JP2002278061A - Positive type photosensitive resin precursor composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali developable positive type photosensitive resin precursor composition. SOLUTION: The positive type photosensitive resin precursor composition comprises a polymer (a) a based on a structural unit of formula (1) (where R<1> is a di- to octavalent >=2C organic groups; R<2> is a di- to hexavalent >=2C organic group; R<3> is H or a 1-20C organic group; (n) is an integer 10-100,000; (m) is an integer of 0-2; and (p) and (q) are each an integer of 0-4 but p+q>0) and a photosensitive agent (b). The photosensitive agent (b) is a condensation product of a phenol compound having at least three hydroxyl groups and quinone diazide and a product obtained by condensing at least three molecules of quinone diazido in one molecule of the phenol compound occupies >=50% of the entire photosensitive agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive polyimide precursor composition suitable for a surface protective film, an interlayer insulating film and the like of a semiconductor element, in which a portion exposed to ultraviolet light is dissolved in an alkaline aqueous solution.

[0002]

2. Description of the Related Art Positive heat-resistant resin precursor compositions in which exposed portions are dissolved by development include polyamic acid to which quinonediazide is added, soluble polyimide having hydroxyl group to which quinonediazide is added, and hydroxyl group. There have been known polyamides having quinonediazide added thereto. As for the quinonediazide compound, a fluorine-containing quinonediazide (JP-A-4-31860)
And quinonediazides containing an isopropyl residue (JP-A-7-281441).

[0003]

However, when quinonediazide is added to ordinary polyamic acid, the solubility of the carboxyl group of polyamic acid is high due to the dissolution inhibiting effect of quinonediazide on alkali. There was a problem that it could not be obtained. In addition, in the case of adding a soluble polyimide resin having a hydroxyl group, 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. Points were problems. Even when a quinonediazide is added to a polyamide resin having a hydroxyl group, there are problems in that the structure is limited in order to obtain solubility, and that the resin obtained after heat treatment is inferior in solvent resistance.

In view of the above, the present invention provides a positive heat-resistant resin composition having a high residual film ratio during development, a small shrinkage ratio during curing, and a good pattern shape. It is in.

[0005]

That is, the present invention provides:
A positive photosensitive resin precursor composition comprising (a) a polymer having a structural unit represented by the general formula (1) as a main component and (b) a photosensitizer, wherein (b) the photosensitizer has a hydroxyl group. (B) a condensate of a phenol compound having at least three quinonediazides and quinonediazide, wherein at least three quinonediazides are condensed in one molecule of the phenol compound, wherein (b) 50% or more of the entire photosensitive agent It is a photosensitive resin precursor composition.

[0006]

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(Wherein R ¹ is a group having 2 or more carbon atoms)
A valent to octavalent organic group, R ² is a divalent to hexavalent organic group having two or more carbon atoms, R ³ is hydrogen,
To 20 to 20 organic groups. n is 10 to 10000
An integer up to 0, m represents an integer from 0 to 2, and p and q represent an integer from 0 to 4. However, p + q> 0. )

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer having a structural unit represented by the general formula (1) as a main component in the present invention is a polymer having an imide ring, an oxazole ring, or another cyclic structure by heating or an appropriate catalyst. It can be By having a ring structure, heat resistance and solvent resistance are dramatically improved.

The general formula (1) represents a polyamic acid having a hydroxyl group. Due to the presence of the hydroxyl group, the solubility in an aqueous alkali solution is better than that of a polyamic acid having no hydroxyl group. In particular, among the hydroxyl groups, phenolic hydroxyl groups are more preferable than solubility in an aqueous alkali solution. Further, by having a fluorine atom in the general formula (1) at 10% by weight or more, when developing with an aqueous alkali solution,
Since moderate water repellency appears at the interface of the film, penetration of the interface can be suppressed. However, when the fluorine atom content exceeds 20% by weight, the solubility in an aqueous alkali solution decreases, the organic solvent resistance of the polymer formed into a cyclic structure by heat treatment decreases, and the solubility in fuming nitric acid decreases. Not preferred. As described above, it is preferable that the fluorine atom is contained in an amount of 10% by weight to 20% by weight.

In the general formula (1), R ¹ represents a structural component of an acid dianhydride. The acid dianhydride contains an aromatic ring and has 1 to 4 hydroxyl groups. It is preferably a divalent to octavalent organic group having 2 or more carbon atoms, and more preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms.

Specifically, those having a structure represented by the general formula (2) are preferred. In this case, R ⁴ and R ⁶ are preferably those containing an aromatic ring in view of the heat resistance of the obtained polymer. Among them, particularly preferred structures include those such as trimellitic acid, trimesic acid, and naphthalene tricarboxylic acid residues. R ⁵ has 3 to 3 carbon atoms.
A trivalent to hexavalent organic group having a hydroxyl group selected from 20 is preferable. Further, the hydroxyl group is preferably located at a position adjacent to the amide bond. As such examples, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-hydroxy-4-aminophenyl) hexafluoropropane containing a fluorine atom, bis (3-amino-4-aminophenyl) hexafluoropropane, 3-amino-4-hydroxyphenyl) propane, bis (3-hydroxy-4-aminophenyl) propane, 3,3′-diamino-4,4 ′
-Dihydroxybiphenyl, 3,3'-diamino-4,
Examples thereof include those in which the amino group of 4'-dihydroxybiphenyl, 2,4-diamino-phenol, 2,5-diaminophenol, and 1,4-diamino-2,5-dihydroxybenzene is bonded.

R ⁷ and R ⁸ are preferably hydrogen and / or an organic group having 1 to 20 carbon atoms. When the number of carbon atoms is more than 20, the solubility in an alkali developer decreases.
o and s represent 1 or 2, and r represents an integer of 1 to 4. When r is larger than 5, the properties of the obtained heat-resistant resin film deteriorate.

