JP2001235860A - Positive photosensitive resin precursor composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali developable positive photosensitive resin precursor composition. SOLUTION: The positive photosensitive resin precursor composition contains (a) a polymer based on structural units of formula I and/or formula II, (b) a compound having a phenolic hydroxyl group and (c) an esterified quinonediazido compound.

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 As a positive type heat-resistant resin precursor composition in which an exposed portion is dissolved by alkali development, a composition obtained by adding naphthoquinonediazide to polyamic acid (JP-A-52-13315), A solution obtained by adding naphthoquinonediazide to a soluble polyimide obtained (JP-A-64-60630) and a product obtained by adding naphthoquinonediazide to a polyamide having a hydroxyl group (JP-A-56-60).
27140) and the like.

However, in the case where naphthoquinone diazide is added to ordinary polyamic acid, the desired pattern can be obtained in most cases because the solubility of the carboxyl group of polyamic acid is high due to the dissolution inhibiting effect of naphthoquinone diazide on alkali. There was no problem. Then, in order to control the alkali solubility of the polyamic acid, a polyamic acid derivative in which the carboxyl group of the polyamic acid is protected with an ester group has been developed. However, in the case where naphthoquinone diazide is added to this polyamic acid derivative, the dissolution inhibiting effect of naphthoquinone diazide on alkali becomes very large, and in most cases, a desired pattern can be obtained, but development cannot be performed in a short time (hereinafter referred to as , And low resolution) and not resolving a fine pattern (hereinafter referred to as low resolution).

[0004]

In view of the above drawbacks,
The present invention is a resin composition obtained by adding a compound having a phenolic hydroxyl group and a naphthoquinonediazide compound to a polyimide precursor synthesized using a specific terminal blocking agent, almost before exposure to an alkaline developer. Since it does not dissolve and easily dissolves in an alkaline developer upon exposure, it can be developed in a short time (hereinafter referred to as high sensitivity) with less film loss due to development, and further resolves fine patterns (hereinafter high resolution). ), Which led to the invention.

[0005]

The present invention relates to (a) a polymer having a structural unit represented by the general formula (1) and / or (2) as a main component, and (b) a phenolic hydroxyl group. A positive-type photosensitive resin precursor composition comprising a compound having a quinonediazide compound (C) and an esterified quinonediazide compound.

[0006]

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Wherein R ¹ is a divalent to octavalent organic group having at least 2 carbon atoms, and R ² is at least 2
A divalent to hexavalent organic group having at least two carbon atoms, R ³
Represents hydrogen or an organic group having 1 to 20 carbon atoms, and R ⁴ represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 10 carbon atoms. R ⁵ represents a hydrocarbon group having at least one unsaturated hydrocarbon group having 1 to 10 carbon atoms, a nitro group, a methylol group, an ester group, or a hydroxyalkynyl group. n is an integer from 10 to 100,000, m is an integer from 0 to 2, and p and q are integers from 0 to 4. p + q> 0. )

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer having a structural unit represented by the general formula (1) and / or the general formula (2) as a main component in the present invention means an imide ring or an oxazole ring by heating or an appropriate catalyst. And other polymers having a cyclic structure. By having a ring structure, heat resistance and solvent resistance are dramatically improved.

The above-mentioned general formulas (1) and (2) represent polyamic acid having a hydroxyl group. Due to the presence of the hydroxyl group, the solubility in an aqueous alkali solution is higher than that of a polyamic acid having no hydroxyl group. Will also be good. In particular, among the hydroxyl groups, phenolic hydroxyl groups are more preferable than solubility in an aqueous alkali solution. When the fluorine atom is contained in the general formula (1) or the general formula (2) in an amount of 10% by weight or more, when the film is developed with an aqueous alkali solution, the water repellency appears at the interface of the film. And so on. 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) or the general formula (2), R
¹ represents a structural component of an acid dianhydride. The acid dianhydride contains an aromatic ring, has 1 to 4 hydroxyl groups, and is a divalent having at least 2 or more carbon atoms. It is preferably an organic group having a valence of 8 to 8, more preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms.

