JP2000351845A - Photosensitive polyamide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyamide having a specified structure which can give a positive photoresist having good sensitivity and resolution, showing excellent stability, and having high-level heat resistance and mechanical performances. SOLUTION: This polyamide has a structural units represented by formula I. In formula I, R1 is a tetravalent organic group; R2 is a divalent organic group; and one of R3 and R4 is a group represented by formula II, and the other is a monovalent organic group, hydroxyl, or a group represented by formula II, provided that they may be the same or different from each other when both of them are groups represented by formula II). In formula II, R5 is a 2-10C organic group; R6 is a 1-6C organic group, provided that R5 and R6 may be bonded to each other to form a ring; Q is a naphthoquinonediazide group represented by formula III or IV. The polyamide is obtained by introducing an alcohol having a naphthoquinonediazidosulfonamide group into a polyamic acid through ester linkages.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive polyamide.

[0002]

2. Description of the Related Art Hitherto, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor element. This polyimide resin is generally provided in the form of a photosensitive polyimide precursor composition, and can be easily formed by applying, patterning with active light rays, developing, and thermal imidization treatment. It has the feature that the process can be significantly shortened as compared with photosensitive polyimide. As the material for the above purpose, various materials have already been disclosed for the negative type. However, since many negative-working photosensitive materials use a crosslinking reaction, the exposed portion swells due to a developing solution, which is disadvantageous in performing high-resolution fine processing. Furthermore, a positive photosensitive heat-resistant material may be required in the process, and a positive photosensitive heat-resistant material has been desired.

In the conventional developing process, it is necessary to use a large amount of an organic solvent such as N-methyl-2-pyrrolidone as a developing solution. Is coming. In response to this, various proposals have recently been made for heat-resistant photosensitive resin materials that can be developed with a dilute alkaline aqueous solution, similarly to photoresists.

[0004] Examples thereof include a method in which naphthoquinonediazide is added to polyamic acid (Japanese Patent Laid-Open No. 52-13315) and a method in which a naphthoquinonediazide compound is added to soluble hydroxyl polyimide (Japanese Patent Publication No. 64-6063).
No. 0) is known.

However, when a naphthoquinone diazide is added to a polyamic acid, the desired pattern can be obtained in most cases because the solubility of the carboxyl group of the polyamic acid is high due to the dissolution inhibiting effect of the naphthoquinone diazide in an alkali developing solution. There was a problem that it was not possible. In addition, in the case where naphthoquinonediazide is added to soluble hydroxyl polyimide, although the problems just described have been reduced, the structure is limited in order to make it soluble, and the solvent resistance of the obtained polyimide resin is poor. Was a problem. In these systems to which naphthoquinonediazide is added, the effect of naphthoquinonediazide is low, and as a result, high sensitivity is not obtained.

On the other hand, by introducing naphthoquinonediazide into a polymer, high sensitivity is aimed at, and a method of introducing naphthoquinonediazidesulfonic acid ester into a hydroxyl group of a soluble polyimide (Macromolecule).
s, 23, 4796, 1990), and a method of introducing naphthoquinonediazide into a polyamic acid via an amide bond (JP-A-6-258835).

However, when a naphthoquinonediazidesulfonic acid ester is introduced into a hydroxyl group of a soluble polyimide, the structure is limited in order to make the polymer soluble, and the sensitivity is increased because naphthoquinonediazide is introduced as a sulfonic acid ester. There was a problem that it would be lower. On the other hand, in the case where naphthoquinonediazide is introduced into a polyamic acid via an amide bond, since the polyamic acid amide is used, the stability of the polymer is reduced and the main chain is broken at the time of imidization, thereby reducing the molecular weight. There was a problem that the physical properties of the formed film deteriorated, and it was not a material that could withstand practical use.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a heat-resistant positive photoresist composition which can be developed with an alkaline aqueous solution, has good sensitivity and resolution, exhibits excellent stability, and furthermore, has a surface protection property for semiconductor devices. An object of the present invention is to provide a polyamide which is a heat-resistant resin precursor which satisfies a high level of heat resistance and mechanical performance required for a film and an interlayer insulating film.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a polyamide capable of achieving the above object can be obtained by introducing an alcohol having naphthoquinonediazidesulfonic acid amide into a polyamic acid via an ester bond. The inventors have found that the present invention has been completed and completed the present invention.