In the general formula (1), R ¹ (COOR ³ ) m (O
H) Among the compounds in which p is represented by the general formula (2), preferred compounds include those having the structures shown below, but are not limited thereto.

[0014]

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Further, as long as the solubility in alkali, the photosensitivity and the heat resistance are not impaired, it can be modified with tetracarboxylic acid or dicarboxylic acid having no hydroxyl group. For example, aromatic tetracarboxylic acids such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, and diphenylsulfonetetracarboxylic acid, and two carboxyl groups thereof were converted to methyl groups or ethyl groups. Diester compounds, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, and diester compounds in which two carboxyl groups are converted to methyl groups or ethyl groups, terephthalic acid, isophthalic acid, diphenyletherdicarboxylic acid, naphthalenedicarboxylic acid Examples thereof include aromatic dicarboxylic acids such as acids, and aliphatic dicarboxylic acids such as adipic acid. These are preferably modified by not more than 50 mol% of the acid component, more preferably not more than 30 mol%. If the denaturation is more than 50 mol%, the solubility in alkali and the photosensitivity may be impaired.

In the above general formula (1), R ² represents a structural component of a diamine. Among them, preferred examples of R ² include those having an aromatic group and a hydroxyl group in view of the heat resistance of the obtained polymer, and specific examples thereof include bis (amino-hydroxy) having a fluorine atom. -Phenyl) hexafluoropropane, having no fluorine atom, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine,
Examples thereof include compounds such as diaminophenol and dihydroxybenzidine and those having structures represented by general formulas (3), (4) and (5).

Among them, R ⁹ and R ^{11 in} the general formula (3), R ^{13 in} the general formula (4), and R ^{16 in the} general formula (5) represent an aromatic ring or a hydroxyl group depending on the heat resistance of the obtained polymer. Is preferred. R ^{10 of} the general formula (3), R ^{12 of} the general formula (4),
R ¹⁴ and R ¹⁵ in the general formula (5) are preferably an organic group having an aromatic ring from the viewpoint of the heat resistance of the obtained polymer. Further, t and u in the general formula (3) represent an integer of 1 or 2, and v in the general formula (4) and w in the general formula (5) represent an integer of 1 to 4.

Specific examples in which R ² (OH) q in the general formula (1) is represented by the general formula (3) are shown below.

[0019]

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A specific example in which R ² (OH) q in the general formula (1) is represented by the general formula (4) is shown below.

[0021]

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Specific examples in which R ² (OH) q in the general formula (1) is represented by the general formula (5) are shown below.

[0023]

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In the general formula (3), R ⁹ and R ¹¹ each represent a trivalent to tetravalent organic group having a hydroxyl group selected from 2 to 20 carbon atoms. Those having a ring are preferred. Specifically, hydroxyphenyl, dihydroxyphenyl, hydroxynaphthyl, dihydroxynaphthyl, hydroxybiphenyl, dihydroxybiphenyl, bis (hydroxyphenyl) hexafluoropropane, bis (hydroxyphenyl) propane, bis (hydroxyphenyl) ) Represents a sulfone group, a hydroxydiphenylether group, a dihydroxydiphenylether group and the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used. R ¹⁰ has 2 carbon atoms
Represents a divalent organic group of up to 30. An aromatic divalent group is better than the heat resistance of the obtained polymer. Examples of such a group include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. Examples thereof include aliphatic cyclohexyl groups and the like.

In the general formula (4), R ¹² and R ¹⁴ represent a divalent organic group having 2 to 20 carbon atoms. An aromatic divalent group is better than the heat resistance of the obtained polymer. Examples of such a group include a phenyl group, a biphenyl group,
Examples thereof include a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. In addition, an aliphatic cyclohexyl group and the like can also be used. R ¹³ is
It represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms, and preferably has an aromatic ring from the heat resistance of the obtained polymer. Specifically, hydroxyphenyl, dihydroxyphenyl, hydroxynaphthyl, dihydroxynaphthyl, hydroxybiphenyl, dihydroxybiphenyl, bis (hydroxyphenyl) hexafluoropropane, bis (hydroxyphenyl) propane, bis (hydroxyphenyl) )
It represents a sulfone group, a hydroxydiphenyl ether group, a dihydroxydiphenyl ether group, or the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.

In the general formula (5), R ¹⁵ has 2 to 2 carbon atoms.
Represents a divalent organic group selected from 0. A divalent group having an aromatic group is preferred from the viewpoint of heat resistance of the obtained polymer. Examples of such a group include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. However, an aliphatic cyclohexyl group or the like can also be used. R ¹⁶ represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms, and preferably has an aromatic ring from the heat resistance of the obtained polymer. Specifically, hydroxyphenyl, dihydroxyphenyl, hydroxynaphthyl, dihydroxynaphthyl, hydroxybiphenyl, dihydroxybiphenyl, bis (hydroxyphenyl) hexafluoropropane, bis (hydroxyphenyl) propane, bis (hydroxyphenyl) ) Represents a sulfone group, a hydroxydiphenylether group, a dihydroxydiphenylether group and the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.

Further, it can be modified with another diamine component in the range of 1 to 40 mol%. Examples of these include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone and their aromatics. Examples thereof include compounds in which an aromatic ring is substituted with an alkyl group or a halogen atom. Such examples include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone, and aromatics thereof. Aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the like, such as compounds in which an aromatic ring is substituted with an alkyl group or a halogen atom, may be mentioned. When such a diamine component is copolymerized in a range of more than 40 mol%, the heat resistance of the obtained polymer is reduced.