Specifically, those having a structure represented by the general formula (3) are preferable. In this case, R ⁶ and R ⁸ are divalent to tetravalent organic groups selected from C 2 to C 20. As shown, those containing an aromatic ring are preferable in view of the heat resistance of the obtained polymer. Among them, particularly preferable structures include those such as trimellitic acid, trimesic acid, and naphthalene tricarboxylic acid residues. R ⁷ is preferably a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. Further, the hydroxyl group is preferably located at a position adjacent to the amide bond. Examples of such a compound include bis (3-amino-4-hydroxyphenyl) hexafluoropropane and bis (3-
(Hydroxy-4-aminophenyl) hexafluoropropane, containing no fluorine atom, bis (3-amino-4-
(Hydroxyphenyl) propane, bis (3-hydroxy-4-aminophenyl) propane, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxybiphenyl, 2, 4-diamino-phenol, 2,5-diaminophenol,
Examples thereof include those in which the amino group of 1,4-diamino-2,5-dihydroxybenzene is bonded.

R ⁹ and R ^{10 in} the general formula (3) represent hydrogen,
And / or an organic group having 1 to 20 carbon atoms is preferable. When the carbon number is 20 or more, the solubility in an alkali developing solution is reduced.

In the general formula (3), o and s represent integers of 0 to 2, and r represents an integer of 1 to 4. r
Is 5 or more, the properties of the obtained heat-resistant resin film deteriorate.

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

[0015]

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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, diphenylether dicarboxylic 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%. When the modification is performed at 50 mol% or more, the solubility in alkali and the photosensitivity may be impaired.

In general formula (1) or general formula (2), R
² represents a structural component of the diamine. In this, R ²
As a preferable example, a compound having an aromatic group and a hydroxyl group is preferable in view of the heat resistance of the obtained polymer. As a specific example, bis (amino-
(Hydroxy-phenyl) hexafluoropropane, having no fluorine atom, diaminodihydroxypyrimidine,
Examples thereof include compounds such as diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, and dihydroxybenzidine, and those having structures represented by general formulas (4), (5), and (6).

Among them, R ¹¹ , R ¹³ ,
R ¹⁵ in the general formula (5) and R ¹⁸ in the general formula (6) are preferably an aromatic ring or an organic group having a hydroxyl group from the viewpoint of heat resistance of the obtained polymer. R ¹² in general formula (4), general formula (5)
R ¹⁴ and R ^{16 in} the formula and R ¹⁷ in the general formula (6) are preferably an organic group having an aromatic ring in view of the heat resistance of the obtained polymer. Further, t and u in the general formula (4) represent an integer of 1 or 2, and v in the general formula (5) and w in the general formula (6) represent an integer of 1 to 4.

In the general formula (1) or the general formula (2), R
Specific examples in which ² (OH) q is represented by the general formula (4) are shown below.

[0020]

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

[0022]

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R of the general formula (1) or (2)
Specific examples of ² (OH) q represented by the general formula (6) are shown below.

[0024]

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In the general formula (4), R ¹¹ and R ¹³ 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 ¹² 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 (5), R ¹⁴ and R ¹⁶ 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 ¹⁵ 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, a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxynaphthyl group, a dihydroxynaphthyl group, a hydroxybiphenyl group, a dihydroxybiphenyl group, a bis (hydroxyphenyl) hexafluoropropane group, a bis (hydroxyphenyl) propane group, a 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 (6), R ¹⁷ 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 ¹⁸ 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 viewpoint of 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 an amount of 40 mol% or more, the heat resistance of the obtained polymer decreases.

R ^{3 in the} general formula (1) or (2) represents hydrogen or an organic group having 1 to 20 carbon atoms. From the stability of the obtained positive photosensitive resin precursor solution, R
³ is preferably an organic group, but is preferably hydrogen in view 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. From the above, R ³ is
It is preferable that at least one hydrocarbon group having 1 to 16 carbon atoms is contained, and the others are hydrogen atoms.

