JP3419874B2 - Polyamic acid composition and liquid crystal element - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamic acid composition which can be suitably used for forming a polyimide film pattern by exposure and development, a polyamic acid composition which is imidized at a low temperature, and this polyamic acid. The present invention relates to a liquid crystal element having the polyimide film as a liquid crystal alignment film.

[0002]

2. Description of the Related Art Conventionally, a polyimide resin has been widely used as a liquid crystal alignment film for liquid crystal display elements, an insulating film or a protective film for semiconductor devices and the like.

For example, in a semiconductor device, a protective film (passivation film) is formed on the surface of a semiconductor substrate on which an element is formed for the purpose of protecting the element from the external environment and enhancing its reliability.
Is provided. As a material of this protective film, a polyimide resin excellent in electrical characteristics such as insulation, radiation resistance, and heat resistance is widely used. Also, as an interlayer insulating film in a semiconductor device having a multilayer wiring structure,
Due to the above characteristics, polyimide resin is widely used.

Such a polyimide resin film can be easily formed from its precursor polyamic acid. That is, first, a polyamic acid varnish is applied to the surface of a predetermined substrate and dried to form a film. Further, this film is subjected to a heat treatment to imidize the polyamic acid by a cyclization reaction to form a polyimide film. After that, a general photolithography technique is applied to form a predetermined polyimide film pattern. This method is widely used in semiconductor manufacturing processes because it can employ stabilization treatment at a relatively low temperature.

In recent years, in order to simplify the steps of the semiconductor manufacturing process, it has been attempted to use a polyamic acid composition having a function as a photoresist for pattern formation. For example, a photosensitive polyamic acid containing a photosensitizer and a polyamic acid derivative composed of a repeating unit represented by the following general formula (A), that is, having a side chain of an organic group having a hydroxyl group directly bonded to an aromatic ring. There is a method of using the composition (JP-A-4-218051).

[0006]

[Chemical 14] The following two methods are used to synthesize this polyamic acid derivative. (I) First, a polyamic acid is produced by reacting a tetracarboxylic dianhydride and a diamine compound. Next, a polyamic acid derivative is synthesized by reacting this polyamic acid with an alcohol compound, an amine compound or an alkoxy compound having a hydroxyl group directly bonded to an aromatic ring in the presence of a dehydrating agent. (Ii) First, tetracarboxylic dianhydride and an alcohol compound having a hydroxyl group directly bonded to an aromatic ring,
React with an amine compound or an alkoxy compound.
Next, a polyamic acid derivative is synthesized by subjecting the produced compound and a diamine compound to dehydration condensation. However, in any of these methods, a side reaction occurs during the dehydration reaction, and some polymers gelate due to cyclization. Therefore, the polyamic acid composition has a problem that its solubility in a developing solution is lowered, and a polyimide film pattern formed using this composition has insufficient resolution. Further, in particular, with the method (ii), it was difficult to obtain a high molecular weight polyamic acid derivative, and it was difficult to form a polyimide film pattern having a high degree of polymerization.

On the other hand, in the liquid crystal display element, it is necessary to orient the liquid crystal well. In order to form a liquid crystal alignment film to achieve this purpose, after applying a polyamic acid varnish on the surface of the ITO transparent electrode or the like formed on a transparent substrate, to form a polyimide film by imidization,
The most commonly used method is rubbing the obtained film. However, this method requires a heat treatment at 300 ° C. or higher when imidizing the polyamic acid, and thus has a problem that the color filter provided in the color liquid crystal display device is discolored.

To solve this problem, a varnish of polyimide resin soluble in an organic solvent is directly applied to the surface of the substrate to form a polyimide film. However, such a polyimide resin causes a problem when the dual domain technology for aligning liquid crystals in two different directions in each pixel is applied for the purpose of widening the viewing angle of the liquid crystal display device. That is, in order to achieve the dual domain, first, the polyimide film is rubbed in one direction, and then a photoresist is formed so as to cover half of each pixel, and this is used as a mask and the rubbing process is performed again in the other direction. Give. In this case, when the photoresist pattern covering half of the pixel is formed by exposure and development, the polyimide resin soluble in the organic solvent is attacked by the developing solution, and as a result, the display function of the liquid crystal display device deteriorates.

[0009]

As described above, the polyimide film pattern formed using the conventional photosensitive polyamic acid composition has problems such as insufficient resolution. Further, in the manufacturing process of a liquid crystal display device or the like, when forming a polyimide film as a liquid crystal alignment film,
Conventionally, heat treatment at a high temperature was required to imidize the polyamic acid, which had a problem that the display characteristics of the liquid crystal display device were adversely affected.

In view of the above problems, the present invention provides a polyamic acid composition capable of forming a polyimide film pattern having sufficient resolution and good adhesion to a substrate, and a polyimide film can be formed by heat treatment at a low temperature. An object is to provide a polyamic acid composition.

[0011]

Means and Actions for Solving the Problems The polyamic acid composition of the first invention of the present application has the following general formulas (1) to (5).
And at least one selected from the group consisting of compounds represented by

[Chemical 15] A polyamic acid represented by the following general formula (11),

[Chemical 16] And a photosensitizer.

The polyamic acid composition of the second invention of the present application is
At least one selected from the group consisting of compounds represented by the following general formulas (1) to (5) and derivatives thereof,

[Chemical 17] A polyamic acid represented by the following general formula (11),

[Chemical 18] It is characterized by containing a dissolution inhibitor and a compound which generates an acid upon irradiation with light.

The polyamic acid composition of the third invention of the present application is
At least one selected from the group consisting of compounds represented by the following general formulas (1) to (10) and derivatives thereof,

[Chemical 19]

[Chemical 20] Polyamic acid represented by the following general formula (11)

[Chemical 21] It is characterized by containing and.

The polyamic acid composition of the fourth invention of the present application is
At least one selected from the group consisting of compounds represented by the following general formulas (1) to (4) and (6) to (10) or derivatives thereof;

[Chemical formula 22]

[Chemical formula 23] A polyamic acid represented by the following general formula (11),

[Chemical formula 24] It is characterized by containing a tertiary amine.

The polyamic acid compositions of the first and second inventions of the present application have photosensitivity and are used, for example, to form a polyimide film pattern to be a passivation film or an interlayer insulating film of a semiconductor device, or as a photoresist. To be These polyamic acid compositions have the effect of improving resolution in such applications.

The polyamic acid compositions of the third and fourth inventions of the present application are used, for example, to form a polyimide film to be a liquid crystal alignment film of a liquid crystal display device. Since these polyamic acid compositions can be imidized at a lower temperature than before, it is possible to prevent discoloration of the color filters provided in the color liquid crystal display device.

The present invention will be described in more detail below.

First, the polyamic acid represented by the general formula (11) contained in any of the polyamic acid compositions of the first to fourth inventions of the present application will be described. The polyamic acid used in the present invention is not particularly limited as long as it has a repeating unit represented by the general formula (11). Such polyamic acid can be synthesized by reacting tetracarboxylic dianhydride and diamine.

The tetracarboxylic dianhydride used in the synthesis of the polyamic acid is not particularly limited. For example, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7 -Naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ', 4
4'-biphenyltetracarboxylic dianhydride, 2,
2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [3-
(3,4-Dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-dicarboxyphenyl) Sulfone dianhydride,
Bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, butanetetracarboxylic Acid dianhydride, 2,2-
Bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, 1,4-bis (3,4-
Dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl)-
1,1,3,3-tetramethyldisiloxane dianhydride,
Examples thereof include cyclobutane-1,2,3,4-tetracarboxylic dianhydride and tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

The diamine used for synthesizing the polyamic acid is not particularly limited, but aromatic diamine is preferable. For example, m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4 '.
-Diaminodiphenyl sulfide, 2,2-bis (4-
Aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ketone, 4,
4'-diaminodiphenyl ketone, 4,4'-diaminobenzanilide, bis (4-aminophenyl) dimethylsilane, 1,3-bis (4-aminophenyl) -1,
1,3,3-tetramethyldisiloxane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4
-Aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 4-methyl-2,4-bis (4-aminophenyl) -1-pentene, 4-methyl-
2,4-bis (4-aminophenyl) -2-pentene,
1,4-bis (α, α-dimethyl-4-aminobenzyl) benzene, imino-di-p-phenylenediamine,
1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6) -amino-1- (4-aminophenyl) -1, 3,3-trimethylindane, bis (4-aminophenyl) phosphine oxide, 4,
4'-diaminoazobenzene, 4,4'-diaminodiphenylurea, 4,4'-bis (4-aminophenoxy)
Biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) Benzophenone, 4,4'-
Bis (3-aminophenoxy) diphenyl sulfone,
4,4′-bis (4-aminophenoxy) diphenyl sulfone, 4,4′-bis [4- (α, α-dimethyl-4
-Aminobenzyl) phenoxy] benzophenone, 4,
4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenyl sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 3,5-diamino- 1-hydroxybenzene, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4,4'-dihydroxy-3,3'-diaminobiphenyl, 2,2-bis (4-amino-3-hydroxyphenyl) Propane, 2,2-bis (3-amino-4)
-Hydroxyphenyl) propane, bis (3-amino-)
4-hydroxyphenyl) sulfide, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) methane, 2,2- Examples thereof include bis (4-amino-3-hydroxyphenyl) hexafluoropropane and 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The hydrogen atom of the aromatic ring of these aromatic diamines is at least one selected from the group consisting of chlorine atom, fluorine atom, bromine atom, methyl group, methoxy group, cyano group, phenyl group, amino group and the like. It may be substituted. Furthermore, in addition to the above-mentioned aromatic diamine, for example, dimethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 1,2- bis (3-amino-propoxy) ethane, H ₂ N- (CH _{2)
3 -O- (CH 2) 2 -O-} (CH 2) 3 -NH 2,
1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylisopropane , 1,4-xylylenediamine, 2,6-diaminopyridine, 2,4-diamino-S-triazine, 1,3-bis (γ-aminopropyl) -1,1,3,3-tetramethyldisiloxane ,
1,4-bis (γ-aminopropyldimethylsilyl) benzene, 1,3-bis (4-aminobutyl) -1,1,
3,3-tetramethyldisiloxane, 1,1,3,3-
Examples thereof include tetramethyldisiloxane and 1,3-bis (γ-aminopropyl) -1,1,3,3-tetraphenyldisiloxane. These diamines may be used alone or in combination of two or more.

In the present invention, in order to synthesize the polyamic acid having the repeating unit represented by the general formula (11), the tetracarboxylic dianhydride and the diamine are polycondensed in an organic solvent according to a conventional method. The organic solvent used at this time is, for example, N, N-dimethylformamide, N, N-dimethylacetamide or N-methyl-2-.
Pyrrolidone, N-methyl-ε-caprolactam, γ-butyrolactone, sulfolane, N, N-dimethylsulfoxide, N, N, N ′, N′-tetramethylurea, tetrahydrofuran, methylcellosolve acetate, diglyme, cyclohexanone and the like can be mentioned. . Further, in the synthesis of such a polyamic acid, the preferable mixing ratio of the tetracarboxylic dianhydride and the diamine is a molar ratio of 0.
It is 9 to 1.1: 1, and it is more preferable to mix both components in equimolar amounts. The reaction condition is the reaction temperature-1.
The reaction time is 0 to 100 ° C. and the reaction time is 0.5 to 24 hours. Unlike the polyamic acid represented by the general formula (A), the polyamic acid having the repeating unit represented by the general formula (11) is synthesized without a dehydration reaction, and therefore does not gel.