That is, the present invention provides a polyamide having a structural unit represented by the following general formula (1).

[0011]

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(Where R _{1 is a} tetravalent organic group, R _{2 is} a divalent organic group, R ₃ and R ₄ are one groups represented by the following general formula (2), and the other is a monovalent organic group) Or a group represented by the following general formula (2): When both R ₃ and R ₄ are groups represented by the following general formula (2), R ₃ and R ₄ are the same But may be different.)

[0013]

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(Where R _{5 is} an organic group having 2 to 10 carbon atoms;
R ₆ : an organic group having 1 to ₆ carbon atoms, including the case where R ₅ and R ₆ are linked to form a ring. Q: Formula (3) or (4)
And naphthoquinonediazide represented by )

[0015]

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[0016]

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The above polyamide is typically synthesized by the following method.

First, a tetracarboxylic dianhydride represented by the following general formula (5) is reacted with an alcohol compound serving as a base of R ₃ and R ₄ in the formula (1) in the presence of a basic catalyst, followed by esterification. To form a half ester of the formula (6).

[0019]

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[0020]

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(Here, R ₁ , R ₃ , R _{4 in} the tetracarboxylic dianhydride of the formula (5) and the compound of the formula (6)
Is synonymous with R ₁ , R ₃ and R ₄ in the formula (1). The compound (6) and the diamino compound H ₂ N—R ₂ —NH
₂ (R ₂ is R ₂ as defined in the formula (1)), and a dehydration condensation agent, by reacting in an organic solvent, a polyamide having the formula (1) is synthesized.

The tetracarboxylic dianhydride used as the formula (5) includes, for example, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 3 ′, 4′-benzophenonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,2 5,6-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2, 3,3 ', 4'
-Biphenyltetracarboxylic dianhydride, diphenyl ether-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenyl ether-2,3,2', 3'-tetracarboxylic dianhydride, diphenyl ether-2 , 3,
3 ′, 4′-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride,
2,2-bis [5- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [5-
(2,3-dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, perylene-3, Solubility of 4,9,10 tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 2,2 '-(3,4-dicarboxyphenylhexafluoropropane dianhydride, and polyamide in aqueous alkali solution In order to further increase the value, tetracarboxylic dianhydride having a phenolic hydroxyl group, for example, at least one compound selected from the group consisting of the following formulas (7) to (10) can be used.

[0023]

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(Wherein X is selected from hexafluoroisopropylidene, isopropylidene, sulfonyl, carbonyl and oxygen)

[0025]

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[0026]

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[0027]

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On the other hand, a diamino compound (NH ₂ —R ₂ —NH
₂ ) includes, for example, m-phenylenediamine, p-
Phenylenediamine, 2,4-tolylenediamine, 3,
3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylsulfone, 4,
4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-
Diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylketone, 4,4'-diaminodiphenylketone, 3,4'-diaminodiphenylketone, 2,2'-bis (4-aminophenyl ) Propane, 2,2′-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-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, 4,4'-diaminobiphenyl,
4,4'-diaminobenzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, o-toluidinesulfone, 2,2 -Screw (4-
Aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) Benzene, 9,9-bis (4-aminophenyl) anthracene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-di- (3-aminophenoxy) diphenylsulfone, 4,4′-diamino Benzanilide, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6) -amino-1-
(4-aminophenyl) -1,3,3-trimethylindane, bis (p-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- (4
-Aminophenoxy) phenyl] hexafluoropropane, 2,2bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4'-bis [4- (4-aminophenoxy) phenyl] sulfone,