The following general formula (7), which is a structural component in the general formula (1), is a component derived from a primary monoamine which is a terminal blocking agent.

[0031]

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In the general formula (7), R ⁴ is a hydrogen atom,
It represents a monovalent group selected from a hydroxyl group and a hydrocarbon group having 1 to 10 carbon atoms. Among them, a hydrogen atom, a hydroxyl group and a hydrocarbon group having 1 to 4 carbon atoms are preferable, and a hydrogen atom, a hydroxyl group, a methyl group and a t-butyl group are particularly preferable. Also,
R ⁵ is a monovalent group selected from a hydrocarbon group having 1 to 10 carbon atoms containing at least one unsaturated hydrocarbon group, a hydroxyalkenyl group, a nitro group, a methylol group, and an ester group. R ⁵ is a vinyl group, an ethynyl group, a propynyl group, an allyl group, 3-hydroxy-3-methyl-
A 1-butynyl group, a 3-hydroxy-3-methyl-1-pentynyl group, a 3-hydroxy-3-ethyl-1-pentynyl group, a nitro group, a methylol group, and an ester group are preferred, and a vinyl group and an ethynyl are particularly preferred. Group, propynyl group, allyl group and 3-hydroxy-3-methyl-1-butynyl group.

The introduction ratio of the component represented by the general formula (7) is preferably in the range of 0.1 to 40 mol%, particularly preferably 1 to 30 mol%, based on the diamine component.

Further, m of the general formula (1) or (2)
Represents the number of carboxyl groups, and represents an integer from 0 to 2. In the general formula (1) or the general formula (2), n indicates 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 naphthoquinonediazidesulfonic acid ester is added to a solution of the polyhydroxyamide, so that a portion exposed to ultraviolet rays can be removed with an aqueous alkaline solution. A resin precursor composition can be obtained.

Further, in order to improve the adhesiveness to the substrate, an aliphatic group having a siloxane structure may be copolymerized at R1 and R2 as long as the heat resistance is not reduced. Specifically, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, or the like is used as a diamine component in an amount of 1 to 10;
Those obtained by copolymerizing mol% are exemplified.

The positive photosensitive resin composition of the present invention may be composed of only the structural unit represented by the general formula (1) or (2), or may be copolymerized with another structural unit. It may be a union or a blend. In that case, it is preferable that the content of the structural unit represented by the general formula (1) or (2) is 50 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 using a known method by replacing a part of the diamine with a terminal blocking agent which is a monoamine. For example, a method of reacting a tetracarboxylic dianhydride with a diamine compound at a low temperature, a method of obtaining a diester with a tetracarboxylic dianhydride and an alcohol, and then reacting the diester with a diamine in the presence of a condensing agent, The diester can be obtained by using an anhydride and an alcohol, and then the remaining dicarboxylic acid is converted to an acid chloride and reacted with a diamine to synthesize the diester.

The terminal blocking agent used in the present invention introduced into the polymer can be easily detected by the following method.
For example, a polymer having a terminal blocking agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component, which are constituent units of the polymer, and this is subjected to gas chromatography (GC).
In addition, the terminal blocking agent used in the present invention can be easily detected by NMR measurement. Separately, the polymer component into which the terminal blocking agent has been introduced is directly subjected to pyrolysis gas chromatography (PGC), infrared spectrum and C13 NMR.
It can be easily detected by spectrum measurement.