Although the molecular weight of the polyamic acid thus synthesized is not particularly limited, it is desirable that the polyamic acid has a high molecular weight such that a film having sufficient physical strength can be obtained when applied to a substrate. Therefore, from this viewpoint, the logarithmic viscosity of the polyamic acid (measured at 30 ° C. in a N-methyl-2-pyrrolidone solution at a polymer concentration of 0.5 g / dl)
Is preferably 0.10 dl / g or more.

Further, in the present invention, in order to control the molecular weight in the synthesis of polyamic acid, phthalic anhydride,
Dicarboxylic acid anhydrides such as maleic anhydride, succinic anhydride, and nadic acid anhydride, or monoamines such as aniline, aminophenol, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, and tetracarboxylic acid It can be used in combination with dianhydride and diamine as appropriate.

The polyamic acid synthesized under the above conditions may be used as a solution. Alternatively, the polyamic acid solution may be poured into a poor solvent such as water, methanol, ethanol, isopropyl alcohol, or acetone to precipitate a polymer, and the polymer may be washed, dried, and recovered as a solid before use.

If desired, the polyamic acid composition of the present invention may contain an organic solvent-soluble polyimide having a repeating unit represented by the following general formula (12).
This polyimide is obtained by cyclizing a polyamic acid that is a precursor thereof. This cyclization is performed by heat treatment or chemical treatment. In the method by heat treatment, the polyamic acid solution is heated in the presence of an organic solvent that forms an azeotropic mixture with water such as toluene, xylene, and chlorobenzene to cause a cyclization reaction, while azeotropically distilling off water as a by-product. Generates polyimide. In the method by chemical treatment, a polyamic acid solution is treated with a dehydrating agent such as acetic anhydride, polyphosphoric acid, triphenylphosphine, triphenylphosphite, dicyclohexylcarbodiimide, triethylamine, pyridine, choline chloride, sodium acetate, manganese acetate, or cobalt acetate. In the presence of a catalyst, -20 to 150
By reacting for 1 minute to 24 hours in the temperature range of C, a cyclization reaction is caused to generate a polyimide. The polyimide synthesized under the above conditions may be used as a solution when prepared as a solution. When prepared as a suspension or slurry, these liquids are poured into a poor solvent such as water, methanol, ethanol, isopropyl alcohol, or acetone to precipitate a polymer, which is washed and dried to collect it as a solid. You may use it after doing.

[0026]

[Chemical 25] In the polyamic acid composition of the present invention, the general formula (11)
A polyamic acid having a repeating unit represented by
When the polyimide having the repeating unit represented by 2) is used in combination, the compounding amount of the polyimide is allowed up to 80% by weight in the total amount. 80% by weight of polyimide
When it exceeds, the adhesion between the obtained polyimide film and the substrate tends to be weak. When the polyamic acid composition of the present invention is used as a photosensitive resin composition and the amount of polyimide is more than 80% by weight, both exposed and unexposed areas are less likely to dissolve in an alkaline developing solution during pattern formation. However, it may be difficult to form a pattern with excellent resolution.

In the polyamic acid composition of the present invention, a polyamic acid derivative having a repeating unit represented by the general formula (A) and having a phenolic hydroxyl group introduced into its side chain may be used in combination. However, the mixing ratio is up to 70% by weight, preferably up to about 60% by weight, based on the total amount of the polyamic acid and the polyimide to be added as necessary.

Next, the polyamic acid composition of the first invention of the present application will be described in detail.

The polyamic acid composition of the first invention of the present application is
A compound containing at least one selected from the group consisting of the compounds represented by the general formulas (1) to (5) or a derivative thereof, the polyamic acid represented by the general formula (11), and a photosensitizer. is there.

In the first invention of the present application, general formulas (1) to
The compound represented by (5) or a derivative thereof has a phenolic hydroxyl group. These compounds have a function of suppressing the solubility of polyamic acid in an alkali developing solution.

Examples of the carboxylic acid compound represented by the general formula (1) include hydroxybenzoic acid. Examples of the carboxylic acid compound represented by the general formula (2) include hydroxyphenylacetic acid, hydroxyphenylpyruvic acid, and hydroxycinnamic acid. Examples of the carboxylic acid compound represented by the general formulas (3) and (4) include hydroxynaphthoic acid. Examples of the carboxylic acid ester or carboxylic acid amide represented by the general formula (5) include hydroxybenzoic acid-N, N-dimethylaminomethyl, hydroxybenzoic acid-N, N-diethylaminomethyl, and hydroxybenzoic acid 2-N, N-. Dimethylaminoethyl, 2-N, N-diethylaminoethyl hydroxybenzoate, 3-N, N-hydroxybenzoic acid
Dimethylaminopropyl, hydroxybenzoic acid 3-N,
N-diethylaminopropyl, hydroxybenzoic acid 2-
N, N-dimethylaminopropyl, 2-N, N-diethylaminopropyl hydroxybenzoate, 1-methyl-2-N, N-dimethylaminoethyl hydroxybenzoate,
1-Methyl-2-N, N-diethylaminoethyl hydroxybenzoate, 4-N, N-dimethylaminobutyl hydroxybenzoate, 4-N, N-diethylaminobutyl hydroxybenzoate, 3-methyl-3 hydroxybenzoate
-N, N-dimethylaminopropyl, 3-methyl-3-N, N-diethylaminopropyl hydroxybenzoate,
2-N, N-dimethylaminoethylhydroxybenzoic acid amide, 2-N, N-diethylaminoethylhydroxybenzoic acid amide, 3-N, N-dimethylaminopropylhydroxybenzoic acid amide, 3-N, N-diethylaminopropylhydroxy Benzoic acid amide, 2-N, N-dimethylaminopropyl hydroxybenzoic acid amide, 2-
Examples thereof include N, N-diethylaminopropylhydroxybenzoic acid amide. In the compounds having a phenolic hydroxyl group represented by the general formulas (1) to (5), the hydroxyl group may be bonded to any position of the aromatic ring such as ortho position, meta position, para position and the like. Further, the derivatives of the compounds represented by the general formulas (1) to (5) means that the hydrogen atom of the aromatic ring of these compounds is further a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, a methyl group or an ethyl group. A compound substituted with a group, a methoxy group or an amino group.

The method for synthesizing the carboxylic acid ester or carboxylic acid amide represented by the general formula (5) is not particularly limited. For example, a method of heating a carboxylic acid represented by the general formula (1) and a tertiary amine represented by the following general formula (13) in the presence of a catalyst can be adopted. At this time, the mixing ratio of the tertiary amine to the carboxylic acid is in the range of 1: 1 to 6 and more preferably in the range of 1: 1 to 3 from the viewpoint of yield. As the catalyst used, sulfuric acid, phosphoric acid, hydrochloric acid or p-toluenesulfonic acid,
Examples thereof include boron trifluoride diethyl ether complex. The heating temperature is set to a temperature at which the tertiary amine refluxes. The heating time is 1 to 10 hours, more preferably 2 to 7 hours.

[0033]

[Chemical formula 26] In the polyamic acid composition of the first invention of the present application, the compounding amount of the compound having a phenolic hydroxyl group represented by the general formulas (1) to (5) is 0.05 to 3.0 with respect to the carboxyl group of the polyamic acid. It is preferable to make it equivalent. If the amount is less than 0.05 equivalent, the photosensitive performance may be insufficient. On the contrary, when the compounding amount exceeds 3.0 equivalents, the viscosity stability during storage deteriorates, and the film slippage during development of the obtained coating film increases. Further, the compounding amount of these compounds is more preferably 0.1 to 2.0 equivalents. When polyimide is blended, a compound having a phenolic hydroxyl group may be added to the amount defined above and may be blended up to 20% by weight with respect to the polyimide.

The photosensitizer used in the first invention of the present application is, for example, an o-quinonediazide compound having at least one o-quinonediazide group in the molecule or a naphthoquinonediazide compound having at least one naphthoquinonediazide group in the molecule. Examples thereof include diazide compounds. Specifically, at least one compound selected from the group consisting of compounds (P-1) to (P-29) represented by the following structural formulas can be used. These photosensitizers also have a slight effect of suppressing the solubility of the polyamic acid in the alkali developing solution.

[0035]

[Chemical 27]

[Chemical 28]

[Chemical 29] Among these photosensitizers, 2, as in the above (P-15),
1,2-naphthoquinonediazide sulfonic acid esters of 3,4-trihydroxybenzophenone, the above (P-1
7) such as 2,3,4,4′-tetrahydroxybenzophenone 1,2-naphthoquinonediazide sulfonic acid esters, 2,3,3 ′ such as (P-22) above,
The 1,2-naphthoquinonediazide sulfonic acid esters of 4,4 ′, 5′-hexahydroxybenzophenone are particularly preferred photosensitizers in the present invention. In (P-17) 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide sulfonic acid ester, 2,3,4,4 by 1,2-naphthoquinonediazide sulfonic acid or its derivative is used. '-
The esterification rate of tetrahydroxybenzophenone is usually 40% of the total number of hydroxyl groups in the benzophenone compound.
It is ~ 100%. In other words, 2, 3, 4,
The average number of naphthoquinonediazides introduced per 1 molecule of 4'-tetrahydroxybenzophenone (the number of hydroxyl groups is 4) is 1.6 to 4, and this sensitizer has 1,2,3 or 4 naphthoquinonediazides introduced. It means a mixture of sulfonates. Similarly, for the compound (P-22), the average number of naphthoquinonediazides introduced per molecule of 2,3,3 ′, 4,4 ′, 5′-hexahydroxybenzophenone (having 6 hydroxyl groups) is 2. 4-
The number of sensitizers is 6, and this sensitizer is a mixture of sulfonates having 1,2,3,4,5, or 6 introduced naphthoquinonediazide.

In the first invention of the present application, the compounding amount of the photosensitizer is preferably 1 to 50% by weight based on the total amount of the polyamic acid and the polyimide compounded as necessary. If the blending amount of the photosensitizer is too small, the sensitivity of the polyamic acid composition will be insufficient. On the other hand, if the amount of the photosensitizer is too large, the characteristics of the obtained polyimide film may be deteriorated due to the residue of the photosensitizer after the pattern formation. A more preferable blending amount of the photosensitizer is 5 to 30% by weight.

If desired, the polyamic acid composition of the first invention of the present application may contain a sensitizer, a dye, a surfactant, an adhesion promoter, an alkali-soluble resin and the like.
Specific examples of the adhesion imparting agent include coupling agents such as aminosilane and epoxysilane. Specific examples of the alkali-soluble resin include poly-p-vinylphenol, poly-o-vinylphenol, poly-m-isopropenylphenol, m- or p-cresol novolac resin, xyresole novolac resin, p-vinylphenol and methacryl. Methyl acid copolymer, p-
Examples thereof include copolymers of isopropenylphenol and maleic anhydride, polymethacrylic acid and the like.