4,4'-bis [4- (α, α-dimethyl-
4-aminobenzyl) phenoxy] benzophenone,
4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4, 4'-diaminobiphenyl, bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (p-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane , 1,4-bis (γ-
Aminopropyldimethylsilyl) benzene, bis (4-
Aminobutyl) tetramethyldisiloxane, bis (γ-
Aminopropyl) tetraphenyldisiloxane, 1,4
Aromatic or aliphatic diamines such as diaminobutane and 1,2-diaminocyclobutane; and hydrogen atoms other than amino groups of these aromatic or aliphatic diamines are chlorine, fluorine, bromine, methyl, methoxy A compound substituted by at least one substituent selected from the group consisting of: a cyano group and a phenyl group; and a compound represented by the following general formula (11):

[0031]

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(Where p is an integer of 2 to 12) or a diamino compound having a phenolic hydroxyl group such as 3,5-diamino-1-hydroxybenzene, , 5-Dihydroxy-1,4-diaminobenzene, 4,6-dihydroxy-1,3-diaminobenzene, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 4,4′-dihydroxy-3,3 '-Diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobenzophenone, 4,4'-dihydroxy-3,3'-diaminobenzophenone, 3,3'-dihydroxy-4,4'
-Diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 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 (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) methane,

Bis (4-amino-3-hydroxyphenyl) methane, 2,2'-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2'-bis (3-amino-4-hydroxyphenyl) Phenyl) hexafluoropropane, 2- (3-hydroxy-4-aminophenyl) -2- (3-amino-4-hydroxyphenyl) hexafluoropropane, 6-hydroxy-2,4-diaminopyrimidine, 2,4-dihydroxy At least one diamino compound selected from the group of -5,6-diaminopyrimidine, 6-hydroxy-2,4-diaminotriazine and the like can be used.

In the polyamide of the present invention, it is essential that at least one of R ₃ and R ₄ in the polymer is a group represented by the formula (2). More preferably, of all R ₃ and R _{4 in} the polyamide, the compound represented by the formula (2)
Is 5% or more. If less than 5% of all the R ₃ and R _{4 in} the polyamide have the structure of the formula (2), the difference in dissolution rate between the exposed and unexposed parts becomes small, and a satisfactory image is obtained. I can't.

In the formula (2), R ₅ has 2 to 1 carbon atoms.
And R ₆ is an organic group having 1 to ₆ carbon atoms. When R ₆ is hydrogen, the alcohol having the structure of the formula (2) before being introduced into the polyamide as R ₃ and R ₄ is unstable, and the obtained polyamide has poor stability. On the other hand, when the carbon number of R ₆ is 7 or more, the solubility of the polyamide in an aqueous alkali solution becomes insufficient, and sufficient performance cannot be obtained. Further, R ₅ and R ₆ may be an alicyclic or aromatic group as long as the above requirements are satisfied, and R ₅ and R ₆ may be linked to form a ring.

In R ₃ and R ₄ , the group other than the group represented by the formula (2) includes a hydroxyl group and a monovalent organic group. A structure having a phenolic hydroxyl group is desirable from the viewpoint of improving the property. Examples of these include a 3-hydroxybenzyl group and a 3,5-dihydroxybenzyl group. Further, in addition to the structural unit of the formula (1), a copolymer polyamide having a structural unit of the formula (1) into which the group of the formula (2) is not introduced as a copolymer component is also included in the present invention. Further, a polyamide in which the group of the formula (2) has not been introduced may be mixed with the polyamide of the present invention.

As the dehydrating condensing agent for synthesizing the polyamide of the present invention, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid,
Cobalt acetate, manganese acetate, stannous chloride, stannic chloride, polyphosphoric acid, triphenyl phosphite, bis-o-
Phenylene phosphate, N, N- (phenylphosphino) bis [2 (3H) -benzothiazolone], general formula R-
A carbodiimide derivative represented by N = C = NR ', for example, dicyclohexylcarbodiimide (DCC) and the like.