The compound having a phenolic hydroxyl group used in the present invention includes, for example, Bis-Z, Bis
OC-Z, BisOPP-Z, BisP-CP, Bis
26X-Z, BisOTBP-Z, BisOCHP-
Z, BisOCR-CP, BisP-MZ, BisP-
EZ, Bis26X-CP, BisP-PZ, BisP
-IPZ, BisCR-IPZ, BisOCP-IP
Z, BisOIPP-CP, Bis26X-IPZ, B
isOTBP-CP, TekP-4HBPA (tetrakis P-DO-BPA), TrisP-HAP, Tris
P-PA, BisOFP-Z, BisRS-2P, Bi
sPG-26X, BisRS-3P, BisOC-OC
HP, BisPC-OCHP, Bis25X-OCH
P, Bis26X-OCHP, BisOCHP-OC,
Bis236T-OCHP, methylenetris-FR-C
R, BisRS-26X, BisRS-OCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC,
BIP-PC, BIR-PC, BIR-PTBP, BI
R-PCHP, BIP-BIOC-F, 4PC, BIR
-BIPC-F, TEP-BIP-A (the above, trade name,
Manufactured by Asahi Organic Materials Industry Co., Ltd.).

Among these, preferred compounds having a phenolic hydroxyl group include, for example, Bis-Z, B
isP-EZ, TekP-4HBPA, TrisP-H
AP, TrisP-PA, BisOCHP-Z, Bis
P-MZ, BisP-PZ, BisP-IPZ, Bis
OCP-IPZ, BisP-CP, BisRS-2P,
BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, BIP-PC,
BIR-PC, BIR-PTBP, BIR-BIPC-
F and the like. Among these, particularly preferred compounds having a phenolic hydroxyl group include, for example, Bi
s-Z, TekP-4HBPA, TrisP-HAP,
TrisP-PA, BisRS-2P, BisRS-3
P, BIR-PC, BIR-PTBP, BIR-BIP
C-F. By adding the compound having a phenolic hydroxyl group, the obtained resin composition hardly dissolves in an alkali developing solution before exposure, and easily dissolves in an alkali developing solution upon exposure. The development is easy in a small amount and in a short time.

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

The esterified quinonediazide compound (c) to be added to the present invention is preferably a compound having a phenolic hydroxyl group and a sulfonic acid of naphthoquinonediazide bonded by an ester. The compound having a phenolic hydroxyl group used here may be the same as or different from the compound having a phenolic hydroxyl group in (b). Such compounds include Bis-Z, B
isP-EZ, TekP-4HBPA, TrisP-H
AP, TrisP-PA, BisOCHP-Z, Bis
P-MZ, BisP-PZ, BisP-IPZ, Bis
OCP-IPZ, BisP-CP, BisRS-2P,
BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC,
BIR-PC, BIR-PTBP, BIR-PCHP,
BIP-BIOC-F, 4PC, BIR-BIPC-
F, TEP-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, methylene bisphenol, BisP-AP (trade name, Honshu Chemical Industry) And the like. Preferred are compounds obtained by introducing 4-naphthoquinonediazidosulfonic acid or 5-naphthoquinonediazidosulfonic acid via a ester bond into a compound such as (manufactured by Co., Ltd.), but other compounds can also be used. .

When the molecular weight of the naphthoquinonediazide compound used in the present invention is 1000 or more, the heat resistance of the resulting film is reduced because the naphthoquinonediazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, and the mechanical properties are deteriorated. Problems, such as poor adhesion and reduced adhesiveness, may occur. From such a viewpoint, the preferred molecular weight of the naphthoquinonediazide compound is 300 to 100.
0. More preferably, it is 350 to 800. The amount of the naphthoquinonediazide compound to be added is preferably 1 to 100 parts by weight of the polymer.
To 50 parts by weight.

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 with an underlying substrate such as a silicon wafer, a silane coupling agent, a titanium chelating agent or the like is 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, or an aluminum chelating agent is added to 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. Substrates include silicon wafers, ceramics,
Gallium arsenide is used, but is not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, and roll coating. The thickness of the coating varies depending on the coating method, the solid concentration of the composition, the viscosity, and the like, but the coating is usually applied so that the thickness after drying is 0.1 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 is preferably performed using an oven, a hot plate, infrared rays or the like at a temperature in the range of 50 to 150 degrees for 1 minute 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 by 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. .