The polyamic acid composition of the first invention of the present application is
Usually, it is used as a varnish in a state of being dissolved in an organic solvent. The organic solvent is not particularly limited as long as it dissolves the polyamic acid, the polyimide that is blended if necessary, the compounds represented by the general formulas (1) to (5), and the components of the photosensitizer. Specifically, ketone solvents such as cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, cellosolve solvents such as butyl cellosolve acetate, ethyl acetate, butyl acetate, ester solvents such as isoamyl acetate, Ether solvents such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, N, N-
Solvents such as dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, γ-butyrolactone, sulfolane, xylene, toluene, chlorobenzene, m-cresol, ethylene glycol and propylene glycol. Can be mentioned. These solvents may be used alone or in combination of two or more.

A method for forming a polyimide film pattern using the polyamic acid composition of the first invention of the present application as a photosensitive resin composition will be described below. Generally, a polyimide film pattern is formed through the steps of forming a coating film, drying, exposing, developing with an alkali developing solution, and heat curing. Here, the case where a composition containing 1,2-naphthoquinonediazide sulfonate as a photosensitizer is used will be described.

First, the varnish of the polyamic acid composition of the first invention of the present application is filtered to remove fine contaminants, and then coated on a semiconductor substrate by a spin coating method or a dipping method to form a resin layer. The composition of the present invention has excellent solubility in an organic solvent and thus has improved coatability, and is suitable for forming a thick film.

Next, after drying this resin layer at about 60 to 100 ° C. for about 1 to 30 minutes, the layer is subjected to X-ray, visible light, infrared light, ultraviolet light, excimer through a desired pattern mask. Irradiate energy rays such as laser light. At this time, in the exposed portion of the resin layer, the 1,2-naphthoquinonediazide portion (a) of the photosensitizer is converted into a ketene (b) by a photochemical reaction as described below.

[0042]

[Chemical 30] Next, the exposed resin layer is subjected to a development treatment by using an alkali developing solution by a spray method, paddle development or the like. Examples of the alkaline developer include potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, potassium hydrogencarbonate, ammonium phosphate, aqueous solutions of inorganic alkali such as ammonia, or propylamine, butylamine, Examples of the organic alkaline aqueous solution include monoethanolamine, ethylenediamine, trimethylenediamine, trimethylammonium hydroxide, hydrazine, tetramethylammonium hydroxide, and trimethylhydroxyethylammonium hydroxide. Further, in these aqueous solutions, methanol, ethanol, 2-propanol, ethylene glycol, ethyl cellosolve, butyl cellosolve, diethylene glycol, ethyl carbitol, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, etc. A mixture of organic solvents can also be used. Thus, if an alkaline aqueous solution is used as the developing solution without using an organic solvent,
It is possible to prevent the pattern from swelling due to the developer.

In this developing treatment, in the unexposed portion of the resin layer, the compounds represented by the general formulas (1) to (5) and the 1,2-naphthoquinonediazide sulfonic acid ester are polyamic acid which is the resin portion in the composition. Since the alkali solubility of the polymer is suppressed, the solubility in the developing solution is lower than that of the polymer alone. At this time, among the compounds of the general formulas (1) to (5), particularly when a carboxylic acid ester or a carboxylic acid amide represented by the general formula (5) is blended, the following chemical formula ( As shown in 14), an ionic bond occurs between the amino group (N) of the carboxylic acid derivative and the carboxyl group (O) of the polyamic acid. Therefore, since a polyamic acid derivative having a phenolic hydroxyl group in the side chain is substantially produced without undergoing a chemical reaction, the effect of suppressing the solubility of the unexposed area in the alkaline developer is great.

[0044]

[Chemical 31] Here, the carboxylic acid derivative of the general formula (5) may decompose into a carboxylic acid of the general formula (1) and a tertiary amine of the general formula (13) in a varnish. However, in the present invention, the presence of such a tertiary amine in the polyamic acid composition does not particularly impair the photosensitivity. Therefore, in the polyamic acid composition of the first invention of the present application, there is no problem even if a part or all of the carboxylic acid derivative of the general formula (5) is decomposed into a carboxylic acid and a tertiary amine.

On the other hand, in the exposed portion of the resin layer, the ketene (b) is further converted into the carboxylic acid (c) by the water content in the developing solution as described below. The carboxyl group in the carboxylic acid (c) reacts with an alkali metal ion or ammonium ion in the alkali developing solution to form a salt, so that the exposed portion of the resin layer is dissolved in the developing solution. That is, this development process leaves only the unexposed portion and a predetermined pattern is formed. Therefore, when the polyamic acid composition of the first invention of the present application is blended with 1,2-naphthoquinonediazide sulfonate as a photosensitizer, the exposed part thereof is generally a positive type which is solubilized in a developing solution. Functions as a photosensitive material.

[0046]

[Chemical 32] After the development treatment, for the purpose of removing the developer residue in the resin layer and the like, a rinsing treatment with water, alcohol, acetone or the like may be carried out, followed by a baking treatment.

Further, the resin layer having a predetermined pattern after the development processing is heated at a constant temperature. As a result, the solvent component remaining in the coating film is volatilized, the polyamic acid in the resin component is cyclized to change into an imide structure, and the carboxylic acid compound and the photosensitizer are removed. Thus, a pattern of the polyimide film having the following repeating unit (15) is formed.

[0048]

[Chemical 33] In this heating process, room temperature to final heating temperature of 150 to 4
It is desirable to gradually raise the temperature to 50 ° C. and heat. The reason for this is that when the final heating temperature is lower than 150 ° C., when the polyimide having the repeating unit (15) is formed, the polyamic acid in the resin component may not imidize and may partially remain, possibly impairing thermal stability. If the temperature exceeds 450 ° C., the imidized polymer may decompose.

Further, using the polyamic acid composition of the first invention of the present application, a polyimide film is formed by another method in which a coating film is formed, dried and exposed, followed by heat treatment and further development with an alkali developing solution. A pattern may be formed. In this method, the condition of heat treatment applied to the resin layer after exposure is a temperature of about 90 to 200 ° C., preferably 90 to 200 ° C.
It is about 5 seconds to 60 minutes at 140 degreeC. In this case, depending on the type of 1,2-naphthoquinonediazide sulfonic acid ester blended in the composition, in the exposed portion of the resin layer, the ketene (b) generated by the exposure is further combined with active hydrogen in the polyamic acid or polyimide. As a result of the reaction, the polymer chains are cross-linked. Therefore, in this exposed portion, the molecular weight increases and the solubility in the alkali developing solution becomes low. On the other hand, in the unexposed portion of the resin layer, 1,2-naphthoquinonediazide sulfonate is partially decomposed by the heat treatment. Therefore, in the unexposed area,
-The ability of the naphthoquinone diazide sulfonic acid ester originally possessed to suppress the alkali solubility of the polyamic acid is reduced or eliminated, and the naphthoquinone diazide sulfonate is solubilized in an alkali developing solution. Therefore, only the exposed portion of the resin layer remains due to the development process, and a predetermined pattern is formed.

Therefore, the polyamic acid composition of the first invention of the present application complies with the pattern forming process including 1,2-naphthoquinonediazide sulfonic acid ester as a photosensitizer and the above-described heat treatment after exposure. In some cases, the exposed portion may function as a negative photosensitive material that becomes insoluble in a developing solution.

As described above, by using the polyamic acid composition of the first invention of the present application, it is possible to form a passivation film having a sharp relief pattern having excellent heat resistance without using a photoresist. In particular, the dehydration reaction is not required in the step of synthesizing the polyamic acid, so that gelation can be prevented, and the swelling of the pattern by the developing solution can be prevented because the alkaline aqueous solution is used as the developing solution in the developing treatment after the pattern exposure. Therefore, it becomes possible to form a polyimide film pattern with high resolution. Furthermore, since it is possible to polymerize the polyamic acid in the step of synthesizing the polyamic acid, it is possible to obtain a polyimide film pattern having sufficient adhesion to the substrate.

The polyamic acid composition of the first invention of the present application can also be applied to a photoresist for fine processing. In this case, after the resin layer is formed on the substrate, exposed, and developed sequentially as described above, the resin layer having a predetermined pattern obtained as necessary is heated and baked at 90 to 180 ° C. Then, using the pattern of the resin layer formed on the substrate as an etching mask, the substrate is processed by dry etching or wet etching according to a conventional method. The dry etching method is preferable especially when a fine pattern of 3 μm or less is formed. As the wet etching agent at this time, a hydrofluoric acid aqueous solution, an ammonium fluoride aqueous solution or the like is used when the silicon oxide film is an etching target, and a phosphoric acid aqueous solution, an acetic acid aqueous solution, or nitric acid is used when the aluminum is an etching target. An aqueous solution or the like is used, and when a chromium-based film is to be etched, an aqueous cerium ammonium nitrate solution or the like is used. As the dry etching gas, CF ₄ ,
C ₂ F ₆ , CCl ₄ , BCl ₃ , Cl ₂ , HCl, H ₂
Etc., and these gases are used in combination as necessary. The etching conditions determine the concentration of the wet etching agent in the reaction tank, the concentration of the dry etching gas, the reaction temperature, the reaction time, etc., based on the combination of the type of substance forming the fine pattern and the polyamic acid composition. However, the method is not particularly limited. After such etching, the pattern of the resin layer made of the polyamic acid composition of the present invention remaining on the substrate is removed by using a release agent (for example, HE-1 manufactured by Wako Pure Chemical Industries, Ltd.) or oxygen gas plasma. Thus, when the polyamic acid composition of the first invention of the present application is applied to a photoresist for microfabrication, the effect of improving the resolution can be obtained, just as when it is used for forming a polyimide film pattern.

Next, the polyamic acid composition of the second invention of the present application will be described.

The polyamic acid composition of the second invention of the present application is
At least one selected from the group consisting of compounds represented by the following general formulas (1) to (5) and derivatives thereof, a polyamic acid represented by the general formula (11) described above, a dissolution inhibitor, and light irradiation. And a compound capable of generating an acid.

Since the polyamic acid having the repeating unit represented by the general formula (11) and the compounds represented by the general formulas (1) to (5) are the same as those described above, the description thereof is omitted here. Further, also in the polyamic acid composition of the second invention of the present application, the polyimide having the repeating unit represented by the general formula (12) and the polyamic acid having the repeating unit represented by the general formula (A) can be used in combination. It is similar to the first invention. Further, also in the polyamic acid composition of the second invention of the present application, a sensitizer, a dye, a surfactant, an adhesion-imparting agent, and an alkali-soluble resin may be blended, if necessary.

The dissolution inhibitor used in the second invention of the present application is a compound that inhibits the solubility of the polyamic acid in an alkaline developer when the compounds represented by the general formulas (1) to (5) coexist. And a compound having an acid labile group. Specifically, the diazide compounds (P-1) to (P-29), (P-1) to
(P-29) in X is _{-CO 2 C (CH 3) 3} , -
C (CH _{3) 3} or -Si (CH _{3) 3,} compound, and the following structure compound represented by the formula (P-30)
To at least one compound selected from the group consisting of (P-35), that is, an aromatic compound containing a tert-butyl group or a trimethylsilyl group, or phenyl benzoate can be used.

