JPH08113708A - Photosensitive polymer composition - Google Patents

Abstract

PURPOSE: To obtain a photosensitive polymer composition having high sensitivity, patterning accuracy of high resolution, neither reducing solubility nor causing crack of resin in long-term leaving to stand/preservation in a film-forming process, by blending a polyamic acid with a uracil derivative, a bisazide compound and a specific amine compound. CONSTITUTION: This composition comprises (A) a polyamic acid of formula I (R<1> is a tetrafunctional aromatic group; R<2> is a bifunctional aromatic group), (B) a uracil derivative of formula II (R<3> is H, CH3 , COOH or COOCH3 ), (C) a bisazide compound of the formula N3 - -R<4> -N3 (R<4> is a bifunctional or trifunctional organic group) and (D) an amine compound of formula III (R<5> to R<7> are each H, a lower alkyl, phenyl or a lower alkenyl; R<3> is an alkylene) [e.g. 2-(N,N-dimethylamino)ethyl acrylate] as essential components. For example, 100 pts.wt. of component A is preferably blended with 1-50 pts.wt. of the component B, 0.1-50 pts.wt. of the component C and 1-100 pts.wt. of the component D.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive polymer composition which is highly sensitive and has high resolution and is capable of stable pattern formation, and a pattern forming method using the same.

[0002]

2. Description of the Related Art Conventionally, a photosensitive polymer composition which is a heat-resistant polymer has been prepared by adding a carbon-carbon dimer which can be dimerized or polymerized by actinic radiation to polyamic acid which is a precursor of a polyimide resin as a component thereof. A composition in which a compound containing a heavy bond, an amino group or a quaternized salt thereof is introduced through an ionic bond (JP-B-54-145794), and a composition containing a bisazide compound as a photocrosslinking agent ( Japanese Patent Publication 57-
168942), a composition in which a photosensitive group is introduced into the carboxyl group of polyamic acid by an ester bond (Japanese Patent Publication No. 55-3).
No. 0207, Japanese Patent Publication No. 55-41422) and the like are proposed.

[0003]

However, a large amount of actinic radiation exposure is required to form a pattern with the composition (1), and the sensitivity is low for practical use, and the composition (1) has a low sensitivity after the polyamic acid film is formed. If it is left for a long time, the polyamic acid film absorbs moisture and its solubility is lowered, so that stable patterning cannot be formed. Similarly, in the case of developing a polyamic acid film left for a long time with a general aprotic polar solvent such as N-methyl-2-pyrrolidone, resin cracks are generated on the entire surface of the polyamic acid film during development, In practical application, there were great restrictions on the patterning formation process. That is, the compositions (1) and (2) have the drawback that it is necessary to complete the process from application of the polyamic acid on the substrate to pattern formation in several hours.

In addition, the composition (1) has the drawback that the polyimide resin in the exposed area is eluted during development and high-precision patterning is not formed, which not only complicates the manufacturing process of the resin itself, but also introduces a photosensitive group. However, there is a drawback that chlorine ions remain in the final polyimide resin film obtained due to the dehydrochlorination reaction, and the electrical characteristics and the reliability of the device using this resin are poor.

The present invention has been made in order to solve the above-mentioned drawbacks and has a high sensitivity and a high resolution, and after the formation of the polyamic acid film, the solubility of the polyamic acid is lowered due to the absorption of moisture of the polyamic acid after being left for a long time, and at the time of development. The present invention aims to provide a highly heat-resistant photosensitive polymer composition which does not generate resin cracks and has an extremely stable patterning forming ability, and a highly reliable patterning forming method using the same.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that the above object can be achieved by using a resin composition described later. It is completed.