[0057]

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.

Preparation of Photosensitive Polyimide Precursor Film On a 6-inch silicon wafer, a photosensitive heat-resistant resin precursor composition (hereinafter referred to as varnish) having a thickness of 1 after prebaking was used.
The coating was applied to a thickness of 0 μm, and then prebaked at 120 ° C. for 3 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) to obtain a photosensitive polyimide precursor film.

Method for measuring 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 (Nikon Corporation i-line stepper NSR-175)
5-i7A), the reticle with the cut pattern was set, and the exposure time was changed to perform i-line exposure (intensity of 365 nm).

Development A 2.38% aqueous solution of tetramethylammonium hydroxide was sprayed at 50 rpm for 10 seconds using a developing device of SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd. After that, it was left still for 60 seconds at 0 rotation, and rinsed with water at 400 rotations.
The mixture was shaken off at 3000 rpm 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 Sensitivity After exposure and development, an exposure time for forming a 50 μm line-and-space pattern (1 L / 1 S) in a one-to-one width (hereinafter referred to as an optimum exposure time) was determined.

Calculation of Resolution After exposure and development, the minimum pattern size at the optimal exposure time for forming a 50 μm line-and-space pattern (1 L / 1 S) in a one-to-one width was defined as the resolution.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride (a) 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 by a rotary evaporator and poured into 1 liter of toluene to obtain an acid anhydride (a).

[0065]

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Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (b) 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 (b). The obtained solid was used for the reaction as it was.

[0068]

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Synthesis Example 3 Synthesis of hydroxyl-containing diamine (c) 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.

[0071]

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Synthesis Example 4 Synthesis of Hydroxyl Group-Containing Diamine (d) 2-amino-4-nitrophenol (15.4 g, 0.1 g)
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.

[0073]

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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.
Using g, a quinonediazide compound (1) was obtained in the same manner as in Synthesis Example 5.

[0075]

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Synthesis Example 6 Synthesis of quinonediazide compound (2) Under dry nitrogen flow, TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 15.31 g (0.05 mol) and 5
-Naphthoquinonediazidosulfonyl chloride 40.2
8 g (0.15 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 1,4-dioxane 5
Quinonediazide compound (2) in the same manner as in Synthesis Example 5 using 15.18 g of triethylamine mixed with 0 g.
I got

[0077]

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Synthesis Example 7 Synthesis of quinonediazide compound (3) Under a dry nitrogen stream, 4-isopropylphenol 6.81
g (0.05 mole) and 13.43 g (0.05 mole) of 5-naphthoquinonediazidosulfonyl chloride in 1,4
-Dissolved in 450 g of dioxane and brought to room temperature. Here, quinonediazide compound (3) was obtained in the same manner as in Synthesis Example 5 using 5.06 g of triethylamine mixed with 50 g of 1,4-dioxane.

[0079]

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Synthesis Example 8 Synthesis of quinonediazide compound (4) 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 (4) was obtained in the same manner as in Synthesis Example 8.

[0081]

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Similarly, the compounds having a phenolic hydroxyl group used in Examples and Comparative Examples are shown below.

[0083]

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Example 1 3.2 g (0.016 mol) of 4,4'-diaminodiphenyl ether and 1.24 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane under a stream of dry nitrogen
(0.005 mol), and 1.20 g (0.00) of 4-allylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) as a terminal blocking agent.
9 mol) with N-methyl-2-pyrrolidone (NMP) 50
g. To this, 21.4 g (0.03 mol) of the hydroxy group-containing acid anhydride (a) was added together with 14 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, a solution prepared by diluting 7.14 g (0.06 mol) of N, N-dimethylformamide dimethyl acetal with 5 g of NMP was added dropwise over 10 minutes. After the addition, the mixture was stirred at 50 ° C. for 3 hours.