[0057]

[Chemical 34] In the second invention of the present application, the amount of the dissolution inhibitor is preferably 1 to 60% by weight based on the total amount of the polyamic acid and the polyimide that is added as necessary. If the amount of the dissolution inhibitor is too small, the sensitivity of the polyamic acid composition becomes insufficient, while if the amount of the dissolution inhibitor is too large, the properties of the obtained polyimide film deteriorate due to the residue of the dissolution inhibitor after pattern formation. There is a risk. A more preferable amount of the dissolution inhibitor is 5 to 30% by weight.

In the second invention of the present application, examples of the compound which generates an acid upon irradiation with light include CF ₃ SO ₃ ⁻ , p
^{_{-CH 3 phSO 3 -, p-}} NO 2 phSO 3 - (p
h: a phenylene group) and other anion-containing diazonium salts, phosphonium salts, sulfonium salts, iodonium salts and other onium salts, organic halogen compounds, naphthoquinonediazide-4-sulfonic acid esters and the like. Among them, the organic halogen compound is a compound that forms hydrohalic acid upon irradiation with light. Examples of such compounds include US Pat. No. 3,515,552, US Pat. No. 3,779,778 and West German Patent Publication No. 2
The thing disclosed by 243621 is mentioned. Compounds other than organic halogen compounds are disclosed in JP-A-54-74728.
JP-A-55-24113, JP-A-55-7774
No. 2, JP-A-60-3626, JP-A-60-1385.
39, JP-A-56-17345 and JP-A-50-3
No. 6209. A specific example of such a compound is di (p-tert-butylphenyl).
Diphenyliodonium trifluoromethanesulfonate, benzointosylate, orthonitrobenzyl p-
Toluene sulfonate, triphenyl sulfonium trifluoromethane sulfonate, tri (tert-butylphenyl) sulfonium trifluoro methane sulfonate, benzenediazonium p-toluene sulfonate,
4- (di-n-propylamino) -benzonium tetrafluoroborate, 4-p-tolyl-mercapto-2,5
-Diethoxy-benzenediazonium hexafluorophosphate, tetrafluoroborate, diphenylamine-
4-diazonium sulfate, 4-methyl-6-trichloromethyl-2-pyrone, 4- (3,4,5-trimethoxystyryl) -6-trichloromethyl-2-pyrone, 4- (4-methoxystyryl)- 6- (3,3,3
-Trichloropropenyl) -2-pyrone, 2-trichloromethylbenzimidazole, 2-tribromomethylquinone, 2,4-dimethyl-1-tribromoacetylbenzene, 4-dibromoacetylbenzoic acid, 1,4-bis-
Dibromomethylbenzene, tris (dibromomethyl)-
S-triazine, 2- (6-methoxy-naphthyl-2-
Yl) -4,6-bis-trichloromethyl-S-triazine, 2- (naphthyl-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (naphthyl-2)
-Yl) -4,6-bis-trichloromethyl-S-triazine, 2- (benzopyran-3-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-methoxy-anthran-1 -Yl) -4,6-bis-trichloromethyl-S-triazine, 2- (phenanth-9)
-Yl) -4,6-bis-trichloromethyl-S-triazine, 1,2-naphthoquinonediazide-4-sulfonic acid ester and the like.

In the second invention of the present application, the compounding amount of the compound capable of generating an acid upon irradiation with light is 0.0 with respect to the total amount of the polyamic acid and the polyimide compounded as necessary.
It is preferably 1 to 20% by weight, more preferably 0.1 to 10% by weight. If the blending amount is less than 0.01% by weight, sufficient photosensitivity cannot be imparted, while the blending amount is 20%.
If the content exceeds 10% by weight, the coating property on the substrate during pattern formation, the strength of the coating film, and the adhesion to the substrate may deteriorate.

The polyamic acid composition of the second invention of the present application also comprises
Like the first invention of the present application, it is usually used as a varnish in a state of being dissolved in an organic solvent. The formation of a polyimide film pattern using the polyamic acid composition of the second invention of the present application is generally performed through the steps of forming a coating film, drying, exposing, developing with an alkali developing solution, and heat curing.

The state of the resin layer after the exposure step will be described. In the unexposed area of the resin layer, the polyamic acid, which is the resin component in the composition, is insolubilized in the alkaline developer due to the interaction with the dissolution inhibitor. On the other hand, in the exposed portion of the resin layer, an acid is generated from the compound contained in the composition which generates an acid upon irradiation with light, and the dissolution inhibitor is decomposed by this acid, so the dissolution inhibiting ability of the dissolution inhibitor disappears. ,
The solubility in an alkaline developer is increased. Therefore, when the developing treatment with the alkaline developing solution is performed, the exposed portion is dissolved in the developing solution, while the unexposed portion remains and a predetermined pattern is formed. That is, the polyamic acid composition of the second invention of the present application generally functions as a positive photosensitive material in which the exposed portion is solubilized in a developing solution.

The resin layer after exposure was formed on a hot plate,
You may heat-process in an oven etc. at 70-120 degreeC for 30 second-5 minutes, and after promoting the reaction of the acid produced by exposure and a dissolution inhibitor, you may develop. In addition, after the development treatment, a rinsing treatment and a baking treatment may be performed for the purpose of removing the developer residue in the resin layer. Further, the resin layer having a predetermined pattern after development is heated at a constant temperature to be imidized to form a pattern of a polyimide film. The heating conditions are the same as in the case of the first invention of the present application.

Even when the polyamic acid composition of the second invention of the present application as described above is used, a polyimide film pattern can be formed with high resolution just as in the case of the first invention of the present application. Moreover, the compound used in the polyamic acid composition of the second invention of the present invention to generate an acid upon irradiation with light generally generates an acid upon irradiation with a small amount of energy rays, and therefore more than the first invention of the present application. A polyimide film pattern can be formed with high sensitivity.

Next, the polyamic acid composition of the third invention of the present application will be described.

The polyamic acid composition of the third invention of the present application is
It contains a compound represented by the general formulas (1) to (10) and a polyamic acid having a repeating unit represented by the general formula (11). The compounds represented by the general formulas (1) to (10) all have the action of lowering the temperature of the imidization reaction.

Since the polyamic acid having the repeating unit represented by the general formula (11) and the compounds represented by the general formulas (1) to (5) are the same as those described above, the description thereof is omitted here. Further, also in the polyamic acid composition of the third invention of the present application, the polyimide having the repeating unit represented by the general formula (12) and the polyamic acid having the repeating unit represented by the general formula (A) can be used in combination. It is similar to the first invention. Further, also in the polyamic acid composition of the third invention of the present application, a dye, a surfactant, an adhesion-imparting agent, and an alkali-soluble resin may be blended, if necessary.

The compounds represented by formulas (6) to (10) will be described. Examples of the compound represented by the general formula (6) include aminobenzoic acid. Examples of the compounds represented by the general formulas (7) and (8) include aminophenol. Examples of the compound represented by the general formula (9) include phenolsulfonic acid. Examples of the compound represented by the general formula (10) include hydroxybenzaldehyde. Among these compounds, the compound represented by the general formula (9) is particularly preferable because it significantly lowers the temperature of the imidization reaction. In the compounds represented by the general formulas (6) to (10), the hydroxyl group or the amino group is an ortho position, a meta position, or an aromatic ring,
Although it may be bonded to any of the para positions, it is preferably bonded to the meta position or the para position. Further, the derivatives of the compounds represented by the general formulas (6) to (10) means that the hydrogen atom of the aromatic ring of these compounds is further a hydroxyl group, a halogen atom, a cyano group, a nitro group, a methyl group, an ethyl group or a methoxy group. A compound substituted with a group or an amino group.

In the polyamic acid composition of the third invention of the present application, the compounding amount of the compounds represented by the general formulas (1) to (10) and the derivative thereof is 0.05 to 3. It is preferably 0 equivalent.
When the compounding amount of these compounds is less than 0.05 equivalent, a polyimide film cannot be obtained by low temperature heat treatment. vice versa,
When the compounding amount of these compounds exceeds 3.0 equivalents, the viscosity stability during storage deteriorates. Further, the compounding amount of these compounds is more preferably 0.1 to 2.0 equivalents.

In the polyamic acid of the third invention of the present application,
When the carboxylic acid ester or carboxylic acid amide represented by the general formula (5) is mixed, a part or all of the carboxylic acid ester or carboxylic acid amide may be decomposed into a carboxylic acid and a tertiary amine.

Next, formation of a polyimide film as a liquid crystal alignment film using the polyamic acid composition of the third invention of the present application will be described. FIG. 1 is a vertical cross-sectional view of a liquid crystal cell of a liquid crystal display device having a polyimide film as a liquid crystal alignment film.
As shown in the figure, a pair of substrates 1 on which electrodes 2 and a liquid crystal alignment film 3 are formed are arranged so as to face each other, and a liquid crystal 4 is injected into the interior of the pair to form a liquid crystal cell.

The substrate 1 is not particularly limited as long as it is transparent, and specifically, a glass substrate or the like can be used. CVD is performed on such a substrate 1 by using an ordinary transparent conductive material such as tin oxide, indium oxide, and ITO.
The electrode 2 is formed by, for example, Next, the varnish of the polyamic acid composition of the third invention of the present application is applied on the electrode 2 formed on the surface of the substrate 1 and heat-treated. This heat treatment is performed at a temperature of 60 to 180 ° C., which is lower than the conventional temperature, and for 0.5 to 10 hours, which is the same level as the conventional temperature. By this heat treatment, the solvent component remaining in the coating film is volatilized, and the polyamic acid in the resin component is changed to an imide structure by cyclization,
Further, the compounds (1) to (10) and the tertiary amine are removed to form a polyimide film. The thickness of the polyimide film formed at this time may normally be about 20 to 200 nm.

After that, the liquid crystal alignment film 3 is formed by subjecting the obtained polyimide film to a rubbing treatment according to a conventional method.
Further, the electrode 2 and the liquid crystal alignment film 3 are formed on the substrate 1 in this way.
Then, the substrates 1 are arranged at a predetermined interval so that the liquid crystal alignment films 3 on the substrate 1 face each other, and a liquid crystal 4 is injected between the substrates 1 to form a liquid crystal cell.

As described above, when the polyamic acid composition of the third invention of the present application is used, imidization can be carried out at a lower temperature than before, so that the display function of the liquid crystal display device is deteriorated by heat treatment at high temperature as in the prior art. Can be prevented.

Next, the polyamic acid composition of the fourth invention of the present application will be described.

The polyamic acid composition of the fourth invention of the present application is
The compounds containing the compounds represented by the general formulas (1) to (4) and (6) to (10), the polyamic acid having the repeating unit represented by the general formula (11), and the tertiary amine.
The polyamic acid composition of the fourth invention of the present application has the general formulas (1) to (1) having an action of lowering the temperature of the imidization reaction.
0) except that the compound of the general formula (5) is excluded and the tertiary amine is contained as an essential component, and other components are the same as those of the third invention of the present application. Is.