That is, the present invention provides (A) a polyamic acid represented by the following general formula:

[0008]

[Chemical 9] (However, in the formula, R ¹ represents a tetravalent aromatic group and R ² represents a divalent aromatic group.) (B) A uracil derivative represented by the following general formula:

[0009]

[Chemical 10] (However, in the formula, R ³ is —H, —CH ₃ , —COOH, —C
OOCH ₃ represents a) (C) azido compounds represented by the following general formula and

[0010]

Embedded image N ₃ —R ⁴ —N ₃ (wherein R ⁴ represents a divalent or trivalent organic group) (D) An amine compound represented by the following general formula

[0011]

[Chemical 12] (Wherein R ⁵ , R ⁶ , and R ⁷ represent hydrogen, a lower alkyl group, a phenyl group, or a lower alkenyl group, and R ⁸ represents an alkylene group, which may be the same or different) It is a photosensitive polymer composition characterized by the following. Further, this photosensitive polymer composition is applied on a substrate and dried to expose a photosensitive substrate obtained by irradiating with an actinic ray, followed by heat treatment, and then the unexposed portion is subjected to an aprotic polar solvent. It is a pattern forming method characterized by dissolving and removing with.

The present invention will be described in detail below.

The (A) polyamic acid used in the present invention is obtained by the reaction of an acid component and a diamine component.
This is represented by the above general formula 9. It may be a repeating unit of the general formula, or another repeating unit, or a copolymer with another repeating unit. It is desirable to select the combination of these acid component and diamine component in consideration of heat resistance, mechanical properties, electrical properties, etc. of the polyimide film after final curing.

Examples of the acid component of polyamic acid include
Pyromellitic acid, 1,2,3,4-benzenetetracarboxylic acid,
1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3 ′, 4,4′- Bicyclohexyl tetracarboxylic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic acid, 3,3 ', 4,4'- Biphenyl tetracarboxylic acid, 2,3,3 ', 4'-biphenyl tetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid,
2,3,3 ', 4'-benzophenone tetracarboxylic acid, 3,
3 ', 4,4'-biphenyl ether tetracarboxylic acid (4,4
′ -Oxydiphthalic acid), 2,3,3 ′, 4′-biphenyl ether tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxy) Phenyl) propane, bis (3,4-dicarboxyphenyl)
Methane, bis (2,3-dicarboxyphenyl) methane, 1,
1-bis (2,3-dicarboxyphenyl) ethane, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid, 2, 3,3 ', 4'-diphenylsulfone tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid Carboxylic acid, 3,4,9,10-tetracarboxyperylene, 2,
2-bis [4- (3,4-dicarboxyphenoxy) phenyl]
Examples thereof include anhydrides such as propane and 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane, or lower alkyl esters thereof. These may be used alone or as a mixture. it can.