R ^{3 in the} general formula (1) represents hydrogen or an organic group having 1 to 20 carbon atoms. R ³ is preferably an organic group from the viewpoint of the stability of the obtained positive photosensitive resin precursor solution, but is preferably hydrogen from the viewpoint of the solubility of the aqueous alkali solution. In the present invention, a hydrogen atom and an alkyl group can be mixed. By controlling the amount of hydrogen and the organic group of R ^3, the dissolution rate in an alkaline aqueous solution changes, so that a positive photosensitive resin precursor composition having an appropriate dissolution rate can be obtained by this adjustment. . The preferred range is that from 10% to 90% of the R ³ is a hydrogen atom. If the carbon number of R ³ exceeds 20, it will not be dissolved in an aqueous alkaline solution. R ³ than or contains at least one hydrocarbon group of 1 to 16 carbon atoms, it is preferred that the others are hydrogen atoms.

In the general formula (1), m represents the number of carboxyl groups, and represents an integer of 0 to 2. In the general formula (1), n represents the number of repeating structural units of the polymer of the present invention, and preferably ranges from 10 to 100,000.

Polyhydroxyamide can be used instead of polyamic acid as a heat-resistant polymer precursor similar to polyamic acid. Such a polyhydroxyamide can be produced by a condensation reaction between a bisaminophenol compound and a dicarboxylic acid. Specifically, dicyclohexylcarbodiimide (D
A method of reacting a dehydrating condensing agent such as CC) with an acid and adding a bisaminophenol compound thereto, or a method of dropping a solution of dicarboxylic acid dichloride into a solution of a bisaminophenol compound to which a tertiary amine such as pyridine is added. is there.

When a polyhydroxyamide is used, a photosensitive agent such as naphthoquinonediazide sulfonic acid ester is added to a solution of the polyhydroxyamide, so that a portion exposed to ultraviolet rays can be removed with an alkaline aqueous solution. A resin precursor composition can be obtained.

Further, in order to improve the adhesion to the substrate, R ¹ of the general formula (1),
R ² may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, bis (3-
Aminopropyl) tetramethyldisiloxane, bis (p
(Amino-phenyl) octamethylpentasiloxane and the like are copolymerized with 1 to 10 mol%. The positive photosensitive resin composition of the present invention comprises only a structural unit represented by the general formula (1). Or a copolymer or a blend with other structural units. In this case, it is preferable that the content of the structural unit represented by the general formula (1) is 90 mol% or more. The type and amount of the structural unit used in the copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polyimide polymer obtained by the final heat treatment.

The heat-resistant resin precursor of the present invention is synthesized by a known method. For example, tetracarboxylic acid 2 at low temperature
A method of reacting an anhydride with a diamine compound, obtaining a diester by tetracarboxylic dianhydride and an alcohol,
Thereafter, it can be synthesized by a method of reacting with an amine in the presence of a condensing agent, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then converting the remaining dicarboxylic acid into an acid chloride and reacting with an amine.

As the quinonediazide compound to be added to the present invention, a compound in which a sulfonic acid of naphthoquinonediazide is bonded to a phenol compound having at least three hydroxyl groups by an ester.

The quinonediazide compound of the present invention is synthesized by an esterification reaction of such a phenol compound with a 4-naphthoquinonediazidesulfonic acid or a 5-naphthoquinonediazidesulfonic acid compound, and one quinonediazide group is contained in one molecule of the phenol compound. It is a mixture of those that are individually condensed, those that are condensed, those that are condensed, those that are condensed, and those that are further condensed. In the present invention, it is important that at least three quinonediazide groups condensed occupy 50% or more of the entire photosensitive agent. By using a quinonediazide compound satisfying this condition as a photosensitive agent, the residual film ratio during development can be reduced. , High shrinkage during curing, and good pattern after curing can be obtained. At this time, as a measuring method for determining the condensation mixing ratio of the quinonediazide compound, high performance liquid chromatography, gel permeation chromatography, and the like,
In the present invention, the measurement is performed by high performance liquid chromatography using a UV detector.

When a condensate of a phenolic compound having one or two hydroxyl groups and a quinonediazide compound is used as the quinonediazide compound, three or more quinonediazide groups cannot be introduced, so that the pattern shape after curing does not become rectangular, and when curing, The amount of shrinkage may increase, which is not preferable.

Further, a hydroxyl group is added to the quinonediazide compound.
When a condensate of a phenol compound having at least three quinonediazide compounds and at least three quinonediazide groups are used, 50% of the total quinonediazide compound is condensed.
% Or more, the ratio of a large number of quinonediazide groups condensed is increased, so that it is difficult to effectively interact with the polymer chain, and a sufficient effect of suppressing the dissolution of the unexposed portion is not obtained, resulting in a large film loss. There are cases.

For these reasons, the phenol compound used in the quinonediazide compound of the present invention preferably has at least three hydroxyl groups, and more preferably has three to five hydroxyl groups.

As an example of the phenol compound used herein having at least three hydroxyl groups, MT
risPC, TrisP-PHBA, TrisOC-H
AP, TrisP-236S, TrisP-RS, Tr
isP-2S, TrisP-HAP, TrisP-2
P, TrisP-26M, TrisP-26P, Tri
sP-35P, TrisP-236P, BisPC-O
CHP, TrisOCR-PA, TrisP-PA, T
risP-3M6C-2, BisP-RS, TrisP
-3M6C-34, BisPG-26X, BisPG-
P, TekP-E, TekOC-E, Tek26X-T
PA, TPPA-1000P, TPPA-1100-2
C, BisP-PC, BisOC-OC, BisP-2
HBP, BisOC-2HBP, BisP-OCHP,
Bis26X-2HBP, BisPC-PCHP, Bi
s26X-RS, BisRS-PEP, Bis26X-
MBPC, TekP-4HBPA, BisRS-MBO
C, BisPG-MB25, HBP-2344, Bis
PG-P, BisHPMC-RS, Tek26X-MB
SA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR
-OC, BIP-OC, BI26X-OC, BIP-P
C, BIR-PC, BIHQ-PC, BI4MC-P
C, BIR-PTBP, BIR-PCHP, BIR-P
AP, BIR-34X, BIP-BIOC-F, 4P
C, BIR-BIPC-F, and TEP-BIP-A (all trade names, manufactured by Asahi Organic Materials Co., Ltd.), and the like, but other compounds can also be used.

