JP3460679B2 - Positive photosensitive resin precursor composition - Google Patents

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, etc. of a semiconductor device, 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, polyamic acid to which naphthoquinonediazide is added (JP-A-52-13315), a hydroxyl group having a hydroxyl group Naphthoquinone diazide added to the soluble polyimide (JP-A-64-60630), and naphthoquinone diazide added to a polyamide having a hydroxyl group (JP-A-56-56).
No. 27140) was known.

However, in the case where naphthoquinonediazide is added to ordinary polyamic acid, the solubility of the carboxyl group of polyamic acid is higher than the effect of naphthoquinonediazide on alkali dissolution, so that the desired pattern can be obtained in most cases. There was a problem that it did not exist. Therefore, 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, with the addition of naphthoquinonediazide to this polyamic acid derivative, the effect of inhibiting the dissolution of naphthoquinonediazide in alkali becomes very large, and in most cases, the desired pattern can be obtained, but development is not possible in a short time (below. , Low sensitivity) and that a fine pattern is not resolved (hereinafter referred to as low resolution).

[0004]

In consideration 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 by using a specific end-capping agent, and before exposure to an alkali developer. It does not dissolve, but it dissolves easily in an alkaline developer when exposed to light, so there is little film loss due to development, development can be done in a short time (hereinafter referred to as high sensitivity), and fine patterns are resolved (hereinafter, high resolution). It was the invention.

[0005]

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

[0006]

[Chemical 6]

(In the formula, R ¹ is a divalent to octavalent organic group having at least two carbon atoms, and R ² is at least 2
A divalent to hexavalent organic group having 3 or more carbon atoms, R ³
Is hydrogen or an organic group having 1 to 20 carbon atoms, R ⁴ is 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 and having 1 to 10 carbon atoms, a nitro group, a methylol group, an ester group, and a hydroxyalkynyl group. n is an integer from 10 to 100000, 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 In the present invention, a polymer containing a structural unit represented by the general formula (1) and / or the general formula (2) as a main component means an imide ring or an oxazole ring by heating or by a suitable catalyst. , And other polymers having a cyclic structure. By forming a ring structure, heat resistance and solvent resistance are dramatically improved.

The above general formulas (1) and (2) represent a polyamic acid having a hydroxyl group. Due to the presence of the hydroxyl group, the solubility in an alkaline aqueous solution is higher than that of the polyamic acid having no hydroxyl group. Will also be good. Particularly, among the hydroxyl groups, phenolic hydroxyl groups are more preferable than the solubility in the alkaline aqueous solution. In addition, 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 alkaline aqueous solution, water repellency is appropriately exhibited at the interface of the film, so that the interface is not soaked. Can be suppressed. However, if the content of fluorine atoms exceeds 20% by weight, the solubility in an alkaline aqueous solution decreases, the organic solvent resistance of the polymer having a cyclic structure by heat treatment decreases, and the solubility in fuming nitric acid decreases. Not good for Thus, it is preferable that the fluorine atom is contained in an amount of 10% by weight or more and 20% by weight or less.

R in the above general formula (1) or general formula (2)
¹ represents a structural component of an acid dianhydride, and this acid dianhydride contains an aromatic ring, and has 1 to 4 hydroxyl groups, and is divalent having at least 2 or more carbon atoms. It is preferably an organic group having 8 to 8 valences, and more preferably a trivalent or tetravalent organic group having 6 to 30 carbons.

Specifically, those having a structure represented by the general formula (3) are preferable, and in this case, R ⁶ and R ⁸ are divalent to tetravalent organic groups selected from 2 to 20 carbon atoms. Although shown, those containing an aromatic ring are preferable in view of the heat resistance of the obtained polymer, and among them, particularly preferable structures include those such as trimellitic acid, trimesic acid, and naphthalenetricarboxylic acid residues. Further, R ⁷ is preferably a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. Furthermore, the hydroxyl group is preferably located adjacent to the amide bond. As such an example, bis (3-amino-4-hydroxyphenyl) hexafluoropropane containing a fluorine atom, bis (3-
Hydroxy-4-aminophenyl) hexafluoropropane, fluorine-free, 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,
The thing which the amino group of 1,4-diamino-2,5-dihydroxybenzene couple | bonded etc. can be mentioned.

Further, R ⁹ and R ^{10 in} the general formula (3) are 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 lowered.

In the general formula (3), o and s represent integers of 0 to 2 and r represents integers of 1 to 4. r
When the value is 5 or more, the properties of the resulting heat resistant resin film deteriorate.

R in the general formula (1) or the general formula (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]

[Chemical 7]

Further, it may be modified with a tetracarboxylic acid or a dicarboxylic acid having no hydroxyl group as long as the solubility in alkali, the photosensitivity and the heat resistance are not impaired. Examples of this include aromatic tetracarboxylic acids such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, and diphenylsulfonetetracarboxylic acid, and the two carboxyl groups thereof being methyl groups or ethyl groups. Aliphatic tetracarboxylic acids such as diester compounds, butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, and diester compounds in which two carboxyl groups thereof are methyl groups or ethyl groups, terephthalic acid, isophthalic acid, diphenyl ether 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 50 mol% or less of the acid component, more preferably 30 mol% or less. If it is modified by 50 mol% or more, the solubility in alkali and the photosensitivity may be impaired.