As the diamine component of polyamic acid,
For example, 4,4'-diaminodiphenylmethane, 3,3'-
Dimethyl-4,4'-diaminodiphenylmethane, 3,3 ',
5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl- Four,
4'-diaminodiphenylmethane, 4,4'-methylenebis (cyclohexylamine), 3,3'-dimethyl-4,4 '
-Diaminodicyclohexylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 3,3'-diethoxy-4,4'-diaminodiphenylmethane, bis (3-aminophenyl) ether, bis (4-aminophenyl) ) Ether, 3,4'-diaminodiphenyl ether, 3,3'-
Diethyl-4,4'-diaminodiphenyl ether, 3,3 '
-Dimethoxy-4,4'-diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl] ether,
3,3′-dimethyl-4,4′-diaminodiphenyl sulfone, 3,3′-diethyl-4,4′-diaminodiphenyl sulfone, 3,3′-dimethoxy-4,4′-diaminodiphenyl sulfone, 3, 3'-diethoxy-4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-diethyl-4,4'-diaminodiphenylpropane, 3,3 '-Dimethoxy-4,4'-diaminodiphenylpropane,3,3'-diethoxy-4,4'-diaminodiphenylpropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3- Bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 4,4′-diaminodiphenyl sulfide, 3,3 ′
-Dimethyl-4,4'-diaminodiphenyl sulfide,
3,3'-diethyl-4,4'-diaminodiphenyl sulfide, 3,3'-dimethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfide, 2, 2'-diaminodiethyl sulfide, 2,4'-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 1,2-bis (4-aminophenyl) Ethane, 1,1-bis (4-aminophenyl) ethane, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, o-toluidine sulfone, bis [4- (4-
Aminophenoxy) phenyl] sulfone, bis [4- (3-
Aminophenoxy) phenyl] sulfone, 4,4′-diaminodibenzyl sulfoxide, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) ethylphosphine oxide, bis ( 4-aminophenyl) phenylphosphine oxide, bis (4-aminophenyl) -N-phenylamine, bis (4-aminophenyl) -N-methylamine, 1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 1 , 5-Diaminonaphthalene, 1,6-Diaminonaphthalene, 1,7-Diaminonaphthalene, 1,8-Diaminonaphthalene, 2,3-Diaminonaphthalene, 2,6-Diaminonaphthalene, 1,4-Diamino-2-methyl Naphthalene, 1,5-diamino
-2-methylnaphthalene, 1,3-diamino-2-phenylnaphthalene, 9,9-bis (4-aminophenyl) fluorene,
4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl,
3,3'-Dimethyl-4,4'-diaminobiphenyl, 3,4 '
-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-bis (4-
Aminophenoxy) biphenyl, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,
5-diaminotoluene, 1,3-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dichlorobenzene, 1-methoxy-2,4-diaminobenzene, 1,3-diamino-4, 6-dimethylbenzene, 1,4-diamino-2,5-dimethylbenzene, 1,
4-diamino-2-methoxy-5-methylbenzene, 1,4-diamino-2,3,5,6-tetramethylbenzene, 1,4-bis (2-methoxy-4-aminopentyl) benzene, 1, 4-bis (1,1-
Dimethyl-5-aminopentyl) benzene, 1,4-bis (4-
Aminophenoxy) benzene, 3,5-diaminobenzoic acid,
2,5-diaminobenzoic acid, o-xylenediamine, m-xylenediamine, p-xylenediamine, 9,10-bis (4-aminophenyl) anthracene, 3,3′-diaminobenzophenone, 4,4′-diamino Benzophenone, 2,6-diaminopyridine, 3,5-diaminopyridine, 1,3-diaminoadamantane, 3,3′-diamino-1,1,1′-diadamantane, N- (3-aminophenyl) -4 -Aminobenzamide, 4,4'-diaminobenzanilide, 4-aminophenyl-3-aminobenzoate, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexa Fluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [ 4- (2-chloro-4-aminophenyl Phenoxy) phenyl] hexafluoropropane,
1,1-bis (4-aminophenyl) -1-phenyl-2,2,2-trifluoroethane, 1,1-bis [4- (4-aminophenoxy) phenyl] -1-phenyl-2,2 , 2-Trifluoroethane, 1,3-bis (3-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenyl) decafluoropropane, 2,2-bis (3-amino-4-hydroxy) Phenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis (5-amino-4-methylphenyl) hexafluoropropane, 1,4-
Examples thereof include bis (3-aminophenyl) but-1-en-3-yne, which may be used alone or in combination of two or more.

The polyamic acid which is the precursor of this polyimide resin is 0.5 g / N-methyl-2-pyrrolidone 10 ml
As a solution with a concentration of, the logarithmic viscosity at 30 ℃ is 0.2 to 4.0.
And more preferably 0.3 to 2.0. The polyamic acid can be obtained by subjecting an approximately equimolar amount of an acid component and a diamine component to an addition polymerization reaction in an organic solvent at a reaction temperature of 30 ° C. or lower, preferably 20 ° C. or lower for 3 to 12 hours.
As the organic solvent in this polymerization reaction, for example, N, N-
Examples thereof include dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone and hexamethylenephosphoamide. They can be used alone or in combination of two or more.