The tertiary amine used in the fourth invention of the present application is not particularly limited, and in addition to those represented by the general formula (13), trimethylamine, triethylamine,
Pyridine, picoline and the like can be used. These tertiary amines have general formulas (1) to (4) and (6) to
When used in combination with the compound represented by (10), it has the effect of further lowering the temperature of the imidization reaction.

The preferable blending amount of the tertiary amine is 0.05 to 0.3 equivalent to the carboxyl group of the polyamic acid,
More preferably, it is 0.05 to 1.0 equivalent. When the compounding amount of the tertiary amine is less than 0.05 equivalents, as in the third invention of the present application, general formulas (1) to (4) and (6) to (10) are used.
The temperature of the heat treatment for obtaining the polyimide film is not so different as compared with the case of using only the compound shown by. On the contrary, when the compounding amount of the tertiary amine exceeds 3.0 equivalents, the residual amount of the tertiary amine in the polyimide film increases, and the liquid crystal display device is caused by the mixing of the tertiary amine in the liquid crystal. The display function of may deteriorate.

As described above, with the polyamic acid composition of the fourth invention of the present application, a polyimide film can be obtained by heat treatment at a lower temperature than that of the third invention of the present application.

[0079]

EXAMPLES The present invention will now be described in more detail by way of examples. Note that these examples are described for the purpose of facilitating the understanding of the present invention, and do not limit the present invention.

Synthesis Example 1 Synthesis of Carboxylic Acid Derivative 41.4 g (0.30 mol) of 4-hydroxybenzoic acid and 2-hydroxybenzoic acid were placed in a nitrogen-substituted 500 ml reaction flask.
124 g (1.4 mol) of N, N-dimethylaminoethanol was added and sufficiently stirred. Next, 0.6 g of a boron trifluoride diethyl ether complex was added as a catalyst to this suspension.
A solution of 10 g of -N, N-dimethylaminoethanol was gradually added. After the addition was completed, the temperature of the reaction solution was slowly raised, and stirring was continued for 6 hours at the reflux temperature of 2-N, N-dimethylaminoethanol. Then excess 2-N,
N-Dimethylaminoethanol was distilled off, and the residual liquid was distilled under reduced pressure to obtain 59 g of a middle distillate (yield 87%).
The infrared absorption spectrum of the compound obtained in FIG. 2, ¹ H
The NMR spectrum is shown in FIG. 3, and the analytical values and calculated values of each element by elemental analysis are shown in Table 1. The compounds obtained from FIG. 2, FIG. 3 and Table 1 are 4-hydroxybenzoic acid 2
It was confirmed to be -N, N-dimethylaminoethyl.

[0081]

[Table 1] Synthesis Example 2 Synthesis of Polyamic Acid A reaction flask equipped with a stir bar, a thermometer, and a dropping funnel was passed with nitrogen gas dried by phosphorus pentoxide,
12.3 g (0.0375 mol) of 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride, 2.73 g (0.0125 mol) of pyromellitic dianhydride and N-methyl-2-pyrrolidone 60 g was injected. Then, these were sufficiently stirred and mixed, and cooled to 10 ° C. Then, 4,4'-diaminodiphenyl ether 9.41
g (0.047 mol) and 0.75 g (0.003 mol) of 1,3-bis- (γ-aminopropyl) -1,1,3,3-tetramethyldisiloxane in N-methyl-2-
It was dissolved in 40 g of pyrrolidone, and this solution was gradually added dropwise to the reaction flask kept at 10 ° C. The mixed solution thus obtained was stirred at 10 to 15 ° C. for 6 hours to synthesize a polyamic acid. N-methyl-of this polyamic acid
Regarding the 2-pyrrolidone solution (concentration 0.5 g / dl),
When the logarithmic viscosity at 30 ° C. was measured, it was 1.2 dl / g
Met.

Synthesis Example 3 Synthesis of Polyimide In a reaction flask similar to Synthesis Example 2, 3,3 ', 4,
4'-benzophenone tetracarboxylic dianhydride 16.
11 g (0.05 mol) and 50 g of N, N-dimethylacetamide were injected. Then, these were sufficiently stirred, mixed, and cooled to 0 ° C. Next, 18.31 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 50 g of N, N-dimethylacetamide, and this solution was kept at 0 ° C. It was gradually dropped into the reaction flask. The mixture thus obtained is stirred at 0 to 10 ° C. for 6 hours,
Polyamic acid was synthesized. The N-methyl-2-pyrrolidone solution of this polyamic acid (concentration: 0.5 g / dl) was measured for logarithmic viscosity at 30 ° C. to find that it was 0.5 dl.
/ G.

Next, 11.2 g (0.11 mol) of acetic anhydride and 0.2 g (0.0025 mol) of pyridine were dissolved in 10 g of N, N-dimethylacetamide, and this solution was dissolved in N-methyl polyamic acid. It was added to the 2-pyrrolidone solution and stirred at room temperature for 18 hours to cyclize the polyamic acid. Furthermore, the solution thus obtained was poured into a 50% by volume aqueous methanol solution to precipitate polyimide. This was washed and dried to obtain polyimide as a solid.

Example 1 To 20 g of the 20 wt% polyamic acid solution obtained in Synthesis Example 2, 2.2 g of 3-hydroxybenzoic acid was added, and the mixture was sufficiently stirred to give a uniform solution. Next, to this solution, the following (P-1
0.8 g of the photosensitizer of 7) (average ester substitution number 3) was added to N-
After adding a solution dissolved in 4 g of methyl-2-pyrrolidone and stirring sufficiently to prepare a uniform solution, the pore size is 0.5 μm.
A varnish of the polyamic acid composition of the present invention was prepared by filtering with a membrane filter of.

[0085]

[Chemical 35] This varnish was applied onto a silicon wafer having a diameter of 4 inches using a spinner, and this was dried at 90 ° C. for 30 minutes on a hot plate to form a resin layer having a thickness of 4.2 μm. After this, an exposure machine (PLA501 manufactured by Canon Inc.)
The surface of the resin layer was irradiated with ultraviolet rays (11.0 mW / cm ² , 405 nm) for 60 seconds by F) through a predetermined mask (irradiation amount 660 mJ / cm ² ). After the exposure, the silicon wafer was developed with an aqueous solution of tetramethylammonium hydroxide having a concentration of 0.595% by weight at room temperature for 75 seconds, and the unexposed portion was hardly corroded.
A fine and clear relief pattern having a line width of 4 μm was obtained. Further, the obtained relief pattern is applied at 90 ° C. for 3
0 minutes, 150 ° C for 30 minutes, 250 ° C for 30 minutes, 3
It was confirmed that a resolution of 4 μm was achieved without impairing the relief pattern even after the polyamic acid in the resin layer was cyclized to polyimide by heat treatment at 20 ° C. for 30 minutes.

A varnish of the same polyamic acid composition was applied onto a silicon wafer having a diameter of 3 inches by using a spinner and dried on a hot plate at 90 ° C. for 20 minutes to give a resin layer having a thickness of 5 μm. Was formed. After this,
This resin layer was subjected to heat treatment at 150 ° C. for 30 minutes, 250 ° C. for 30 minutes, and 320 ° C. for 30 minutes to cyclize the polyamic acid in the resin layer to form a polyimide film.

Then, a 2 mm square incision is cut into the obtained polyimide film with a knife,
When a peeling test was performed using an adhesive cellophane tape, the polyimide film was not peeled off from the silicon wafer at all. Further, even if this polyimide film was exposed to a saturated steam atmosphere at 120 ° C. and 2 atm for 100 hours and then the same test was performed, no peeling of the polyimide film was observed at all.
It was confirmed that this polyimide film had excellent adhesion to a silicon wafer.

Example 2 To 20 g of the 20 wt% polyamic acid solution obtained in Synthesis Example 2, 3.3 g of 2-N, N-dimethylaminoethyl 4-hydroxybenzoate obtained in Synthesis Example 1 was added, and the mixture was thoroughly added. Stir to give a homogeneous solution. Next, a solution prepared by dissolving 0.8 g of the photosensitizer of (P-17) (average ester substitution number 3) in 4 g of N-methyl-2-pyrrolidone was added to this solution and sufficiently stirred to prepare a uniform solution. Then, the varnish of the polyamic acid composition of the present invention was prepared by filtering with a membrane filter having a pore size of 0.5 μm.

This varnish was applied onto a silicon wafer having a diameter of 5 inches by using a spinner and dried at 90 ° C. for 20 minutes on a hot plate to form a resin layer having a thickness of 5.1 μm. After this, the exposure machine (Canon: P
The surface of the resin layer is irradiated with ultraviolet rays (11.0 mW / cm ² , 405 nm) through a predetermined mask by LA501F).
For 30 seconds (irradiation amount 330 mJ / cm ² ). After exposure, this silicon wafer was developed with an aqueous solution of tetramethylammonium hydroxide having a concentration of 0.595% by weight for 60 seconds. As a result, a fine and clear relief pattern with a line width of 4 μm was obtained with almost no corrosion on the unexposed area. It was Furthermore, the obtained relief pattern has 90 ° C.
For 30 minutes, 150 ° C. for 30 minutes, 250 ° C. for 30 minutes, 320 ° C. for 30 minutes, and even after the polyamic acid in the resin layer is cyclized to polyimide, the relief pattern is not damaged, It was confirmed that a resolution of 4 μm width was achieved. Further, a silicon wafer having a diameter of 3 inches was used to perform an adhesion test with the substrate of the polyimide film by the same operation as in Example 1,
No peeling of the polyimide film was observed at all, and it was confirmed that this polyimide film had excellent adhesion to the silicon wafer.

Example 3 20 g of 20% by weight polyamic acid solution as in Example 2
1.5 g of the polyimide powder obtained in Synthesis Example 3 was added to a solution of 2-N, N-dimethylaminoethyl 4-hydroxybenzoate and 3.3 g and sufficiently stirred to obtain a uniform solution. 0.65 g of the following (P-22) photosensitizer (average ester substitution number 5) was added to this uniform solution with N-methyl-2-pyrrolidone 6:
The solution dissolved in g was added and sufficiently stirred to prepare a uniform solution, which was then filtered through a membrane filter having a pore size of 0.5 μm to prepare a varnish of the polyamic acid composition of the present invention. This varnish was spin-coated on a silicon wafer in the same manner as in Example 2 and dried to form a resin layer having a thickness of 5.0 μm, and then ultraviolet rays (11.0 mW / cm ² were applied through a predetermined mask). , 405 nm) for 30 seconds.

After the exposure, the silicon wafer was exposed to a concentration of 2.
38 wt% tetramethylammonium hydroxide aqueous solution (Tama Chemical Co., trade name AD-10) 100 ml, water 1
When developed with a developing solution consisting of 00 ml, 2 ml of N-methyl-2-pyrrolidone and 2 g of (NH ₄ ) ₂ CO ₃ for 130 seconds, the unexposed part was hardly corroded,
A fine and clear relief pattern having a line width of 4 μm was obtained. Further, a silicon wafer having a diameter of 3 inches was used to perform an adhesion test with a substrate of a polyimide film by the same operation as in Example 1. No peeling of the polyimide film was observed, and the polyimide film was confirmed to be a silicon wafer. It was confirmed to have excellent adhesiveness.