R in the above general formula (1) or general formula (2)
² represents the structural component of the diamine. In this, R ²
As a preferable example of, a polymer having an aromatic group and a hydroxyl group is preferable due to the heat resistance of the obtained polymer, and a specific example thereof has a fluorine atom, bis (amino-
(Hydroxy-phenyl) hexafluoropropane, fluorine atom-free, diaminodihydroxypyrimidine,
Examples thereof include compounds such as diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol and dihydroxybenzidine, and compounds having the structures represented by the general formulas (4), (5) and (6).

Among these, R ¹¹ , R ¹³ in the general formula (4),
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 in view of the heat resistance of the obtained polymer. R ¹² in the general formula (4), the 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 integers of 1 or 2, v in the general formula (5) and w in the general formula (6) represent integers from 1 to 4.

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

[0020]

[Chemical 8]

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]

[Chemical 9]

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

[0024]

[Chemical 10]

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, which is aromatic due to the heat resistance of the resulting polymer. Those having a ring are preferable. Specifically, hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxyphenyl) ) Represents a sulfone group, a hydroxydiphenyl ether group, a dihydroxydiphenyl ether group, and the like. Further, aliphatic groups such as hydroxycyclohexyl group and dihydroxycyclohexyl group can also be used. R ¹² has 2 carbon atoms
It represents a divalent organic group up to -30. An aromatic divalent group is preferable to the heat resistance of the obtained polymer, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. Other than these, an aliphatic cyclohexyl group and the like can also be used.

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 preferable to the heat resistance of the obtained polymer. Examples of such groups include a phenyl group, a biphenyl group,
Examples thereof include a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group, but in addition to these, an aliphatic cyclohexyl group can also be used. R ¹⁵ is
A trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms is shown, and one having an aromatic ring is preferable 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. Further, aliphatic groups such as hydroxycyclohexyl group and dihydroxycyclohexyl group can also be used.

In the general formula (6), R ¹⁷ has 2 to 2 carbon atoms.
It represents a divalent organic group selected from 0. Due to the heat resistance of the obtained polymer, an aromatic divalent group is preferable, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group and a diphenylsulfone group. However, other than this, 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 one having an aromatic ring is preferable from the heat resistance of the resulting polymer. Specifically, hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxyphenyl) ) Represents a sulfone group, a hydroxydiphenyl ether group, a dihydroxydiphenyl ether group, and the like. Further, aliphatic groups such as hydroxycyclohexyl group and dihydroxycyclohexyl group can also be used.

It is also possible to modify with another diamine component in the range of 1-40 mol%. Examples of these are phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone or aromatic compounds thereof. Examples thereof include compounds in which the group ring is substituted with an alkyl group or a halogen atom. Examples of such compounds include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone or aromatic compounds thereof. Examples thereof include compounds in which the group ring is substituted with an alkyl group or a halogen atom, such as aliphatic cyclohexyldiamine and methylenebiscyclohexylamine. When 40 mol% or more of such a diamine component is copolymerized, 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 resulting positive photosensitive resin precursor solution, R
^{Although 3} is preferably an organic group, hydrogen is preferred from the viewpoint of solubility in an alkaline aqueous solution. In the present invention, hydrogen atoms and alkyl groups can be mixed. By controlling the amounts of hydrogen and organic groups in R ^3, the dissolution rate in the alkaline aqueous solution changes, and therefore, by this adjustment, a positive photosensitive resin precursor composition having an appropriate dissolution rate can be obtained. . A preferable range is that 10% to 90% of R ³ is a hydrogen atom. If R ³ has more than 20 carbon atoms, it will not dissolve in the alkaline aqueous 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]

[Chemical 11]

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

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

Further, m in the general formula (1) or the general formula (2)
Represents the number of carboxyl groups and represents an integer from 0 to 2. N in the general formula (1) or general formula (2) represents the number of repeating structural units of the polymer of the present invention, and is preferably in the range of 10 to 100,000.

Polyhydroxyamide may be used in place of polyamic acid as a heat-resistant polymer precursor similar to polyamic acid. A method for producing such a polyhydroxyamide can be obtained by subjecting a bisaminophenol compound and a dicarboxylic acid to a condensation reaction. Specifically, dicyclohexylcarbodiimide (D
CC) such as a dehydration condensing agent and an acid are reacted, and a bisaminophenol compound is added thereto, or a solution of dicarboxylic acid dichloride is added dropwise to a solution of a bisaminophenol compound to which a tertiary amine such as pyridine is added. is there.