As the uracil derivative (B) used in the present invention, those represented by the above general formula 10 are used. In the above general formula, R ³ is —H, —CH ₃ , —COO.
H, although -COOCH ₃ or the like, in consideration of the solubility of the solvent can be R ³ is -COOH, orotic acid -COOCH _3, used preferably orotic acid methyl ester. The mixing ratio of the uracil derivative is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the above polyamic acid. If the amount is less than 1 part by weight, a sufficient sensitizing effect cannot be obtained, and if it exceeds 50 parts by weight, the compound is precipitated in the polyamic acid solution or on the formed coating film, which is not preferable.

The most important thing in the present invention is that the uracil derivative has a dramatic photocrosslinking sensitizer function for the (C) bisazide compound described below, and the polyimide film is left in the same compound for a long time. It was found that even in the heat treatment to such an extent that the moisture absorbed by the method can be completely evaporated, it has a structure in which it can be rapidly developed with a general aprotic polar solvent.

That is, since the uracil derivative exerts a dramatic sensitizing effect on the crosslinking agent of the bisazide compound,
By adding a very small amount of the bisazide compound, which is smaller than the conventional amount used, not only the sensitivity for practical use can be obtained, but also the crosslinking ability with higher sensitivity can be obtained. Further, the bisazide compound (eg, 2,6-bis- (paraazidobenzal) -4-methylcyclohexanone) which has been used as a photosensitizer component of a photoresist material is
Since the compatibility with polyamic acid having a high polarity is low, precipitation occurs when forming a coating film, and the solubility in a resin solvent is low and the addition amount is limited, so that a highly sensitive product cannot be obtained. It does not precipitate when sensitized with a uracil derivative, and a sufficient sensitivity can be obtained with an extremely small amount of addition, so that even a bisazide compound having low compatibility can be sufficiently put into practical use.

Further, the uracil derivative has a secondary amine having an active proton in the same structure, and the secondary amine is further activated by an electron-withdrawing effect by an adjacent carbonyl group. By adding the uracil derivative having this structure to the polyamic acid synthesized in the aprotic polar solvent, the solubility of the polyimide film can be significantly improved. For example, a conventional polyamic acid is coated on a substrate using a spin coater,
Heat treat at ~ 95 ° C for 3 minutes to a film thickness of 10 μm, then
When heat-treated at 0 ° C for 5 minutes and completely dissolved in a developer mixed with N-methyl-2-pyrrolidone and 7: 3 volume of methanol, a dissolution time of about 200 seconds was required. The polyamic acid added in parts by weight can be dissolved in about 30 to 40 seconds. This phenomenon can prevent a decrease in solubility of the polyimide film due to being left for a long period of time. That is, when a conventional polyamic acid was applied on a substrate to form a polyimide film and the polyimide film was left in that state, the solubility decreased with the standing time. The rate of decrease depends on the environment in which it is left, and it decreases greatly in a high humidity environment.
About 24 hours required about 3 times the initial dissolution time. Further, in the polyimide film after standing, a resin crack was generated on the entire surface of the coating film during dissolution by the developing solution. The main cause of these was the moisture absorption of the polyimide film, but once the moisture that has once absorbed is completely evaporated by heat treatment, it is necessary to heat treatment conditions of 100 ° C or higher to restore the initial solubility.
When the conventional polyamic acid is treated under this condition, the dissolution time becomes long, so that it is not practical.

The (C) bisazide compound used in the present invention is not limited to its structure as long as it is represented by the above general formula 11 and has a photocrosslinking ability superior to the conventional one. . As R ⁴ , a compound having an aromatic azide group at both ends of the molecule is preferably used, and examples of the basic skeleton include alkylene, chalcone and cyclohexanone type compounds. Further, those having improved solubility of these compounds may be used. The blending ratio of the bisazide compound is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the above polyamic acid. It is more preferably in the range of 0.1 to 20 parts by weight. If the amount is less than 0.1 parts by weight, sufficient sensitivity cannot be obtained, and if it exceeds 100 parts by weight, it may be precipitated in the resin or the coating film, which is not preferable. Compounds that are completely insoluble in aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethylacetamide, and dimethylformamide may precipitate in the resin or coating film. However, in the present invention, there is a problem with bisazide compounds such as 2,6-bis- (paraazidobenzal) -4-methylcyclohexanone, which has been considered to be impractical due to its low solubility. Sufficient sensitivity can be obtained with an addition amount in the range not present.