To 40.0 g of the obtained solution, 2.0 g of the naphthoquinonediazide compound (1) shown above and 1.0 g of Bis-Z (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a compound having a phenolic hydroxyl group. Was added to obtain a varnish A of a photosensitive polyimide precursor composition. Using the obtained varnish, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed as described above, and the varnish was evaluated for sensitivity, residual film ratio, and resolution.

Example 2 Diamine (b) 1 obtained in Synthesis Example 2 under a stream of dry nitrogen
3.6 g (0.0225 mol), 4 g
-Ethynyl aniline (manufactured by Fuji Photo Film Co., Ltd.)
29 g (0.0025 mol) was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). 17.5 g (0.025 mol) of the hydroxy group-containing anhydride (a) was added together with 30 g of pyridine, and the mixture was reacted at 60 ° C. for 6 hours. After completion of the reaction, the solution was poured into 2 liters of water, and a precipitate of polymer solid was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 20 hours.

10 g of solid polymer thus obtained
2 g of the naphthoquinonediazide compound (2) shown above and BisRS-2P (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a compound having a phenolic hydroxyl group
2.0 g and 1 g of vinyltrimethoxysilane were dissolved in 30 g of gamma-butyrolactone to obtain a varnish B of a photosensitive polyimide precursor composition. Using the obtained varnish, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed as described above, and the varnish was evaluated for sensitivity, residual film ratio, and resolution.

Example 3 16.06 g (0.0425 mol) of the diamine compound (c) obtained in Synthesis Example 3 under a stream of dry nitrogen and 4-vinylaniline (Tokyo Kasei Kogyo Co., Ltd.) as a terminal blocking agent Made)
0.3 g (0.025 mol), 1.24 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane
(0.005 mol) was dissolved in 50 g of NMP. Here, 12.4 g (0.04 mol) of 3,3 ′, 4,4′-diphenylethertetracarboxylic anhydride was added to NMP21.
g, and allowed to react at 20 ° C. for 1 hour.
The reaction was performed at 0 ° C. for 2 hours. Here maleic anhydride 0.9
After adding 8 g (0.01 mol) and stirring at 50 ° C. for 2 hours,
N, N-dimethylformamide diethyl acetal 1
A solution obtained by diluting 4.7 g (0.1 mol) with 5 g of NMP was added dropwise over 10 minutes. After the addition, the mixture was stirred at 50 ° C. for 3 hours.

To 30 g of the obtained solution, 1.6 g of the naphthoquinonediazide compound (3) shown above and TrisP-PA (trade name, as a compound having a phenolic hydroxyl group)
0.8 g of Honshu Chemical Industry Co., Ltd. was dissolved to obtain a varnish C of a photosensitive polyimide precursor composition. Using the obtained varnish, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed as described above, and the varnish was evaluated for sensitivity, residual film ratio, and resolution.

Example 4 6.08 g (0.025 mol) of the diamine compound (d) obtained in Synthesis Example 4 and 4.21 g (0.021 mol) of 4,4′-diaminodiphenyl ether were obtained under a stream of dry nitrogen. 0.62 g (0.0025 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and 0.21 g (0.3%) of 3-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) as a terminal blocking agent. 0015 mol) with NMP7
0 g was dissolved. Hydroxyl group-containing acid anhydride (a)
24.99 g (0.035 mol), 3,3 ′, 4,4 ′
-Biphenyltetracarboxylic dianhydride 4.41 g
(0.015 mol) was added at room temperature together with 25 g of NMP, and the mixture was stirred at room temperature for 1 hour and then at 50 ° C. for 2 hours. Then, 17.6 g of glycidyl methyl ether
(0.2 mol) diluted with 10 g of NMP,
Stirred at 70 ° C. for 6 hours.

To 40 g of this polymer solution, 2.5 g of the naphthoquinonediazide compound (4) shown above and BIR-PC (trade name, as a compound having a phenolic hydroxyl group)
2.0 g of Asahi Organic Materials Industry Co., Ltd.) was dissolved to obtain a varnish D of a photosensitive polyimide precursor composition. Using the obtained varnish, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed as described above, and the varnish was evaluated for sensitivity, residual film ratio, and resolution.