Further preferred examples of the phenol compound having 3 to 5 hydroxyl groups include TrisP.
-PHBA, TrisP-RS, TrisP-HAP,
TrisP-26P, TrisP-PA, BisP-R
S, BisPG-26X, TekP-E, BisP-P
C, BisP-2HBP, Bis26X-MBPC, T
ekP-4HBPA, BisHPMC-RS (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIR
-PC, BIHQ-PC, BIR-PTBP (trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.) and the like.

Preferred phenol compounds among the phenol compounds used for the quinonediazide compound are shown below.

[0042]

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The 4-naphthoquinonediazidosulfonyl ester compound has an absorption in the i-line region of a mercury lamp, and
The 5-naphthoquinonediazidosulfonyl ester compound is suitable for g-line exposure because its absorption extends to the g-line region of a mercury lamp. In the present invention, 4
-Naphthoquinonediazidosulfonyl ester compound, 5
Any of -naphthoquinonediazidosulfonyl ester compounds can be preferably used, but it is preferable to select 4-naphthoquinonediazidosulfonyl, an ester compound or a 5-naphthoquinonediazidosulfonylester compound depending on the wavelength to be exposed. Further, a naphthoquinonediazidosulfonyl ester compound in which a 4-naphthoquinonediazidosulfonyl group and a 5-naphthoquinonediazidosulfonyl group are used together in the same molecule can be obtained. May be used in combination.

The quinonediazide compound has a molecular weight of 1
When it is 500 or more, the quinonediazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that problems such as a decrease in heat resistance of the obtained film, a decrease in mechanical properties, and a decrease in adhesiveness may occur. . From such a viewpoint, a preferable quinonediazide compound has a molecular weight of 300 to 1500. More preferably, 350
１1200.

The addition amount of such a quinonediazide compound is preferably from 1 to 50 parts by weight, more preferably from 3 to 40 parts by weight, based on 100 parts by weight of the polymer.

By adding a material having such a structure,
It is possible to obtain a film having a high residual film ratio after development, a small shrinkage ratio during curing, and a good pattern after curing.

Further, if necessary, surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ethanol and the like may be used for the purpose of improving the wettability between the photosensitive heat-resistant precursor composition and the substrate. Alcohols, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane may be mixed. In addition, inorganic particles such as silicon dioxide and titanium oxide, or powder of polyimide can also be added.

Further, in order to enhance the adhesiveness to an underlying substrate such as a silicon wafer, a silane coupling agent, a titanium chelating agent and the like are added to the varnish of the photosensitive heat-resistant resin precursor composition in an amount of 0.5 to 10% by weight. Alternatively, the underlying substrate can be pre-treated with such a chemical solution.

When added to the varnish, a silane coupling agent such as methylmethacryloxydimethoxysilane, 3-aminopropyltrimethoxysilane, etc., a titanium chelating agent, and an aluminum chelating agent are added to the polymer in the varnish in an amount of 0.5 to 10%. % By weight.

When treating the substrate, the above-mentioned coupling agent is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. The solution in which 5 to 20% by weight is dissolved is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment, or the like. In some cases, then 50 ° C to 300 ° C
The reaction between the substrate and the coupling agent proceeds by applying a temperature up to

Next, a method for forming a heat-resistant resin pattern using the photosensitive heat-resistant precursor composition of the present invention will be described.

The photosensitive heat-resistant precursor composition is applied on a substrate. As the substrate, a silicon wafer, ceramics, gallium arsenide, or the like is used, but is not limited thereto. Spin coating using a spinner as a coating method,
There are methods such as spray coating and roll coating.
The coating thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like.
To 150 μm.

Next, the substrate coated with the photosensitive heat-resistant precursor composition is dried to obtain a photosensitive heat-resistant precursor composition film. Drying uses an oven, a hot plate, infrared rays, etc. The film loss in the unexposed area after development is greatly reduced, the amount of shrinkage during curing is small, and a good pattern after curing can be obtained. And 1 in the range of 50 to 150 degrees
It is preferable to carry out for a few minutes to several hours.

Next, the photosensitive heat-resistant precursor composition film is exposed to actinic radiation through a mask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, i-line (365 nm), h-line (405 nm), and g of a mercury lamp are used.
Preferably, a line (436 nm) is used.

The pattern of the heat-resistant resin is formed by removing the exposed portion using a developing solution after the exposure. As a developing solution, an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamine An aqueous solution of an alkaline compound such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine is preferred. In some cases, a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Even if alcohols such as isopropanol, ethyl lactate, esters such as propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone are used alone or in combination of several kinds. Good. After development, it is rinsed with water. Here, rinsing treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.

After the development, the film is converted into a heat-resistant resin film by applying a temperature of 200 to 500 degrees. This heat treatment is carried out for 5 minutes to 5 hours while selecting the temperature and increasing the temperature stepwise, or while selecting a certain temperature range and continuously increasing the temperature. As an example, heat treatment is performed at 130 degrees, 200 degrees, and 350 degrees for 30 minutes each. Alternatively, a method of linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be used.

The heat-resistant resin film formed from the photosensitive heat-resistant precursor composition according to the present invention is used for applications such as a passivation film of a semiconductor, a protective film of a semiconductor element, and an interlayer insulating film of a multilayer wiring for high-density mounting. .

[0058]

The present invention will be described below with reference to examples and techniques, but the present invention is not limited to these examples. In addition, evaluation of the photosensitive heat-resistant resin precursor composition in an Example was performed by the following method.