The amine compound (D) used in the present invention is not particularly limited as long as it is a compound represented by the general formula 12 and can react efficiently with the above-mentioned bisazide compound. As specific compounds, for example, 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 3- (N, N-dimethylamino) propyl acrylate, 3- (N, N-dimethylamino) propyl methacrylate, 4- (N, N-dimethylamino) butyl methacrylate, 4- (N, N-dimethylamino) butyl acrylate, 5- (N, N-dimethylamino) pentyl acrylate, 5- (N, N-dimethylamino) pentyl methacrylate, 6- (N, N-dimethylamino) hexyl acrylate, 6- (N, N-dimethylamino) hexyl methacrylate, sorbitan acid 3- (N, N-dimethylamino) ) Propyl, 2- (N, N-dimethylamino) ethyl sorbitan, 4- (N, N-dimethylamino) sorbitanate Le, and these may be used alone or in combination. The mixing ratio of these amine compounds is 1 to 10 parts by weight with respect to 100 parts by weight of the above-mentioned polyamic acid.
It is preferable to add 0 part by weight. If the blending amount is less than 1 part by weight or more than 100 parts by weight, the sensitivity is low, and the storage stability of the polyamic acid to be mixed is adversely affected, which is not preferable.

The photosensitive polymer composition of the present invention contains the above-mentioned polyamic acid, uracil derivative, bisazide compound and amine compound as essential components, but other components, if necessary, may be added as long as they do not deviate from the object of the present invention. Correspondingly, inorganic fillers such as silica, calcium carbonate, magnesium carbonate, sodium carbonate, talc, bentonite, thixotropic agents, colorants such as phthalocyanine green, defoaming agents,
A coupling agent, a leveling agent and the like can be added and blended to produce the composition.

The photosensitive polymer composition thus obtained is used to form a pattern, one example of which will be described.

The photosensitive polymer composition is coated on a substrate using a spin coater and heat-treated at 80 to 95 ° C. for 3 minutes to adjust the film thickness to 1 to 30 μm, preferably 3 to 10 μm. Then, exposure is carried out through a normal negative type photomask, then heat treatment is carried out at about 110 to 140 ° C. for 5 to 30 seconds, and then the unexposed portion is dissolved and removed by an aprotic polar solvent. At that time, if the temperature of the heat treatment after exposure is low or if the time is short,
Not only is sufficient sensitivity not obtained, but the initial solubility cannot be restored. The developing method is preferably a dipping method or a spray method, but is not particularly limited.
As the developing solution, a resin solvent such as N-methyl-2-pyrrolidone, dimethylacetamide or dimethylformamide, which is a general aprotic polar solvent, may be used alone or
You may mix and use alcohols, such as methanol and ethanol. After the development, by rinsing with an alcohol-based rinsing solution, methanol, ethanol, propanol or the like, it is possible to obtain a resin pattern having excellent resolution and a sharp end surface. The resin pattern thus obtained can be imidized by a final heat treatment at 200 to 400 ° C. to form a polyimide resin pattern having high heat resistance.

[0026]

The photosensitive polymer composition of the present invention contains a polyamic acid, a uracil derivative, a bisazide compound, and a specific amine compound to form a polyamic acid film with high sensitivity and high resolution, and after leaving it for a long time. However, the solubility does not decrease, and the use of this composition enables a stable patterning forming method.

[0027]

The present invention will be described below with reference to examples.
The invention is not limited by these examples.