[0092]

[Chemical 36] Examples 4 to 9 With the raw material compositions shown in Tables 2 and 3, the above Synthesis Examples 2 and 3 were performed.
Sample N used in Examples 4 to 9 by the same method as
o. 1 to 8 polyamic acids or polyimides were synthesized (in Tables 2 and 3, the N-methyl-2-pyrrolidone solution of N-methyl-2-pyrrolidone having a concentration of 0.5 g / dl of the polyamic acid obtained in the synthesis was used for the logarithmic viscosity at 30 ° C. The solvent used was N-methyl-2-pyrrolidone alone).

Thereafter, in the same manner as in Examples 1 to 3, a polyamic acid solution (N-methyl-2-pyrrolidone solution having a polymer concentration of 20% by weight), an aromatic carboxylic acid compound, a polyimide,
The photosensitizer and N-methyl-2-pyrrolidone were mixed in the respective predetermined amounts shown in Table 4 to prepare varnishes of the polyamic acid compositions of Examples 4 to 9. The abbreviations used in Tables 2 to 4 represent the compounds shown below.

Tetracarboxylic acid dianhydride PMDA: Pyromellitic acid dianhydride BTDA: 3,3 ', 4,4'-Benzophenone tetracarboxylic acid dianhydride 6FDA: 2,2-bis (3,4-dicarboxyl) Phenyl) hexafluoropropane dianhydride DSDA: bis (3,4-dicarboxyphenyl) sulfone dianhydride diamine 6FAP: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane ODA: 4,4 '-Diaminodiphenyl ether BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane BAPH: 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane TSL: 1,3- Bis (γ-aminopropyl) -1,
1,3,3-Tetramethyldisiloxanecarboxylic acid compound PEA-1: 4-hydroxybenzoic acid 2-N, N-dimethylaminoethyl PEA-2: 3-hydroxybenzoic acid 2-N, N-dimethylaminoethyl PEA -3: 2-N, N-dimethylaminoethyl-3-
Hydroxybenzoic acid amide sensitizer (P-17) and (P-22) These varnishes were subjected to film formation, exposure, development and heat treatment on a silicon wafer in the same manner as in Examples 1 to 3 to form a polyimide film. A pattern was formed. Table 4 shows the varnish composition, the initial film thickness during film formation, the light irradiation amount during exposure, the developer concentration during development, the development time, and the resolution of the obtained pattern. As is clear from Table 4, Examples 4-9
The polyimide film pattern was formed with high resolution.

Further, with respect to the polyamic acid compositions of Examples 4 to 9, a polyimide film was formed on a silicon wafer in the same manner as in Example 1 and a peeling test was conducted. In all cases, the polyimide film was not peeled off from the silicon wafer at all. I was not able to admit. Then, the polyimide film was exposed to the same saturated water vapor as in Example 1 and then subjected to the same test. As a result, there was no peeling of the polyimide film, and these polyimide films were found to have high adhesion to a silicon wafer. confirmed.

[0096]

[Table 2]

[Table 3]

[Table 4] Example 10 In the same manner as in Synthesis Example 2 described above, sample No. The polyamic acid of No. 9 was synthesized (Table 5 also shows the logarithmic viscosity at 30 ° C. for the N-methyl-2-pyrrolidone solution of the polyamic acid obtained by the synthesis (concentration: 0.5 g / dl). The organic solvent is N-methyl-2-pyrrolidone alone).

Then, the sample No. 27.8 g of a polyamic acid solution of 9 (18% by weight), 3-hydroxybenzoic acid 2
-N, N-dimethylaminoethyl (PEA-2) 2.0
g, naphthalene-2-carboxylic acid-t as a dissolution inhibitor
1.0 g of ert-butyl ester and 0.3 g of triphenylsulfonium hexafluoroantimonate as a compound that generates an acid upon irradiation with light were mixed, and 2 g of N-methyl-2-pyrrolidone was further added to obtain a uniform solution. Next, this solution was passed through a filter having a pore size of 0.5 μm to remove insoluble matter, to prepare a varnish of the polyamic acid composition of the present invention.

This varnish was spin-coated on a silicon wafer having a diameter of 4 inches and dried at 90 ° C. for 20 minutes to give a thickness of 4 μm.
m resin layer was formed. Then, using an exposure device (PLA-501FA manufactured by Canon Inc.), the surface of the resin layer was exposed to ultraviolet rays (11.
5 mW / cm ² , 405 nm) for 15 seconds. After exposure, 2.3 of tetramethylammonium hydroxide
It was immersed in an 8% by weight aqueous solution for 50 seconds for development, and rinsed by washing with water. After the obtained pattern was dried, the cross section of the pattern was observed by a scanning electron microscope to examine the resolution, and it was found that a fine pattern having a line width of 4 μm was obtained without eroding the unexposed portion. It was Further, when using a silicon wafer having a diameter of 3 inches, an adhesion test with a substrate of a polyimide film was conducted by the same operation as in Example 1, no peeling of the polyimide film was observed, and the polyamic acid composition of the present invention was found. It was confirmed that according to the method, a polyimide film having excellent adhesion to a silicon wafer can be formed.

Examples 11 to 19 Similar to Example 10, the raw material composition shown in Table 5 was used for Example 11
Sample Nos. 10 to 18 polyamic acids were synthesized (Table 5 also shows the logarithmic viscosity at 30 ° C. for the N-methyl-2-pyrrolidone solution of the polyamic acid having a concentration of 0.5 g / dl obtained in the synthesis. The organic solvent is N-methyl-2-pyrrolidone alone).

18% by weight of polyamic acid solution, aromatic carboxylic acid derivative, dissolution inhibitor,
Compounds that generate an acid upon irradiation with light and N-methyl-2
-Pyrrolidone was blended in the predetermined amounts shown in Table 6 to prepare varnishes of the polyamic acid compositions of Examples 11 to 19.

The abbreviations newly used in Tables 5 and 6 are shown below.

Tetracarboxylic dianhydride BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride diamine DDS: 4,4'-diaminodiphenyl sulfone dissolution inhibitor

[Chemical 37] A compound that generates an acid when exposed to light

[Chemical 38] These varnishes were subjected to film formation, exposure, development and heat treatment on a silicon wafer in the same manner as in Examples 1 to 3 to form a polyimide film pattern. Table 6 shows the varnish composition, the initial film thickness during film formation, the light irradiation amount during exposure, the developer concentration during development, the development time, and the resolution of the obtained pattern. As is clear from Table 6, Examples 11 to 11
Also in No. 19, the polyimide film pattern was formed with high resolution. Further, the polyamic acid composition shown in Table 6 is
Since the light irradiation amount for obtaining the resolution equivalent to that in Table 4 is low, it can be seen that the sensitivity is high.

Further, with respect to the polyamic acid compositions of Examples 11 to 19, a polyimide film was formed on a silicon wafer in the same manner as in Example 1 and a peeling test was conducted. In all cases, no peeling of the polyimide film from the silicon wafer was observed. I was not able to admit. Then, the polyimide film was exposed to the same saturated water vapor as in Example 1, and then the same adhesion test was performed. As a result, there was no peeling of the polyimide film, and these polyimide films showed no adhesion to the silicon wafer. It was confirmed to be high.

[0104]

[Table 5]

[Table 6] Example 20 Sample No. Polyamic acid solution of 17 (18% by weight) 29
g, 1.3 g of 3-hydroxybenzoic acid, 1.1 g of naphthalene-2-carboxylic acid-tert-butyl ester as a dissolution inhibitor, and 0.32 g of triphenylsulfonium hexafluoroantimonate as a compound that generates an acid by light irradiation. After mixing, 2 g of N-methyl-2-pyrrolidone was further added to make a uniform solution. Next, this solution is passed through a filter having a pore size of 0.5 μm to remove insoluble matter,
A varnish of the polyamic acid composition of the present invention was prepared.

This varnish was spin-coated on a silicon wafer having a diameter of 4 inches and dried at 90 ° C. for 30 minutes to give a thickness of 3.
An 8 μm resin layer was formed. Then, using an exposure device (PLA-501FA manufactured by Canon Inc.), the surface of the resin layer was exposed to ultraviolet rays (1) through a mask having a predetermined pattern.
It was irradiated with 1.5 mW / cm ² , 405 nm) for 20 seconds. After the exposure, it was immersed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at room temperature for 60 seconds for development, and rinsed by washing with water. After the obtained pattern was dried, the cross section of the pattern was observed with a scanning electron microscope, and it was found that a fine pattern having a line width of 4 μm was obtained without eroding the unexposed portion. Further, using a silicon wafer having a diameter of 3 inches, an adhesion test with a substrate of a polyimide film was conducted by the same operation as in Example 1, and no peeling of the polyimide film was observed. It was confirmed to have excellent adhesiveness.

Example 21 In a reaction flask similar to Synthesis Example 2, 3,3 ', 4,
4'-benzophenone tetracarboxylic dianhydride 6.4
5 g (0.02 mol) and 25 g of N, N-dimethylacetamide were charged, sufficiently stirred and cooled to 0 ° C.
Then, to this suspension, 7.32 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
(0.02 mol) of N, N-dimethylacetamide 30
The solution dissolved in g was gradually added dropwise. 0-1 after dropping
Stirring was continued at 0 ° C. for 8 hours to obtain a polyamic acid. The obtained polyamic acid had N-methyl-concentration of 0.5 g / dl.
The logarithmic viscosity at 30 ° C. of the 2-pyrrolidone solution was 0.72 dl / g.

Next, 4.5 g of acetic anhydride and 0.5 g of triethylamine were added to this solution, and stirring was continued at 10 ° C. for 4 hours. This reaction liquid was mixed with 10 l of methanol and 10 l of water.
Was injected into the mixture to obtain a polymer precipitate. This polymer was separated by filtration, washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide.

2.5 g of the obtained polyimide, sample No.
14 g of a polyamic acid solution of 9; 1.7 g of 2-hydroxybenzoic acid, 2-N, N-dimethylaminoethyl; 1.3 g of naphthalene-2-carboxylic acid-tert-butyl ester as a dissolution inhibitor; As a compound to be mixed, 0.4 g of triphenylsulfonium hexafluoroantimonate was mixed, and 12 g of N, N-dimethylacetamide was further added to obtain a uniform solution. Next, this solution was passed through a 0.5 μm filter to remove insoluble matter, to prepare a varnish of the polyamic acid composition of the present invention. This varnish was subjected to film formation, exposure, development, and heat treatment under exactly the same conditions as in Example 1 to form a polyimide film pattern. As a result, a relief pattern having a film thickness of 4 μm and a thickness of 4 μm was obtained.

Further, in the same manner as in Example 1, a polyimide film was formed on a silicon wafer and a peeling test was conducted.
No peeling of the polyimide film was observed from the silicon wafer. Then, the polyimide film was exposed to saturated water vapor as in Example 1, and the same adhesion test was performed. As a result, the polyimide film was not peeled off at all, and the polyimide film had high adhesion to the silicon wafer. Was confirmed.