Method for Measuring Condensation Ratio of Photosensitive Agent (HPLC Measurement) 5 mg of a photosensitizer was dissolved in acetonitrile for high performance liquid chromatography (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a 5 g solution of acetonitrile. Column for high performance liquid chromatography (HPLC) manufactured by Seisakusho (Shim-pack)
VP-ODS 150mmL × 4.6mmφ)
Eluent acetonitrile: 0.01 wt% phosphoric acid aqueous solution =
9: 1, UV detector measurement wavelength 254 nm, flow rate 1.0
The measurement was performed under the conditions of mL / min and a column temperature of 40.0 ° C. The area ratio of each obtained condensate peak was defined as the condensation ratio of the photosensitive agent.

Preparation of Photosensitive Polyimide Precursor Film A photosensitive heat-resistant resin precursor composition (hereinafter referred to as varnish) was applied on a 6-inch silicon wafer so that the film thickness after prebaking was 7 μm, and then hot. Using a plate (Mark-7 manufactured by Tokyo Electron Limited), 12
Prebaking was performed at 0 ° C. for 3 minutes to obtain a photosensitive polyimide precursor film.

Measurement method of film thickness Lambda Ace STM-6 manufactured by Dainippon Screen Mfg. Co., Ltd.
The measurement was carried out at a refractive index of 1.64 using No. 02. Exposure Exposure machine (i-line stepper DSW-8000 manufactured by GCA)
The reticle with the pattern cut was set therein, and the exposure time was changed (intensity of 365 nm) to perform i-line exposure. 1. Development Using a developing device of Mark-7 manufactured by Tokyo Electron Co., Ltd., tetramethylammonium hydroxide was used at 50 rotations.
A 38% aqueous solution was sprayed for 10 seconds. After this, 6
Let stand for 0 second, rinse with water at 400 rotations, 300
The mixture was shaken off at 0 rotation for 10 seconds and dried.

Calculation of residual film ratio The residual film ratio was calculated according to the following equation. Residual film ratio (%) = film thickness after development / film thickness after pre-bake × 1
Calculation of Shrinkage Ratio The prepared photosensitive polyimide precursor film was subjected to 140 under a nitrogen stream (oxygen concentration 20 ppm or less) using an inert oven INH-21CD manufactured by Koyo Thermo System Co., Ltd.
30 ° C. for 30 minutes and then heated to 350 ° C. for 1 hour to 35
Heat treatment was performed at 0 ° C. for 1 hour to produce a cured film. The shrinkage was calculated according to the following equation. Shrinkage (%) = (film thickness after pre-bake−film thickness after cure) ÷ film thickness after pre-bake × 100.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) under a stream of dry nitrogen
18.3 g (0.05 mol) and 34.2 g (0.3 mol) of allyl glycidyl ether were added to gamma-butyrolactone 1
The solution was cooled to -15 ° C. To this, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of gamma butyrolactone was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After dropping, 4 ° C at 0 ° C
Allowed to react for hours. This solution was concentrated using a rotary evaporator, and then added to 1 liter of toluene to obtain an acid anhydride (1).

[0064]

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Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (1) 18.3 g (0.05 mol) of BAHF was added to acetone 100
The resulting solution was dissolved in propylene oxide (17.4 g, 0.3 mol) and cooled to -15 ° C. A solution of 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride dissolved in 100 ml of acetone was added dropwise thereto. After dropping,
The reaction was carried out at −15 ° C. for 4 hours, and then returned to room temperature. The precipitated white solid was separated by filtration and dried at 50 ° C. in vacuo.

30 g of the solid was placed in a 300 ml stainless steel autoclave, dispersed in 250 ml of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Here, hydrogen was introduced by a balloon, and the reduction reaction was performed at room temperature. After about 2 hours, it was confirmed that the balloon did not deflate any more, and the reaction was terminated. After completion of the reaction, the mixture was filtered to remove the palladium compound as a catalyst, and concentrated by a rotary evaporator to obtain a diamine compound (1). The obtained solid was used for the reaction as it was.

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Synthesis Example 3 Synthesis of hydroxyl group-containing diamine (2) 15.4 g of 2-amino-4-nitrophenol (0.1
Mol) in acetone 50 ml, propylene oxide 30 g
(0.34 mol) and cooled to -15 ° C. A solution prepared by dissolving 11.2 g (0.055 mol) of isophthalic chloride in 60 ml of acetone was gradually added dropwise thereto. After the completion of the dropwise addition, the reaction was carried out at -15 ° C for 4 hours. Thereafter, the temperature was returned to room temperature, and the generated precipitate was collected by filtration.

This precipitate was dissolved in 200 ml of GBL, 3 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. A balloon containing hydrogen gas was attached thereto, and stirring was continued at room temperature until the balloon of hydrogen gas did not shrink any more, and further stirred for 2 hours with the balloon of hydrogen gas attached. After completion of the stirring, the palladium compound was removed by filtration, and the solution was concentrated to a half volume with a rotary evaporator. Ethanol is added here and recrystallized,
Crystals of the desired compound were obtained.

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Synthesis Example 4 Synthesis of Hydroxyl Group-Containing Diamine (3) 15.4 g of 2-amino-4-nitrophenol (0.1
Mol) in acetone, 100 ml of propylene oxide
Dissolved in 7.4 g (0.3 mol) and cooled to -15 ° C. Here, 20.4 g of 4-nitrobenzoyl chloride
(0.11 mol) dissolved in 100 ml of acetone was gradually added dropwise. After the completion of the dropwise addition, the reaction was carried out at -15 ° C for 4 hours. Thereafter, the temperature was returned to room temperature, and the generated precipitate was collected by filtration. Thereafter, a crystal of the target compound was obtained in the same manner as in Synthesis Example 2.

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Synthesis Example 5 Synthesis of quinonediazide compound (1) 7.21 g (0.05%) of 2-naphthol under a stream of dry nitrogen
Mol) and 13.43 g (0.05 mol) of 5-naphthoquinonediazidosulfonyl chloride in 450 g of 1,4-dioxane and brought to room temperature. Here, triethylamine 5.06 mixed with 50 g of 1,4-dioxane was used.
g was added dropwise so that the temperature inside the system did not become 35 ° C. or higher. After the addition, the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. The precipitate was dried with a vacuum drier to obtain a quinonediazide compound (1). When HPLC measurement was performed on the obtained quinonediazide compound (1) as described above, quinonediazide 1 condensate was 100%,
The proportion of quinonediazide groups condensed 3 or more is 0%
Met.