Example 5 15.56 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane under a stream of dry nitrogen
(0.0425 mol), 1.00 g (0.0%) of 4-allylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) as a terminal blocking agent.
075 mol) with N-methyl-2-pyrrolidone (NMP)
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 dropped so that the internal temperature did not exceed 0 ° C. did. After completion of the dropwise addition, stirring was continued at -15 ° C for 6 hours.

After the completion of the reaction, the solution was poured into 3 l of water to collect a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours.

The polymer powder 1 thus obtained was
2.0 g of the naphthoquinonediazide compound (2) and 1.0 g of Bis-Z (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) are dissolved in 30 g of NMP in 0.0 g to prepare a photosensitive polybenzoxazole precursor composition. A varnish E was obtained. Using the obtained varnish, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed as described above, and the varnish was evaluated for sensitivity, residual film ratio, and resolution.

Example 6 Diamine (b) 1 obtained in Synthesis Example 2 under a stream of dry nitrogen
3.6 g (0.0225 mol), 4 g
-(3-aminophenyl) -2-methyl-3-butyne-
0.44 g (0.0025 mol) of 2-ol (trade name: M-APACB, manufactured by Fuji Photo Film Co., Ltd.) was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP).
Here, 17.5 g of hydroxy group-containing acid anhydride (a)
(0.025 mol) together with 30 g of pyridine,
The reaction was performed at 60 ° C. for 6 hours. After completion of the reaction, the solution is
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 solid polymer thus obtained
2 g of the naphthoquinonediazide compound (2) shown above and BIR-PC (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.) 2.0 as a compound having a phenolic hydroxyl group
g and 1 g of vinyltrimethoxysilane were dissolved in 30 g of gamma-butyrolactone to obtain a varnish F of a photosensitive polyimide precursor composition. Using the obtained varnish, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed as described above, and the varnish was evaluated for sensitivity, residual film ratio, and resolution.

Comparative Example 1 3.2 of 4,4'-diaminophenyl ether of Example 1
g was changed to 5.01 g (0.025 mol), and varnish G of a photosensitive polyimide precursor composition was obtained in the same manner as in Example 1, except that the terminal blocking agent 4-allylaniline was not used. . Using the obtained varnish, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed as described above, and the varnish was evaluated for sensitivity, residual film ratio, and resolution.

Comparative Example 2 A varnish H of a photosensitive polyimide precursor composition was obtained in the same manner as in Example 2, except that the terminal blocking agent N-ethynylaniline was not used. Using the obtained varnish, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed as described above, and the varnish was evaluated for sensitivity, residual film ratio, and resolution.

Comparative Example 3 The same procedure as in Example 3 was repeated except that the terminal blocking agent 4-vinylaniline and the compound having a phenolic hydroxyl group, TrisP-PA, were not used. Varnish I was obtained. Using the obtained varnish, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed as described above, and the varnish was evaluated for sensitivity, residual film ratio, and resolution.

Comparative Example 4 A varnish J of a photosensitive polyimide precursor composition was obtained in the same manner as in Example 4, except that the terminal blocking agent 3-nitroaniline was not used. Using the obtained varnish, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed as described above, and the varnish was evaluated for sensitivity, residual film ratio, and resolution.

Comparative Example 5 15.56 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane of Example 5 was added to 1
8.3 g (0.05 mol), except that the terminal blocking agent 4-allylaniline was not used.
Varnish K of photosensitive polybenzoxazole precursor composition
I got As described above, using the obtained varnish, to produce a photosensitive polyimide precursor film on a silicon wafer, exposure,
After development, the varnish was evaluated for sensitivity, residual film ratio, and resolution.

The evaluation results of Examples 1 to 6 and Comparative Examples 1 to 5 are shown in Table 1.