As the organic solvent used for the synthesis of the polyamide, an aprotic polar solvent is usually used, but for the synthesis of the polyamide used in the present invention,
Solvents such as aromatic hydrocarbons, tetrahydrofuran and dioxane can also be used. Specifically, ketone solvents such as cyclohexanone, acetone, methyl ethyl ketone, and methyl isobutyl ketone, cellosolve solvents such as methyl celloselb acetate, methyl celloserub acetate, and butyl celloserub acetate, and ester solvents such as ethyl acetate, butyl acetate, and isoamyl acetate , Tetrahydrofuran, dioxane and other ether solvents, N, N-dimethylformamide, N, N-dimethylacetamide (DMAc), N-
Methyl-2-pyrrolidone (NMP), N-methyl-ε-
Caprolactam, γ-butyrolactone, sulfolane,
At least one solvent selected from the group consisting of solvents such as N, N, N ', N'-tetramethylurea, hexamethylphosphamide, toluene, xylene and the like, or a mixed solvent thereof is used. A polyamide having the structural unit represented by 1) is synthesized. Here, it is particularly important to select a condensing agent and a reaction solvent. As a condensing agent, DCC is preferred from the viewpoint that the reaction conditions are mild and do not contain an ionic component as an impurity. Further, in this case, 1-hydroxybenzotriazole (HOBt) can be used to suppress unnecessary side reactions.
Also, in the reaction solvent, the resulting polymer does not gel,
Amide solvents such as DMAc and NMP are preferred in that they have sufficient dissolving power.

In addition to the above-described method of esterification of an acid anhydride followed by polycondensation of an amide, a polyamic acid is first synthesized from a dicarboxylic anhydride and a diamino compound, and then a polyamic acid is added to the side chain. The polyamide having the structural unit of the above formula (1) can also be synthesized by a method of introducing an alcohol having the structure of the above (2) by esterification.

Further, in order to improve the alkali solubility of the obtained polymer and the mechanical properties of the coating film after heat curing, a structure having an aliphatic unsaturated bond at the molecular chain terminal may be introduced. Good. As the introduction method, it is convenient to use a cyclic dicarboxylic anhydride having an aliphatic unsaturated bond, and this is esterified in a form partially used with the tetracarboxylic dianhydride of the formula (5), followed by esterification. The amide may be polycondensed. Alternatively, after polymerizing a polyamide having a structural unit represented by the formula (1), the acid anhydride having an unsaturated bond at the molecular chain terminal or a derivative thereof may be allowed to act.

The cyclic dicarboxylic anhydride having an aliphatic unsaturated bond includes, for example, 4-phenylethynylphthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, cis-4-cyclohexene-1 , 2-dicarboxylic anhydride and the like, and particularly preferred is 5-norbornene-2,3-dicarboxylic anhydride.

The polyamide containing the structural unit of the formula (1) synthesized by the above method is purified as follows. That is, methanol, ethanol, water, and the like are added to the reaction solution of the polyamide in an amount of about 1 to 2 times the amount of the
After stirring for 1 to 4 hours, the unreacted dehydrating agent is reacted, the precipitate is removed by filtration, and the obtained solution is washed with methanol, ethanol, or water 5 to 100 times the reaction solution. Wash. Thereafter, the polyamide is isolated and purified by drying at room temperature to 60 ° C. in a vacuum.

The composition of the present invention is used by dissolving at least a polyamide having a structural unit represented by the formula (1) in an organic solvent to form a varnish. Examples of the organic solvent used here include NMP, DMAc, γ-butyrolactone, cyclopentanone, cyclohexanone, dimethyl sulfoxide, diethylene glycol dimethyl ether,
Diethylene glycol diethyl ether, diethylene glycol dibutyl ether and the like may be used alone or as a mixture. For the purpose of improving coating properties, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, , 3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate,
A solvent such as methyl-3-methoxypropionate can be mixed and used. At this time, additives such as a sensitizing agent for improving the sensitivity and a silane coupling agent for increasing the adhesiveness to the substrate can be added.

Next, an example of a method for forming an image using the heat-resistant photosensitive composition thus obtained will be described. First, the composition varnish is dried on a substrate to a film thickness of 1 to 5
The coating is performed so as to have a thickness of 0 μm, preferably 5 to 30 μm. At this time, it is also possible to apply an adhesion auxiliary agent such as a silane coupling agent on the base material in advance, and perform a pre-adhesion treatment.