Example 22 2.18 g (0.01 mol) of pyromellitic dianhydride and 2.48 g (0.0 mol) of 3-hydroxybenzyl alcohol
(2 mol) and N-methyl-2-pyrrolidone (10 ml) were stirred and mixed at room temperature for 24 hours to obtain pyromellitic acid di (3-hydroxybenzyl) ester.
Next, a solution prepared by dissolving 2.00 g (0.01 mol) of 4,4'-diaminodiphenyl ether in 10 ml of N-methyl-2-pyrrolidone was added to this solution, and further 4.53 g (0.022 g of dicyclohexylcarbodiimide). (Mol) was dissolved in N-methyl-2-pyrrolidone, and the mixture was stirred at 5 ° C. for 7 hours. The formed precipitate was removed by vacuum filtration. The obtained filtrate was poured into 600 ml of water to precipitate a polyamic acid derivative having a repeating unit represented by the general formula (A), filtered, washed with water, and dried.

Next, 20 g of the 20% by weight polyamic acid solution obtained in Synthesis Example 2 and 2.5 g of the above polyamic acid derivative,
3.8 g of 2-N, N-dimethylaminoethyl 3-hydroxybenzoate and 10 g of N-methyl-2-pyrrolidone
Were stirred and mixed to form a uniform solution. Next, 1.3 g of the photosensitizer (P-17) was added to this solution.
A solution dissolved in 6 g of 2-pyrrolidone was added, and the mixture was sufficiently stirred to prepare a uniform solution, which was then filtered through a membrane filter having a pore size of 0.5 μm to prepare a varnish of the polyamic acid composition of the present invention. did.

When this varnish was exposed and developed in the same manner as in Example 2, a resolution of 3 μm width was obtained. Further, when a peeling test was performed by forming a polyimide film on a silicon wafer having a PSG film formed thereon, no peeling of the polyimide film was observed and it was confirmed that the adhesion was high.

Comparative Example 1 3,3 ', 4,4' were placed in the same reaction flask as in Synthesis Example 2.
-Benzophenone tetracarboxylic dianhydride 12.09
g (0.0375 mol), pyromellitic dianhydride 2.
73 g (0.0125 mol) and 60 g N-methyl-2-pyrrolidone were injected. Then, these were sufficiently stirred and mixed, and cooled to 5 ° C. Then, 17.22 g (0.047 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 1,3
A solution of 0.75 g (0.003 mol) of -bis (γ-aminopropyl) -1,1,3,3-tetramethyldisiloxane dissolved in 20 g of N-methyl-2-pyrrolidone and 20 g of tetrahydrofuran was added at 5 ° C. It was dripped into the said reaction flask hold | maintained at 15 minutes. The mixed liquid thus obtained was stirred at 5 to 15 ° C. for 6 hours to synthesize a polyamic acid. The N-methyl-2-pyrrolidone solution of this polyamic acid having a concentration of 0.5 g / dl had an inherent viscosity of 0.62 dl / g at 30 ° C.

Next, a mixed solution of 11.2 g (0.11 mol) of acetic anhydride, 0.25 g (0.0025 mol) of triethylamine and 20 g of N-methyl-2-pyrrolidone was added to the polyamic acid solution at room temperature. Stir for 4 hours. The solution thus obtained was poured into a 50% by volume aqueous methanol solution to precipitate polyimide. Wash this,
The polyimide produced by drying was obtained as a solid.

Then, a solution prepared by dissolving 5 g of the obtained polyimide and 1 g of the photosensitizer of (P-17) in 20 g of N-methyl-2-pyrrolidone was filtered through a membrane filter having a pore size of 0.5 μm. A photosensitive polyimide varnish was prepared.

This varnish was spin-coated on a silicon wafer having a diameter of 5 inches and dried on a hot plate at 90 ° C. for 20 minutes to form a resin layer having a thickness of 4.9 μm. Then, using the same exposure apparatus and mask as in Example 1, irradiation with ultraviolet rays (11.0 mW / cm ² , 405 nm) for 30 seconds (irradiation amount 330 mJ / cm ² ) was performed, and 1.19% by weight of tetramethylammonium was used. When developed with an aqueous solution of hydroxide for 50 seconds, a clear relief pattern having a line width of 5 μm was obtained.

Also, a varnish of the same photosensitive polyimide was used with a diameter of 3
It was spin-coated on an inch silicon wafer and dried on a hot plate at 90 ° C. for 20 minutes to form a resin layer having a thickness of 5 μm. Then, under nitrogen gas flow, 1
50 ° C for 30 minutes, 250 ° C for 30 minutes, 320 ° C for 3 minutes
Heat treatment was performed for 0 minutes.

Then, the resin layer was cut by 2 mm with a knife.
When a corner-sized cut-out was made and a peeling test was performed using an adhesive cellophane tape, 7 out of 100 resin layers were peeled from the silicon wafer. The resin layer was exposed to a saturated steam atmosphere at 120 ° C. and 2 atm.
When the same test was conducted after the exposure for 00 hours, all the resin layers were peeled off.

Example 23 4.92 g (0.0225 mol) of pyromellitic dianhydride, 21.76 g (0.0675 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride,
16.4 g of 4,4'-diaminodiphenyl ether
(0.0828 mol), 1,3-bis (γ-aminopropyl) -1,1,3,3-tetramethyldisiloxane 1.34 g (0.0054 mol) and 2- (4-aminophenyl)- 0.82 g (0.0036 mol) of 2- (4-hydroxyphenyl) propane was added to N-methyl-2-
Polyamic acid was obtained by reacting in 160 g of pyrrolidone. The N-methyl-2-pyrrolidone solution of this polyamic acid (concentration: 0.5 g / dl) had an inherent viscosity of 0.64 dl / g at 30 ° C. Next, 10 g of this polyamic acid solution (polyamic acid concentration: 22% by weight) and 1.28 g of 2-N, N-dimethylaminoethyl 3-hydroxybenzoate were added to 50 g of N-methyl-2-pyrrolidone, and the mixture was thoroughly mixed at room temperature. After stirring to make a homogeneous solution,
A varnish of a polyamic acid composition was prepared by filtering with a 2 μm filter. Apply this varnish on a KBr plate and
The imidation ratio of the polyamic acid determined from the IR spectrum of the film heat-treated at 10 ° C. for 1 hour was 97%. on the other hand,
For polyamic acid varnishes containing no 2-N, N-dimethylaminoethyl 3-hydroxybenzoate, 110 ° C.
After the heat treatment for 1 hour, the imidization ratio was 0.1%.

The resulting varnish was applied by screen printing on a glass substrate having an indium oxide electrode formed thereon, and then heat-treated at 140 ° C. for 1 hour to cyclize the polyamic acid in the varnish to 0.08 μm. Of polyimide film was formed. A rubbing machine having a roll in which a cloth made of nylon was wound around this polyimide film was used to perform rubbing treatment at a roll speed of 450 RPM and a stage moving speed of 1 cm / sec. Next, the peripheral edges of the pair of substrates having the rubbing-treated liquid crystal alignment film were subjected to 180 ° C. using an epoxy adhesive containing beads as spacers.
Was heated and pressed to cure the adhesive, and a liquid crystal cell having a cell thickness of 15 μm was produced. A nematic liquid crystal (ZLI-1565 manufactured by Merck & Co., Inc.) was injected from the liquid crystal injection port, the injection port was sealed with a photo-curing epoxy resin, and a polarizing plate was attached to both outer surfaces of the substrate to prepare a test liquid crystal display device. Manufactured. When the initial alignment of the liquid crystal was examined using this test liquid crystal display device, the liquid crystal showed good alignment under any of the conditions.

Example 24 Sample No. 2-hydroxybenzoic acid (1.06 g) was added to a 5 wt% N-methyl-2-pyrrolidone solution (20 g) of the polyamic acid solution in Example 2, and the mixture was sufficiently stirred to form a uniform solution, which was then filtered through a 0.2 μm filter. To prepare a varnish. This varnish was applied onto a KBr plate and heat-treated at 110 ° C. for 1 hour. The imidation ratio of the polyamic acid was 89%, which was determined from the IR spectrum of the film. A test liquid crystal display device was manufactured in the same manner as in Example 23, and the initial alignment property of the liquid crystal was examined using this test liquid crystal display device. The liquid crystal showed good alignment property under any conditions.

Example 25 Sample No. 20 g of N-methyl-2-pyrrolidone solution of polyamic acid of 2 (5% by weight) was mixed with 1.06 g of 3-hydroxybenzoic acid, and 0.5 g of triethylamine was added.
Was added and sufficiently stirred to form a uniform solution, which was then filtered through a 0.2 μm filter to prepare a varnish. This varnish was applied on a KBr plate and heat-treated at 110 ° C. for 1 hour. The imidation ratio of polyamic acid determined from the IR spectrum of the film was 97%. A test liquid crystal display device was manufactured in the same manner as in Example 23, and the initial alignment property of the liquid crystal was examined using this test liquid crystal display device. The liquid crystal showed good alignment property under any conditions.

Example 26 Nitrogen gas dried with phosphorus pentoxide was passed into a reaction flask equipped with a stir bar, a thermometer and a dropping funnel, and 19.64 g (0.09 mol) of pyromellitic dianhydride and N were added. 80 g of methyl-2-pyrrolidone were injected. Then, these were sufficiently stirred and mixed, and cooled to 10 ° C. Then 4,4'-diaminodiphenyl ether 1
6.95 g (0.0846 mol) and 1,3-bis-
1.34 g (0.0054 mol) of (γ-aminopropyl) -1,1,3,3-tetramethyldisiloxane was added to N-
This was dissolved in 93 g of methyl-2-pyrrolidone, and this solution was gradually added dropwise to the reaction flask kept at 10 ° C. The thus-obtained mixed solution was stirred at 10 to 15 ° C. for 6 hours, and sample No. Nineteen polyamic acids were synthesized.
This polyamic acid has a concentration of 0.5 g / dl of N-methyl-
When the logarithmic viscosity at 30 ° C. of the 2-pyrrolidone solution was measured, it was 0.83 dl / g.

Then, 10 g of the obtained polyamic acid solution (polyamic acid concentration: 18% by weight) and 1.2 g of 4-hydroxyphenylacetic acid were added to N-methyl-2-pyrrolidone 4
It was added to 0 g and sufficiently stirred at room temperature to form a uniform solution, which was then filtered through a 0.2 μm filter to prepare a varnish of the polyamic acid composition. The IR spectrum of a film obtained by applying this varnish on a KBr plate and heat-treating at 100 ° C. for 1 hour is shown in FIG. The imidization ratio of the polyamic acid determined from this IR spectrum was 98%. On the other hand, in the polyamic acid varnish containing no 4-hydroxyphenylacetic acid, the imidation ratio after heat treatment at 100 ° C. for 1 hour was 0.1%.

