spread on the one liquid crystal alignment film surface, a sealant was printed thereon, and another substrate The orientation of the polarizing light irradiated with the liquid crystal orientation film faced to each other was made parallel so that the sealant was cured to prepare a blank cell. A liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a vacuum injection method and the injection port was sealed to obtain an anti-parallel liquid crystal cell for horizontal alignment mode.

Then, the produced anti-parallel liquid crystal cell for horizontal alignment mode was sandwiched between the polarizing plates, and the liquid crystal cell was rotated in a state in which the backlight was irradiated from the rear part to visually determine whether the liquid crystal was aligned Respectively. At that time, evaluation was made based on the following criteria. Table 20 shows the results.

Evaluation standard

?: Alignment of liquid crystal can be confirmed, and there is no flow alignment

&Amp; cir &amp;: The liquid crystal was oriented, but the flow orientation was slightly observed

?: The liquid crystal was oriented, but a large amount of flow orientation was observed

X: The liquid crystal is not aligned at all

As a result, in any of the liquid crystal cells, the liquid crystal cell not irradiated with light did not exhibit any orientation at all, but in the liquid crystal cell subjected to light irradiation, it was confirmed that the liquid crystal was oriented in accordance with the amount of the compound to be added and the light irradiation amount. In addition, no significant change in orientation was observed even when each liquid crystal cell in which alignment was observed was subjected to isotropic treatment at 130 占 폚 for 30 minutes. That is, it was confirmed that the horizontally oriented cell can be easily produced by appropriately selecting the kind and amount of the additive.

[Table 20]

Claims (6)

At least one polymer selected from a polyimide precursor obtained by polymerization reaction of at least one tetracarboxylic acid component selected from tetracarboxylic acid and a derivative thereof with a diamine component and a polyimide obtained by imidizing the polyimide precursor And a bifunctional compound represented by the following formula [A] having a marmer acid structure introduced into each of two amino groups of the diamine compound.
[Chemical Formula 1]

(Wherein Y represents a divalent organic group derived from the diamine compound, R ₁ and R ₂ are each -H, or a benzene ring, a cyclohexane ring, a heterocycle, a fluorine, an ether bond, an ester bond, May be connected to a part of Y to form a ring, and R ₁ and R ₂ may be the same or different and may be the same or different) A liquid crystal aligning agent comprising the coating liquid for forming a polyimide film according to claim 1. A polyimide film obtained by applying the coating liquid for forming a polyimide film according to claim 1 to a substrate and firing the coating liquid. At least one polymer selected from a polyimide precursor obtained by polymerization reaction of at least one tetracarboxylic acid component selected from tetracarboxylic acid and a derivative thereof with a diamine component and a polyimide obtained by imidizing the polyimide precursor Comprises a polyimide crosslinked with a bifunctional compound represented by the following formula [A] into which a melamine acid structure is introduced into each of two amino groups of a diamine compound.
(2)

(Wherein Y represents a divalent organic group derived from the diamine compound, R ₁ and R ₂ are each -H, or a benzene ring, a cyclohexane ring, a heterocycle, a fluorine, an ether bond, an ester bond, May be connected to a part of Y to form a ring, and R ₁ and R ₂ may be the same or different and may be the same or different) A liquid crystal alignment film comprising the polyimide film according to claim 3 or 4. A liquid crystal display element comprising the liquid crystal alignment film according to claim 5.