Next, after this coating film is dried, exposure is performed through a normal photomask, followed by development processing with an alkaline aqueous solution having an appropriate concentration to transfer a fine resin pattern onto the substrate. it can. The developer used at this time is preferably one capable of completely dissolving and removing the exposed film within an appropriate time, and is preferably an inorganic alkaline aqueous solution such as sodium hydroxide or potassium hydroxide, or propylamine, butylamine, monoethanolamine, tetraethanol or the like. Methyl ammonium hydroxide (TMA
H), an organic alkaline aqueous solution such as choline or the like is used alone or in combination of two or more. In addition, the alkaline aqueous solution may contain an organic solvent such as an alcohol and various surfactants as necessary.

After development, a positive type image of the heat-resistant material precursor is obtained by washing with a rinse solution. The image thus obtained is subjected to a high-temperature heat treatment (about 200 to 400
C), it can be converted to a heat-resistant material having excellent heat resistance, chemical resistance, and mechanical properties, and a cured product having a good relief pattern can be obtained.

[0047]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described based on examples.

[0048]

Example 1 Diphenyl ether-3,3 ', 4,4'-
15.5 g of tetracarboxylic dianhydride (ODPA)
(0.05 mol), 12.6 g (0.09 mol) of 3,5-dihydroxybenzyl alcohol (3,5-DHBA), 3.1 g of alcohol (NMEA) of formula (12)
(0.01 mol) is converted to N-methyl-2-pyrrolidone (NM
P) dissolved in 46.5 g, and pyridine 7.91 g (0.1
Mol), and the mixture was stirred at room temperature for 16 hours to perform esterification.

[0049]

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(Wherein Q represents formula (4)) Next, 1-hydroxybenzotriazole (HOBt) 1
A solution prepared by dissolving 6.2 g (0.12 mol) in 48.7 g of NMP was added, and then 20.6 g (0.1 mol) of dicyclohexylcarbodiimide (DCC) was added to NMP under ice cooling.
A solution dissolved in 20.6 g was added dropwise and stirred for 2 hours. Next, 10.9 g (0.05 mol) of 4,4′-diaminodiphenyl ether (DADPE) was added to NMP3.
A solution dissolved in 2.6 g was added to carry out a reaction. afterwards,
After returning to room temperature and reacting for 3 hours, 5-norbornene-
4.1 g of 2,3-dicarboxylic anhydride (NBA) (0.
03 mol), and the mixture was further stirred for 5 hours. Finally, 3 g of ethanol was added, and the mixture was stirred for 1 hour. Then, the insoluble matter was separated by filtration, the reaction solution was added dropwise to 1 liter of distilled water, the precipitate was collected by filtration, and dried under reduced pressure to obtain the compound of the formula (2). A polyamide having a GPC molecular weight of 10500 (polystyrene equivalent) into which 10% of the structure was introduced was obtained.

100 parts by weight of this polymer was added to NMP200
It was dissolved in parts by weight, and after sufficiently dissolved, the solution was filtered through a 0.2 μm filter made of Teflon to obtain a photosensitive composition varnish.

The varnish was spin-coated on a silicon wafer which had been pre-treated with a silane coupling agent in advance, and a dried film having a thickness of 10 μm was obtained. This coating film was irradiated with ultraviolet light from a super high pressure mercury lamp as a light source while changing the exposure amount through a pattern reticle. After exposure,
The exposed portion was dissolved and removed by immersion in a 2.38% TMAH aqueous solution for 3 minutes, rinsed with purified water, and air-dried in a nitrogen stream.

When this was observed with a microscope, the exposure amount was 2
A line and space of 4 μm were resolved by irradiation of 50 mJ / cm ² , and a favorable and fine positive pattern could be obtained. At this time, the undeveloped portion has an undeveloped film ratio of 9%.
5%, indicating a sufficient alkali dissolution inhibiting ability in unexposed areas.

[0054]

Example 2 9.93 g of 3-hydroxybenzyl alcohol (3-HBA) as an alcohol during esterification
(0.08 mol) and 6.2 g (0.02 mol) of NMEA
A polymer was synthesized in the same manner as in Example 1 except that the GPC molecular weight of 9 introduced with 20% of the structure of the formula (2) was used.
800 (polystyrene equivalent) polyamide was obtained.