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Synthesis Example 6 Synthesis of quinonediazide compound (2) 11.41 g of bisphenol A under a stream of dry nitrogen
(0.05 mol) and 26.86 g (0.1 mol) of 5-naphthoquinonediazidosulfonyl chloride were dissolved in 450 g of 1,4-dioxane, and the mixture was brought to room temperature. here,
Using 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane, a quinonediazide compound (2) was obtained in the same manner as in Synthesis Example 5. The obtained quinonediazide compound (2) was subjected to HPLC measurement as described above. As a result, quinonediazide 1 condensate: 2 condensate = 1%: 9
9%, and the ratio of three or more quinonediazide groups condensed was 0%.

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Synthesis Example 7 Synthesis of quinonediazide compound (3) TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 15.31 g (0.05 mol) and 4
-Naphthoquinonediazidosulfonyl chloride 13.4
3 g (0.05 mol) and 17.46 g (0.065 mol) of 5-naphthoquinonediazidosulfonyl chloride were dissolved in 450 g of 1,4-dioxane and brought to room temperature.
Here, quinonediazide compound (3) was obtained in the same manner as in Synthesis Example 5 using 11.64 g of triethylamine mixed with 50 g of 1,4-dioxane. The obtained quinonediazide compound (3) was subjected to HPLC measurement as described above. As a result, quinonediazide 1 condensate: 2 condensate:
3 condensates = 7%: 37%: 56%, and the ratio of three or more quinonediazide groups condensed was 56%.

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Synthesis Example 8 Synthesis of quinonediazide compound (4) In a dry nitrogen stream, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 21.22 g (0.05 mol) and 4-
Naphthoquinonediazidosulfonyl chloride 13.43
g (0.05 mol), 20.15 g (0.075 mol) of 5-naphthoquinonediazidosulfonyl chloride was added to 1,
It was dissolved in 450 g of 4-dioxane and brought to room temperature. Here, quinonediazide compound (4) was obtained in the same manner as in Synthesis Example 5 using 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane. The obtained quinonediazide compound (4) was subjected to HPLC measurement as described above. As a result, quinonediazide 1 condensate: 2 condensates: 3 condensates = 4%: 29%: 67%, and three or more quinonediazide groups were present. The ratio of the condensed product was 67%.

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Synthesis Example 9 Synthesis of quinonediazide compound (5) 16.1 g (0.05 mol) of BisRS-2P (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 5-naphthoquinonediazidosulfonyl chloride in a dry nitrogen stream 40.29g
(0.15 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 50 g of 1,4-dioxane
Quinonediazide compound (5) was obtained in the same manner as in Synthesis Example 5 using 15.18 g of triethylamine mixed with the above. The obtained quinonediazide compound (5) was subjected to HPLC measurement as described above. As a result, quinonediazide 1 condensate: 2 condensate: 3 condensate: 4 condensate = 2%: 22
%: 41%: 35%, and the ratio of three or more quinonediazide groups condensed was 76%.

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Synthesis Example 10 Quinonediazide Compound (6)
16.1 g (0.05 mol) of BisRS-2P (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 20.15 g of 5-naphthoquinonediazidosulfonyl chloride in a dry nitrogen stream
(0.075 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 1,4-dioxane 50
quinonediazide compound (6) was obtained in the same manner as in Synthesis Example 5 using 7.59 g of triethylamine mixed with g. The obtained quinonediazide compound (6) was subjected to HPLC measurement as described above. As a result, quinonediazide 1 condensate: 2 condensate: 3 condensate: 4 condensate = 21%: 3
4%: 31%: 14%, and the ratio of three or more quinonediazide groups condensed was 45%.

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Synthesis Example 11 Quinonediazide Compound (7)
17.62 g (0.05 mol) of BIR-PC (trade name, manufactured by Asahi Organic Materials Co., Ltd.) and 40.30 g of 5-naphthoquinonediazidosulfonyl chloride under a dry nitrogen stream.
(0.15 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 50 g of 1,4-dioxane
Quinonediazide compound (7) was obtained in the same manner as in Synthesis Example 5 using 15.18 g of triethylamine mixed with The obtained quinonediazide compound (7) was subjected to HPLC measurement as described above. As a result, quinonediazide 1 condensate: 2 condensate: 3 condensate: 4 condensate: 5 condensate =
3%: 19%: 26%: 30%: 22%, and the ratio of three or more quinonediazide groups condensed was 78%.

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Synthesis Example 12 Quinonediazide Compound (8)
23.62 g (0.05 mol) of BIR-BIPC-F (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.) and 4 in a dry nitrogen stream
-Naphthoquinonediazidosulfonyl chloride 53.7
3 g (0.20 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 1,4-dioxane 5
Quinonediazide compound (8) in the same manner as in Synthesis Example 5 using 20.24 g of triethylamine mixed with 0 g
I got The obtained quinonediazide compound (8) was subjected to HPLC measurement as described above. As a result, quinonediazide 1 condensate: 2 condensate: 3 condensate: 4 condensate: 5 condensate: 6 condensate = 2%: 8% : 16%: 28%: 29%:
It was 17%, and the ratio of three or more quinonediazide groups condensed was 90%.