Example 1 A flask equipped with a stirrer, a condenser and a nitrogen inlet tube was placed in a flask.
4,4'-Diaminodiphenyl ether 20.0 g (0.1 mol
) And N-methyl-2-pyrrolidone (4 volumes) and dimethylacetamide (6 volumes) in a reaction solvent at room temperature under a nitrogen atmosphere, 21.8 g (0.1 mol) of pyromellitic dianhydride was divided while paying attention to the rise of the solution temperature. Was added and stirred at room temperature for 10 hours to produce a polyamic acid. To 100 g of this polyamic acid, 15 g of 2- (N, N-dimethylamino) ethyl methacrylate was added and stirred for 12 hours, and then 2,6-bis-
(Paraazidobenzal) -4-methylcyclohexanone
Photosensitive polymer composition (A) was manufactured by adding 0.1 g and 3.0 g of orotic acid.

Example 2 A flask equipped with a stirrer, a cooler and a nitrogen inlet tube was placed in a flask.
4,4'-Diaminodiphenyl ether 20.0g (0.1mol
) And N-methyl-2-pyrrolidone (4 volumes) and dimethylacetamide (6 volumes) in a reaction solvent at room temperature under a nitrogen atmosphere.
3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride 3
2.2 g (0.1 mol) was added in portions while paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for 10 hours to produce a polyamic acid. For 100 g of this polyamic acid, 2- (N,
15 g of N-dimethylamino) ethyl methacrylate was added and stirred for 12 hours, and then 0.1 g of 2,6-bis (paraazidobenzal) -4-methylcyclohexanone and orotic acid
A photosensitive polymer composition (B) was produced by adding 3.0 g.

Example 3 A flask equipped with a stirrer, a condenser and a nitrogen introducing tube was placed.
4,4'-Diaminodiphenyl ether 20.0g (0.1mol
) And N-methyl-2-pyrrolidone (167 g) are added, and 29.4 g (0.1 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is added to the solution at room temperature under a nitrogen atmosphere so that the temperature of the solution may rise. While adding in portions, the mixture was stirred at room temperature for 10 hours to produce a polyamic acid. To 100 g of this polyamic acid, 15 g of 2- (N, N-dimethylamino) ethyl methacrylate was added and stirred for 12 hours, and then 0.1 g of 2,6-bis- (paraazidobenzal) -4-methylcyclohexanone
And 3.0 g of orotic acid were added to produce a photosensitive polymer composition (C).

The photosensitive polymer compositions obtained in Examples 1 to 3 were coated on a silicon wafer using a spin coater and heat-treated at 85 ° C. for 3 minutes to adjust the film thickness to 10 μm. Then, contact exposure was carried out for 30 seconds with a 250 W ultra-high pressure mercury lamp through a negative glass mask. After exposure, heat at 120 ° C for 5 minutes, N-methyl-2-pyrrolidone 7 volumes, methanol 3
Static paddle development for 40 seconds with a volume of developing solution and rinsing with propanol to obtain a resin pattern having a minimum line width of 5 μm. Also,
The photopolymer composition was applied to another silicon wafer in the same manner as above to a thickness of 10 μm, left standing in an environment of 25 ° C / 50% for 3 days, then exposed, then heat-treated and developed.
A resin pattern having a minimum line width of 5 μm was obtained with a developing time of 2 seconds. At this time, the patterning accuracy did not change before and after leaving, and insufficient development did not occur. The resulting pattern is 200-40
Even in the final heat treatment at 0 ° C for 1 to 2 hours, there was no defect in appearance and it reached a practical level. Further, the final cured product was firmly adhered to the silicon wafer, and there was no problem in terms of characteristics. The results are shown in Table 1. All were excellent in the characteristics of the present invention, and the remarkable effects of the present invention could be confirmed.

Comparative Example 1 In Example 1, 2,6-bis- (paraazidobenzal)
-4-methylcyclohexanone 0.1g and orotic acid 3g
A photosensitive polymer composition (D) was produced in the same manner as in Example 1 except that the above was not added.

Comparative Example 2 A photosensitive polymer composition (E) was produced in the same manner as in Example 2 except that 3 g of orotic acid was not added.

Comparative Example 3 A photosensitive polymer composition (F) was produced in the same manner as in Example 3 except that 3 g of orotic acid was not added.