The same operation and processing as in Example 1 were carried out, and a 4 μm line and space were resolved by irradiation with an exposure amount of 300 mJ / cm ² , and a good pattern could be obtained. At this time, the undeveloped portion of the undeveloped portion has a residual film ratio of 97
%, And exhibited a sufficient alkali dissolution inhibiting ability.

[0056]

Example 3 NMEA as alcohol of esterifying agent
30.7 g (0.1 mol), 2,2′- as diamine
Using 17.0 g (0.047 mol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane, without using NBA as a terminal blocking agent, the film thickness after drying of the varnish was 1 μm at the time of evaluation. Polymer synthesis was carried out in the same manner as in Example 1 except that the above-mentioned was used to obtain a polyamide having a GPC molecular weight of 10100 (polystyrene conversion) into which 100% of the structure of the formula (2) had been introduced.

The same operation and processing as in Example 1 were carried out, and a line and space of 3 μm were resolved by irradiation with an exposure amount of 150 mJ / cm ² , and a good pattern could be obtained. At this time, the undeveloped portion remaining after development is 99%.
%, And exhibited a sufficient alkali dissolution inhibiting ability.

[0058]

Comparative Example 1 12.4 g of 3-HBA as an esterifying agent
(0.1 mol), a polyamide having a GPC molecular weight of 10800 (in terms of polystyrene) into which the structure of the formula (2) was not introduced was obtained.

100 parts by weight of this polymer was added to NMP200
After dissolving in 20 parts by weight, quinonediazide represented by the formula (13) was added in an amount of 20 parts by weight, and after sufficiently dissolving, the mixture was filtered through a 0.2 μm Teflon filter to obtain a photosensitive composition varnish. Using the varnish, the same operation and processing as in Example 1 were performed.

[0060]

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(Q in the formula represents the formula (4)) As a result, resolution cannot be achieved by 3 minutes of development as in the embodiment, and finally, 20 minutes or more are required for the development and dissolution of the exposed portion. In addition, the residue in the elution portion was severe, and was not practically usable. Incidentally, the undeveloped portion of the undeveloped portion has a residual film ratio of 70.
%, Which is lower than that of Examples of the present invention.

[0062]

Comparative Example 2 12.4 g of 3-HBA as an esterifying agent
(0.05 mol), and the same operation and treatment as in Comparative Example 1 were performed. As a result, the exposure amount was 700 mJ / c.
With the irradiation of m ² , a line and space of 10 μm could be resolved. However, the undeveloped portion undeveloped film ratio at this time is 5
It was very low at 3%.

[0063]

Comparative Example 3 15.5 g (0.05 mol) of ODPA and 15 g (0.25 mol) of urea were added at 200 ° C. in 100 g of NMP.
, And then cooled to room temperature, and 28.4 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride.
(0.12 mol) and 15.2 g (0.1%) of triethylamine.
15 mol) and reacted at 50 ° C. for another 3 hours. This was poured into water, and the precipitate was separated by filtration and dried to obtain N, N'-1,2-naphthoquinonediazido-5-sulfonyldiphenylethertetracarboxylic imide 1.
5.5 g (0.02 mol), ODPA 24.8 g (0.
08 mol), NBA (0.02 mol) and 150 g of NMP
And 22.0 g (0.11 mol) of DADPE was added thereto and reacted at 50 ° C. for 3 hours. The reaction solution was added dropwise to 1 liter of distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid amide into which 20% of naphthoquinonediazide had been introduced. When this was evaluated in the same manner as in Example 1, a line and space of 10 μm was resolved by irradiation with an exposure amount of 500 mJ / cm ² . However, finally by the irradiation of the exposure amount 1000 mJ / cm ² to perform the same evaluation after 1 week using this varnish 15
A μm line and space could be resolved. Such a decrease in sensitivity was not confirmed in the varnish using the polyamide of the present invention, and it was found that the stability of the varnish was low in the polyamide acid amide type polymer.