Next, a varnish of the polyamic acid composition was applied by screen printing onto a glass substrate on which an ITO electrode was formed, and then heat-treated at 130 ° C. for 1 hour to cool the polyamic acid in the varnish. Film thickness of 80 nm
Of polyimide film was formed. A rubbing machine having a roll in which a cloth made of nylon was wound around this polyimide film was used to perform rubbing treatment at a roll speed of 450 RPM and a stage moving speed of 1 cm / sec. Next, the peripheral edges of the pair of substrates having the rubbing-treated liquid crystal alignment film are
An epoxy-based adhesive containing beads as a spacer was used to heat and pressure bond at 180 ° C. to cure the adhesive, thereby producing a liquid crystal cell having a cell thickness of 15 μm. A nematic liquid crystal (ZLI-1565 manufactured by Merck & Co., Inc.) was injected from the liquid crystal injection port, the injection port was sealed with a photo-curing epoxy resin, and a polarizing plate was attached to both outer surfaces of the substrate to prepare a test liquid crystal display device. Manufactured. When the initial alignment of the liquid crystal was examined using this test liquid crystal display device, the liquid crystal showed good alignment.

Examples 27 to 34 Using the tetracarboxylic dianhydrides and diamines shown below, using the raw material compositions shown in Tables 7 and 8, and in the same manner as in Example 26, sample Nos. 20 to 26 polyamic acids were synthesized (Tables 7 and 8 show N-methyl-2-pyrrolidone solutions of the polyamic acids obtained by the synthesis (concentration: 0.5 g
/ Dl), the logarithmic viscosity at 30 ° C. is also shown. The organic solvent used was N-methyl-2-pyrrolidone alone).

Tetracarboxylic dianhydride BTDA: 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride 6FDA: 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride diamine ODA: 4,4′-diaminodiphenyl ether PA: p-Phenylenediamine BAPB: 4,4′-bis (4-aminophenoxy) biphenyl BAPH: 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane TSL: 1,3-bis (γ- Aminopropyl) -1,
1,3,3-tetramethyldisiloxane

[Table 7]

[Table 8] Hereinafter, in the same manner as in Example 26, the polyamic acid solution, the aromatic compound shown below and N-methyl-2-pyrrolidone were blended in the predetermined amounts shown in Table 9, to prepare a polyamic acid composition. Table 9 shows the imidization temperature and the imidization ratio of these polyamic acid compositions. Moreover, after exposing some of the polyamic acid composition to the liquid crystal display device manufactured by the same method as in Example 26 for 100 hours in the initial alignment of the liquid crystal and the atmosphere of 70 ° C. and 90% relative humidity. The liquid crystal orientation (reliability test) was examined. The results are also shown in Table 9.

Aromatic compound AR-1: 4-hydroxyphenylacetic acid AR-2: 4-hydroxybenzoic acid AR-3: 4-aminophenol AR-4: 4-aminobenzoic acid AR-5: 2-hydroxy-6-naphthoic acid

[Table 9] Further, the sample No. The polyamic acid solution of 19 was spin-coated on a silicon wafer having a diameter of 4 inches to form a resin layer having a thickness of 5 μm. After drying at 90 ℃ for 60 minutes, 150
Heat treatment was performed at 60 ° C. for 60 minutes and at 300 ° C. for 60 minutes to obtain a polyimide film (A) having an imidization ratio of 98%.

On the other hand, sample No. 2.4 g of 4-hydroxyphenylacetic acid was mixed with 20 g of the polyamic acid solution of 19 (polyamic acid concentration: 18% by weight), and the mixture was sufficiently stirred to form a uniform solution, and then the insoluble matter was removed through a 0.5 μm filter. This solution was applied on a silicon wafer having a diameter of 4 inches to a film thickness of 5 μm in the same manner as above and heat-treated at 90 ° C. for 60 minutes and 110 ° C. for 60 minutes to obtain a polyimide film (B) having an imidization ratio of 99%.

Then, a 2 mm square incision-like cut was made in this polyimide film with a knife, and a peeling test was conducted using an adhesive cellophane tape.
No peeling of the polyimide film was observed in both A and B. In addition, when the silicon wafer coated with this polyimide film was exposed to a saturated steam atmosphere at 120 ° C. and 2 atm for 100 hours, the same test was performed.
32 pieces out of 00 pieces were peeled from the surface of the silicon wafer, but in the case of B, peeling was not recognized at all.

Example 35 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride 22.212 g (0.05 mol) was kept at a temperature of 10 ° C. (4-
Aminophenyl) hexafluoropropane 14.708 g
(0.044 mol), 1,3-bis (γ-aminopropyl) -1,1,3,3-tetramethyldisiloxane 1.
491 g (0.006 mol), and N-methyl-2-
A solution consisting of 170 g of pyrrolidone was gradually added over 15 minutes, and then stirred at 10 to 15 ° C for 7 hours. The polyamic acid solution thus synthesized has an inherent viscosity of 0.84 dl
/ G. Next, 10 g of this polyamic acid solution, 4
-0.85 g of phenolsulfonic acid and N-methyl-
2-Pyrrolidone (10 g) was mixed and stirred to form a uniform solution, which was then filtered through a 0.2 μm filter to prepare a varnish. This varnish was applied on a KBr plate, and 100 ° C.
The IR spectrum of the film heat-treated for 5 hours was measured. The imidization ratio of the polyamic acid determined from this IR spectrum was 91%.

Further, when the initial alignment of the liquid crystal was examined by using the test liquid crystal display device in the same manner as in Example 26, good alignment was shown under any conditions.

Example 36 10 g of the polyamic acid solution obtained in Example 35, 0.6 g of p-hydroxybenzaldehyde, and 0.3% of triethylamine.
4 g and 10 g of N-methyl-2-pyrrolidone were mixed and stirred to form a uniform solution, which was then filtered through a 0.2 μm filter to prepare a varnish. Next, the imidization ratio of the polyamic acid was determined in the same manner as in Example 35.
It was 2%. Moreover, when the initial alignment of the liquid crystal was examined, good alignment was shown under any conditions.

[0134]

As described above in detail, according to the present invention, a polyamic acid composition capable of forming a polyimide film pattern having a high degree of polymerization and a high adhesion to a substrate with a high resolution, and a comparatively A polyamic acid composition that is imidized by heat treatment at a low temperature can be obtained.

[Brief description of drawings]

FIG. 1 is a partial vertical cross-sectional view of a liquid crystal cell of a liquid crystal display device.

FIG. 2 is an infrared absorption spectrum diagram of the carboxylic acid derivative obtained in Synthesis Example 1 of the present invention.

FIG. 3 is a ¹ HNMR spectrum diagram of a carboxylic acid derivative obtained in Synthesis Example 1 of the present invention.

FIG. 4 is an infrared absorption spectrum diagram of the polyimide film obtained in Example 26 of the present invention.

[Explanation of symbols]

1 ... Substrate, 2 ... Electrode, 3 ... Liquid crystal alignment film, 4 ... Liquid crystal.

Continuation of front page (56) Reference JP-A-58-160348 (JP, A) JP-A-60-135935 (JP, A) JP-A-61-285254 (JP, A) JP-A-63-100426 (JP , A) JP 2-247617 (JP, A) JP 3-56962 (JP, A) JP 3-259148 (JP, A) JP 4-284455 (JP, A) JP 6-161102 (JP, A) JP-A-6-172646 (JP, A) JP-A-6-214390 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 79/00 -79/08 C08K 3/00-13/08

Claims (12)

(57) [Claims] 1. A compound represented by any one of the following general formulas (1) to (5) and a hydrogen atom of an aromatic ring of these compounds is hydroxy.
Group, carboxyl group, halogen atom, cyano group, nitro
Group, methyl group, ethyl group, methoxy group or amino group
At least one member selected from the group consisting of substituted compounds, and A polyamic acid represented by the following general formula (11): A polyamic acid composition comprising a photosensitizer. 2. The polyamic acid composition according to claim 1, wherein the photosensitizer is a diazide compound. 3. A polyamic acid derivative represented by the following general formula (A): The polyamic acid composition according to claim 1, further comprising: 4. A polyimide represented by the following general formula (12): The polyamic acid composition according to claim 1, further comprising: 5. The compounds represented by the following general formulas (1) to (5) and the hydrogen atom of the aromatic ring of these compounds is hydroxy.
Group, carboxyl group, halogen atom, cyano group, nitro
Group, methyl group, ethyl group, methoxy group or amino group
At least one member selected from the group consisting of substituted compounds, and A polyamic acid represented by the following general formula (11): Suppressing the solubility of polyamic acid in alkaline developers,
It contains a dissolution inhibitor composed of a compound having a group unstable to oxalic acid and a compound which generates an acid upon irradiation with light, and the compounding amount of the components represented by the general formulas (1) to (5) is polyamic acid. The amount of the dissolution inhibitor is 1 to 60% by weight of the polyamic acid, and the amount of the compound that generates an acid upon irradiation with light is the polyamic acid. 0.01 to 20% by weight of the polyamic acid composition. 6. The dissolution inhibitor is a diazide compound, t
The polyamic acid composition according to claim 5, which is at least one selected from the group consisting of an aromatic compound having an ert-butyl group or a trimethylsilyl group, and phenyl benzoate. 7. The compound which generates an acid upon irradiation with light is at least one selected from the group consisting of onium salts, organic halogen compounds, and naphthoquinonediazide-4-sulfonic acid esters. The polyamic acid composition according to 5. 8. A polyimide represented by the following general formula (12): The polyamic acid composition according to claim 5, which comprises: 9. The compounds represented by the following general formulas (1) to (10) and the hydrogen atom of the aromatic ring of these compounds is hydroxy.
Group, carboxyl group, halogen atom, cyano group, nitro
Group, methyl group, ethyl group, methoxy group or amino group
At least one member selected from the group consisting of substituted compounds, and [Chemical 6] Polyamic acid represented by the following general formula (11): The content of the components represented by the general formulas (1) to (10) is 0.05 to 3.0 with respect to the carbonyl group of the polyamic acid.
A polyamic acid composition, which is an equivalent amount. 10. A following general formula (1) to (4) and (6) a compound represented by - (10) as well as compounds thereof
The hydrogen atom of the aromatic ring of the substance is a hydroxyl group, a carboxyl group, or a halo.
Gen atom, cyano group, nitro group, methyl group, ethyl group,
At least one selected from the group consisting of compounds substituted with a methoxy group or an amino group; [Chemical 9] A polyamic acid represented by the following general formula (11): A tertiary amine is contained, and the blending amount of the components represented by the general formulas (1) to (4) and (6) to (10) is 0.05 to 3.0 with respect to the carbonyl group of the polyamic acid. The polyamic acid composition is equivalent, and the compounding amount of the tertiary amine is 0.05 to 3.0 equivalents with respect to the carbonyl group of the polyamic acid. 11. An electrode and a liquid crystal alignment film are formed on the surfaces of a pair of transparent substrates, respectively, and the liquid crystal alignment film is placed inside.
In a liquid crystal device in which a pair of transparent substrates are opposed to each other and liquid crystal is sealed in a gap between them, the liquid crystal alignment film is formed.
Alternatively, a liquid crystal element comprising a polyimide film obtained by imidizing the polyamic acid composition according to 10. 12. A compound represented by the general formula (1) to (5).
The blending amount of the components is based on the carbonyl group of the polyamic acid.
The amount of the photosensitizer blended is 1 to 50% by weight of the polyamic acid.
The polyamid according to claim 1 or 2, wherein
Acid composition.