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Synthesis Example 13 Quinonediazide Compound (9)
In a dry nitrogen stream, 4.1 g (0.01 mol) of BisPG-P (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 2.68 g (0.0 mol of 4-naphthoquinonediazidosulfonyl chloride)
1 mol) 5-Naphthoquinonediazidosulfonyl chloride 10.74 g (0.04 mol) was dissolved in 1,4-dioxane 450 g, and the mixture was brought to room temperature. Here, triethylamine 5.06 mixed with 50 g of 1,4-dioxane was used.
Using g, a quinonediazide compound (9) was obtained in the same manner as in Synthesis Example 5. The obtained quinonediazide compound (9) was subjected to HPLC measurement as described above. As a result, quinonediazide 1 condensate: 2 condensate: 3 condensate: 4 condensate:
5 condensate: 6 condensate = 0%: 9%: 14%: 26%: 3
3%: 18%, and the ratio of three or more quinonediazide groups condensed was 91%.

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Example 1 5.01 g (0.025 mol) of 4,4'-diaminophenyl ether and 1.24 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane under a stream of dry nitrogen
(0.005 mol) with N-methyl-2-pyrrolidone (N
MP) 50 g. Here, 21.4 g (0.03 mol) of the hydroxy group-containing acid anhydride obtained in Synthesis Example 1
Was added together with 14 g of NMP and reacted at 20 ° C. for 1 hour and then at 50 ° C. for 4 hours. Then N, N
-Dimethylformamide dimethyl acetal 7.14 g
(0.06 mol) was added dropwise over 10 minutes. After the addition, the mixture was stirred at 50 ° C. for 3 hours.

To 40 g of the obtained solution, 2 g of the quinonediazide compound (3) obtained in Synthesis Example 7 was added to obtain a varnish A of a photosensitive polyimide precursor composition. As described above, using the obtained varnish, a photosensitive polyimide precursor film is prepared on a silicon wafer, exposed, developed, and after measuring the residual film ratio after development, curing and shrinkage ratio, the pattern shape An evaluation was performed.

Example 2 Under a dry nitrogen stream, 15.1 g (0.025 mol) of the hydroxyl group-containing diamine (1) obtained in Synthesis Example 2 was N-
It was dissolved in 50 g of methyl-2-pyrrolidone (NMP). Here, 17.5 g (0.025 mol) of the hydroxy group-containing anhydride obtained in Synthesis Example 1 was added together with 30 g of pyridine, and reacted at 60 ° C. for 6 hours. After the reaction,
The solution was poured into 21 of water and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 20 hours.

10 g of the solid polymer thus obtained
Was measured and 2 g of the quinonediazide compound (5) obtained in Synthesis Example 9 was dissolved in 30 g of gamma-butyrolactone to obtain a varnish B of a photosensitive polyimide precursor composition. As described above, using the obtained varnish, to prepare a photosensitive polyimide precursor film on a silicon wafer, exposed, developed,
After measuring the residual film ratio after the development, the film was cured to evaluate the shrinkage ratio and the pattern shape.

Example 3 17 g (0.045 mol) of the hydroxyl group-containing diamine compound (2) obtained in Synthesis Example 3 under a stream of dry nitrogen
1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was added to 50 g of NMP.
Was dissolved. Here, 12.4 g of 3,3 ', 4,4'-diphenylethertetracarboxylic anhydride (0.04
Mol) was added together with 21 g of NMP and reacted at 20 ° C. for 1 hour and then at 50 ° C. for 2 hours. 0.98 g (0.01 mol) of maleic anhydride was added thereto, and 50
After stirring at 2 ° C. for 2 hours, 14.7 g (0.1 mol) of N, N-dimethylformamide diethyl acetal was added to 5 g of NMP.
Was added dropwise over 10 minutes. After dripping, 50
Stirred at C for 3 hours.

1.6 g of the quinonediazide compound (7) obtained in Synthesis Example 11 was dissolved in 30 g of the obtained solution to obtain a varnish C of a photosensitive polyimide precursor composition. As described above, using the obtained varnish, a photosensitive polyimide precursor film is prepared on a silicon wafer, exposed, developed, and after measuring the residual film ratio after development, curing and shrinkage ratio, the pattern shape An evaluation was performed.

Example 4 6.08 g (0.025 mol) of the hydroxyl group-containing diamine compound (3) obtained in Synthesis Example 4 under a stream of dry nitrogen.
And 4.51 g of 4,4'-diaminodiphenyl ether
(0.0225 mol) and 0.62 g (0.002 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane
25 mol) was dissolved in 70 g of NMP. 24.99 g (0.035 mol) of the hydroxyl group-containing acid anhydride (1) and 4.41 g (0.015 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride were subjected to NM at room temperature.
The mixture was added together with 25 g of P, and stirred at room temperature for 1 hour and then at 50 ° C. for 2 hours. Then, a solution obtained by diluting 17.6 g (0.2 mol) of glycidyl methyl ether with 10 g of NMP was added, and the mixture was stirred at 70 ° C. for 6 hours.

In 40 g of this polymer solution, 2.5 g of the quinonediazide compound (8) obtained in Synthesis Example 12 was dissolved to obtain a varnish D of a photosensitive polyimide precursor composition. As described above, using the obtained varnish, to prepare a photosensitive polyimide precursor film on a silicon wafer, exposed, developed,
After measuring the residual film ratio after the development, the film was cured to evaluate the shrinkage ratio and the pattern shape.

Example 5 18.3 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane under a stream of dry nitrogen
(0.05 mol) with N-methyl-2-pyrrolidone (NM
P) 50 g, glycidyl methyl ether 26.4 g
(0.3 mol), and the temperature of the solution was cooled to -15 ° C. A solution prepared by dissolving 7.38 g (0.025 mol) of diphenyl ether dicarboxylic acid dichloride and 5.08 g (0.025 mol) of isophthalic acid dichloride in 25 g of gamma-butyrolactone was added dropwise so that the internal temperature did not exceed 0 ° C. did. After dropping, -15 ° C for 6 hours
And continued stirring. After completion of the reaction, the solution was poured into 3 l of water to collect a white precipitate. The precipitate is collected by filtration and washed with water for 3 hours.
After washing twice, it was dried in a vacuum dryer at 80 ° C. for 20 hours.