The photosensitive polymer compositions obtained in Comparative Examples 1 to 3 were coated on a silicon wafer by using a spin coater and heat-treated at 85 ° C. for 3 minutes to adjust the film thickness to 10 μm. Contact exposure was carried out for 30 seconds with a 250 W ultra-high pressure mercury lamp through a negative glass mask. After exposure, heat at 120 ° C for 5 minutes, N-methyl-2-pyrrolidone 7 volumes, methanol 3
After a static paddle development for 50 seconds with a sufficient amount of developing solution and rinsing with propanol, a polyimide resin pattern could not be obtained (in Comparative Examples 2 and 3, a polyimide resin pattern having a minimum line width of 20 to 30 μm was obtained. The obtained resin pattern has a large amount of film slip due to development, and the amount of film slip varies on the wafer.
It was about m. ). Therefore, the development time was examined between 30 and 50 seconds, but patterning could not be obtained because there was no difference in dissolution between the exposed and unexposed areas. In addition, the photosensitive polymer composition was applied to another silicon wafer in the same manner as described above in an amount of 10 μm.
When it was applied to m and left for 3 days in an environment of 25 ° C / 50%, it was exposed to light, then heat-treated and developed, a complete underexposure occurred at a development time of 50 seconds, making patterning impossible ( In Comparative Examples 2 and 3, a developing time of 160 seconds was required in order to further extend the developing time and complete the development). In addition, countless resin cracks were generated in the polyimide film during development.

[0036]

[Table 1] * 1: Patterning is impossible because there is no difference in dissolution between exposed and unexposed areas. * 2: (Film thickness after final curing / film thickness before development) × 100 * 3: Development time after leaving for 24 hours / Development time before leaving * 4: ○: No cracks, ×: Cracks are generated on the entire surface. * 5: ○: Good, ×: Bad.

[0037]

As is apparent from the above description and Table 1, the photosensitive polymer composition and the pattern forming method of the present invention have high sensitivity and high resolution patterning accuracy, and Even if it is left for a long period of time or stored for a long period of time, there is no deterioration in solubility or the occurrence of resin cracks, and it has stable and highly reliable patterning processability, and the product yield can be significantly improved.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03F 7/027 7/038 504

Claims (2)

[Claims] 1. A polyamic acid represented by the following general formula (A): (Wherein R ¹ represents a tetravalent aromatic group and R ² represents a divalent aromatic group) (B) A uracil derivative represented by the following general formula: (However, in the formula, R ³ is —H, —CH ₃ , —COOH, —C
OOCH ₃ ) (C) A bisazide compound represented by the following general formula and N ₃ —R ⁴ —N ₃ (wherein R ⁴ represents a divalent or trivalent organic group) ( D) An amine compound represented by the following general formula: (Wherein R ⁵ , R ⁶ , and R ⁷ represent hydrogen, a lower alkyl group, a phenyl group, or a lower alkenyl group, and R ⁸ represents an alkylene group, which may be the same or different) A photosensitive polymer composition comprising: 2. A polyamic acid represented by the following general formula: (In the formula, R ¹ represents a tetravalent aromatic group, and R ² represents a divalent aromatic group.) (B) A uracil derivative represented by the following general formula: (However, in the formula, R ³ is —H, —CH ₃ , —COOH, —C
OOCH ₃ are expressed) (C) azido compounds represented by the following general formula and embedded image N ₃ -R ⁴ -N ₃ (however, wherein R ⁴ represents a divalent or trivalent organic group) ( D) An amine compound represented by the following general formula: (Wherein R ⁵ , R ⁶ , and R ⁷ represent hydrogen, a lower alkyl group, a phenyl group, or a lower alkenyl group, and R ⁸ represents an alkylene group, and these may be the same or different) After exposing the photosensitive polymer composition to be coated on a substrate, dried and exposed to a photosensitive substrate obtained by irradiating with an actinic ray,
A pattern forming method, which comprises performing heat treatment and then dissolving and removing an unexposed portion with an aprotic polar solvent.