[0103]

[Table 1]

[0104]

According to the present invention, a positive photosensitive resin precursor composition which can be developed with an aqueous alkali solution and has excellent resolution, sensitivity and residual film ratio can be obtained.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission Date] October 2, 2000 (2000.10.
2)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 3

[Correction method] Change

[Correction contents]

[Formula 3] (R ¹¹ and R ¹³ each represent a trivalent to tetravalent organic group having a hydroxyl group selected from 2 to 20 carbon atoms, and R ¹² 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. )

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 501 G03F 7/004 501 7/022 601 7/022 601 H01L 21/027 H01L 21/312 D 21/312 21/30 502R F-term (reference) 2H025 AA01 AA02 AA04 AB16 AB17 AC01 AD03 BE01 BJ04 CB25 CC20 4J002 CM041 EJ036 EJ046 EQ037 FD310 GP03 4J043 PA02 PA19 PB08 PC025 PC065 PC075 PC115 Q3215 TAB31 QB15 TA71 UA121 UA131 UA141 UA151 UA152 UA381 UB011 UB012 UB051 UB061 UB062 UB121 UB122 UB231 UB232 UB301 UB302 VA021 VA022 VA032 VA061 VA062 VA072 WA06 XB09 ZA21 ZB22 5F058 AC02 AC07 AF04 AG01

Claims (5)

[Claims] (1) General formula (1) and / or general formula
A polymer having the structural unit represented by (2) as a main component,
(B) a compound having a phenolic hydroxyl group, and (C)
It contains a quinonediazide compound which is
A positive-type photosensitive resin precursor composition. Embedded image(Where R¹Is a divalent having at least two carbon atoms
To an octavalent organic group, R ^TwoIs at least two carbon atoms
A divalent to hexavalent organic group having an atom, R^ThreeIs hydrogen,
Is an organic group having 1 to 20 carbon atoms, R^FourIs hydrogen atom, water
It represents an acid group or a hydrocarbon group having 1 to 10 carbon atoms. R^Five
Is a carbon containing at least one unsaturated hydrocarbon group
Hydrocarbon group, nitro group, methylol from number 1 to 10
Group, ester group, and hydroxyalkynyl group. n is
An integer from 10 to 100000, m is from 0 to 2
Integers, p and q each represent an integer from 0 to 4. p + q> 0
It is. ) 2. A compound represented by the general formula (1) or the general formula (2):
^2. The positive photosensitive resin precursor composition according to claim ^{1, wherein 1} (COOR ³ ) m (OH) p is represented by the general formula (3). Embedded image (R ⁶ and R ^{8 each} represent a divalent to tetravalent organic group selected from 2 to 20 carbon atoms, and R ⁷ represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. R ⁹ and R ¹⁰ 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.) 3. A compound represented by the general formula (1) or the general formula (2):
^2. The positive photosensitive resin precursor composition according to claim 1, wherein ² (OH) q is represented by the general formula (4). Embedded image (R ¹¹ and R ¹³ each represent a trivalent to tetravalent organic group having a hydroxyl group selected from 2 to 20 carbon atoms, and R ¹² 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. ) 4. A compound represented by the formula (1) or the formula (2):
^2. The positive photosensitive resin precursor composition according to claim 1, wherein ² (OH) q is represented by the general formula (5). Embedded image (R ¹⁴ and R ¹⁶ each represent a divalent organic group having 2 to 20 carbon atoms, and R ¹⁵ represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. Represents an integer from 1 to 4.) 5. R2 of the general formula (1) or the general formula (2)
(OH) q is represented by General formula (6), The positive photosensitive resin precursor composition of Claim 1 characterized by the above-mentioned. Embedded image (R ¹⁷ represents a divalent organic group selected from 2 to 20 carbon atoms, R ¹⁸ is, .w 1 showing a trivalent to hexavalent organic group having a hydroxyl group selected from 3-20C Represents an integer from to 4)