The thus obtained polymer powder 10
g to the quinonediazide compound (4) 2 obtained in Synthesis Example 8.
g of NMP was dissolved in 30 g of NMP to obtain a varnish E of a photosensitive polybenzoxazole precursor composition. As described above, using the obtained varnish, a photosensitive polybenzoxazole precursor film is formed on a silicon wafer, exposed and developed,
After measuring the residual film ratio after the development, the film was cured to evaluate the shrinkage ratio and the pattern shape.

Example 6 40 g of a polyimide precursor solution synthesized in the same manner as in Example 4
The quinonediazide compound (9) 2 obtained in Synthesis Example 13
g was dissolved to obtain a varnish F of a photosensitive polyimide precursor composition. As described above, using the obtained varnish, a photosensitive polyimide precursor film is prepared on a silicon wafer, exposed, developed, and after measuring the residual film ratio after development, curing and shrinkage ratio, the pattern shape An evaluation was performed.

Comparative Example 1 40 g of a polyimide precursor solution synthesized in the same manner as in Example 1
2 g of the quinonediazide compound (1) obtained in Synthesis Example 5
Is dissolved to form a varnish G of the photosensitive polyimide precursor composition.
I got As described above, using the obtained varnish, a photosensitive polyimide precursor film is prepared on a silicon wafer, exposed, developed, and after measuring the residual film ratio after development, curing and shrinkage ratio, the pattern shape An evaluation was performed.

Comparative Example 2 30 g of a polyimide precursor solution synthesized in the same manner as in Example 3
2 g of the quinonediazide compound (2) obtained in Synthesis Example 6
Is dissolved to form a varnish H of the photosensitive polyimide precursor composition.
I got As described above, using the obtained varnish, a photosensitive polyimide precursor film is prepared on a silicon wafer, exposed, developed, and after measuring the residual film ratio after development, curing and shrinkage ratio, the pattern shape An evaluation was performed.

Comparative Example 3 30 g of a polyimide precursor solution synthesized in the same manner as in Example 2
The quinonediazide compound (6) obtained in Synthesis Example 10
1.6 g was dissolved to obtain a varnish I of a photosensitive polyimide precursor composition. As described above, using the obtained varnish, a photosensitive polyimide precursor film is prepared on a silicon wafer, exposed, developed, and after measuring the residual film ratio after development, curing and shrinkage ratio, the pattern shape An evaluation was performed.

The evaluation results of Examples 1 to 6 and Comparative Examples 1 to 3 are shown in Table 1 below.

[0106]

[Table 1]

[0107]

According to the present invention, development can be carried out with an aqueous alkali solution, the amount of film loss during development and the shrinkage after curing are small,
A positive photosensitive resin precursor composition having an excellent pattern shape can be obtained.

Continued on front page F-term (reference) 2H025 AA03 AA04 AA06 AA10 AA20 AB16 AC01 AD03 BE01 CB26 CB43 CB45 CB55 FA17 FA29 4J002 CL061 CL071 EQ036 ET006 GP03

Claims (6)

[Claims] 1. A positive photosensitive resin precursor composition comprising (a) a polymer having a structural unit represented by the general formula (1) as a main component and (b) a photosensitive agent, wherein (b) The photosensitizer is a condensate of a phenolic compound having at least three hydroxyl groups and quinonediazide, and at least three quinonediazides condensed in one molecule of the phenolic compound are (b) 50% or more of the entire photosensitizer. A positive photosensitive resin precursor composition characterized by the following: Embedded image (Wherein R ¹ is a divalent to octavalent organic group having 2 or more carbon atoms, R ² is a divalent to hexavalent organic group having 2 or more carbon atoms, R ³ is hydrogen or carbon Represents an organic group represented by the formulas 1 to 20, n represents an integer from 10 to 100,000, m represents an integer from 0 to 2, p and q each represents an integer from 0 to 4, provided that p + q> 0. .) (B) the photosensitizer is a condensate of a phenol compound having 3 to 5 hydroxyl groups and quinonediazide, wherein 3 to 5 quinonediazides are condensed in one molecule of the phenol compound; The positive photosensitive resin precursor composition according to claim 1, wherein (b) is at least 50% of the total amount of the photosensitive agent. 3. The method according to claim 1, wherein R ¹ (COOR ³ ) m (O
H) p is represented by general formula (2), The positive photosensitive resin precursor composition of Claim 1 or 2 characterized by the above-mentioned. Embedded image (R ⁴ and R ^{6 each} represent a divalent to tetravalent organic group selected from 2 to 20 carbon atoms, and R ⁵ represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. And R ⁷ and R ⁸ represent hydrogen and / or an organic group having 1 to 20 carbon atoms. O and s represent an integer of 0 to 2, and r represents an integer of 1 to 4.) 4. The positive photosensitive resin precursor composition according to claim 1, wherein R ² (OH) q in the general formula (1) is represented by the general formula (3). Embedded image (R ⁹ and R ¹¹ each represent a trivalent to tetravalent organic group having a hydroxyl group selected from 2 to 20 carbon atoms, and R ¹⁰ represents 2 to 30 carbon atoms.
And a divalent organic group selected from the group consisting of: t and u each represent an integer of 1 or 2. ) 5. The positive photosensitive resin precursor composition according to claim 1, wherein R ² (OH) q in the general formula (1) is represented by the general formula (4). Embedded image (R ¹² and R ¹⁴ each represent a divalent organic group having 2 to 20 carbon atoms, and R ¹³ represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. Represents an integer of 1 to 4.) 6. The positive photosensitive resin precursor composition according to claim 1, wherein R ² (OH) q in the general formula (1) is represented by the general formula (5). Embedded image (R ¹⁵ represents a divalent organic group selected from 2 to 20 carbon atoms, and R ¹⁶ represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. W is 1 Represents an integer from to 4)