Further, with respect to the photosensitive composition varnish of each of the above examples, the mechanical properties of the heat-cured film were evaluated. Each composition varnish was uniformly applied onto a silicon wafer using a spin coater, and prebaked on a hot plate at 95 ° C. for 90 seconds to form a coating film having a thickness of 18 μm. This coating film was set in a vertical curing furnace (manufactured by Koyo Lindberg), and subjected to curing (heating imidation hardening treatment) at 350 ° C. for 2 hours in a nitrogen atmosphere to obtain a polyimide film. The cured film was peeled off from the silicon wafer and used for evaluation of mechanical properties. The evaluation method was based on ASTM D-882-88. Table 1 shows the results.

[0065]

[Table 1]

As described above, in the case of the embodiment of the present invention, excellent positive exposure patterning characteristics and high cured film mechanical properties of 40% or more are achieved, and are sufficiently practical. When an aliphatic unsaturated group is introduced into the polymer terminal as in Examples 1 and 2, the physical properties of the cured film are further improved, which is more preferable.

On the other hand, in Comparative Example 1, in which the naphthoquinonediazide compound was added to the varnish, the alkali solubility of the coating film was insufficient, so that industrial-grade patterning characteristics could not be achieved. On the other hand, in the case of Comparative Example 2 in which a carboxyl group was introduced as an amide acid moiety into the polymer to impart alkali solubility, a pattern was obtained, but the naphthoquinone diazide compound was merely increased in solubility of the polymer. As a result, the dissolution inhibiting ability of the unexposed part due to the above-mentioned method does not work sufficiently, so that the undeveloped part has a very low residual film ratio of development and cannot be a practical material. Comparison of these examples with the examples shows the superiority of introducing the naphthoquinonediazide compound into the polymer chain. Further, in the case of a polymer having naphthoquinonediazide in the form of polyamic acid amide as in Comparative Example 3, the sensitivity is remarkably reduced with time, and the practicality is poor. Not at all. Therefore, it is necessary to introduce the naphthoquinonediazide compound into the polymer chain in the form of a polyamic acid ester as in the present invention.

[0068]

The polyamide of the present invention has a structure of a polyamic acid ester into which an alcohol compound containing naphthoquinonediazidesulfonic acid amide has been introduced, thereby improving the sensitivity and stability of naphthoquinonediazide. And polyamic acid ester which enhances mechanical properties after curing.
By using this polyamide, a positive photosensitive composition that can be developed with an aqueous alkali solution, is characterized by high photosensitivity and resolution, and has excellent storage stability is provided. Further, by heating and curing the photosensitive composition using the polyamide of the present invention, a good polyimide film pattern having excellent heat resistance and mechanical properties can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 CM041 ED026 EE056 EH036 EL066 EP016 EU026 EV206 FD206 GQ00 GQ05 4J043 PA02 QB15 QB25 RA05 SA06 SB01 TA12 TA32 TB01 UA121 UA122 UA131 UA132 UA141 UA1 UA1 UA1 UA1 UA1 UB062 UB121 UB122 UB131 UB132 UB151 UB152 UB222 UB281 UB301 UB302 UB321 UB351 UB402 WA09 WA16 XA14 XA16 XA18 XA19 ZA46 ZA60 ZB22

Claims (2)

[Claims] 1. A polyamide having a structural unit represented by the following general formula (1). Embedded image (Provided that R _{1 is a} tetravalent organic group, R _{2 is} a divalent organic group,
R ₃ and R ₄ : one is a group represented by the following general formula (2), and the other is a monovalent organic group, a hydroxyl group, or a group represented by the following general formula (2). When both R ₃ and R ₄ are groups represented by the following formula (2), R ₃ and R ₄ may be the same or different. ) (However, R _5: an organic group having 2 to 10 carbon atoms, R _6: 1 carbon atoms
6 organic group, including the case where R ₅ and R ₆ are linked to form a ring. Q: represents naphthoquinonediazide represented by the formula (3) or (4). ) Embedded image 2. A photosensitive resin composition comprising the polyamide of claim 1 and an organic solvent.