In the case of using polyhydroxyamide, a positive type photosensitive heat-resistant material in which a portion exposed to ultraviolet rays can be removed with an alkaline aqueous solution by adding a photosensitizer such as naphthoquinone diazide sulfonate to a solution of polyhydroxyamide A resin precursor composition can be obtained.

Further, in order to improve the adhesiveness to the substrate, R1 and R2 may be copolymerized with an aliphatic group having a siloxane structure within a range that does not lower the heat resistance. Specifically, as the diamine component, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane and the like are contained in an amount of 1-10.
Examples include those copolymerized by mol%.

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 have the same weight as other structural units. It may be a united body or a blended body. At that time, it is preferable that the structural unit represented by the general formula (1) or the general formula (2) is contained in an amount of 50 mol% or more. The type and amount of structural units used for copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polyimide-based polymer obtained by the final heat treatment.

The heat-resistant resin precursor of the present invention is synthesized by a known method by replacing a part of diamine with a terminal blocking agent which is a monoamine. For example, a method of reacting a tetracarboxylic acid dianhydride and a diamine compound at a low temperature, a method of obtaining a diester from a tetracarboxylic acid dianhydride and an alcohol, and then reacting the diamine in the presence of a condensing agent, a tetracarboxylic acid 2 A diester can be obtained from an anhydride and an alcohol, and then the remaining dicarboxylic acid can be converted to an acid chloride and reacted with a diamine.

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 in which a terminal blocking agent is introduced 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 analyzed by gas chromatography (GC)
Alternatively, the end-capping agent used in the present invention can be easily detected by NMR measurement. Separately from this, the polymer component in which the terminal blocking agent is introduced is directly subjected to pyrolysis gas chromatograph (PGC), infrared spectrum and C13NMR.
It can be easily detected even by spectrum measurement.

Examples of the compound having a phenolic hydroxyl group used in the present invention include Bis-Z and 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 (above, 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 (above, trade name,
Asahi Organic Material Industry Co., Ltd. may be mentioned.

Of these, preferred compounds having a phenolic hydroxyl group are, for example, Bis-Z and 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 etc. are mentioned. Of these, particularly preferable 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 this compound having a phenolic hydroxyl group, the resin composition obtained is hardly dissolved in an alkali developing solution before exposure and easily dissolved in an alkali developing solution after exposure, so that film loss due to development is reduced. Development is facilitated in a short time in a small amount.

The amount of such a compound having a phenolic hydroxyl group added 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.

As the esterified quinonediazide compound (c) added to the present invention, a compound in which a sulfonic acid of naphthoquinonediazide is bound with an ester to a compound having a phenolic hydroxyl group is preferable. The compound having a phenolic hydroxyl group used here may be the same as or different from the compound having a phenolic hydroxyl group of (b). Examples of such compounds include Bis-Z and 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 (these product 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 (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.), naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, methylenebisphenol, BisP-AP (trade name, Honshu Chemical Industry) Compounds of 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid introduced into a compound (such as manufactured by Co., Ltd.) by an ester bond can be exemplified as preferable compounds, 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 naphthoquinonediazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that the heat resistance of the obtained film is lowered and the mechanical properties are lowered. However, there is a possibility that problems such as deterioration of adhesiveness may occur. From this point of view, the preferred naphthoquinonediazide compound has a molecular weight of 300 to 100.
It is 0. More preferably, it is 350 to 800. The amount of such naphthoquinonediazide compound added is preferably 1 with respect to 100 parts by weight of the polymer.
To 50 parts by weight.

If necessary, a surfactant, esters such as ethyl lactate or propylene glycol monomethyl ether acetate, ethanol, etc. may be added 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. Further, inorganic particles such as silicon dioxide and titanium oxide, or polyimide powder can be added.

Further, in order to enhance the adhesiveness to a base substrate such as a silicon wafer, a silane coupling agent, a titanium chelating agent, etc. 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 base substrate can be pretreated with such a chemical solution.

When added to the varnish, a silane coupling agent such as methylmethacryloxydimethoxysilane or 3-aminopropyltrimethoxysilane, a titanium chelating agent or an aluminum chelating agent is added in an amount of 0.5 to 10 with respect to the polymer in the varnish. Wt% is added.

When treating a substrate, the coupling agent described above 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 of 5 to 20% by weight is surface-treated by spin coating, dipping, spray coating, steam treatment or the like. Depending on the case, then 50 to 300 degrees Celsius
The reaction between the substrate and the above coupling agent proceeds by applying the 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 coated on a substrate. Substrates include silicon wafers, ceramics,
Gallium arsenide and the like are used, but not limited to these. Examples of the coating method include spin coating using a spinner, spray coating, and roll coating. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., but the coating film thickness after drying is usually 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 carried out using an oven, a hot plate, infrared rays or the like in the range of 50 to 150 ° C. for 1 minute to several hours.

Next, this photosensitive heat-resistant precursor composition film is exposed to actinic rays through a mask having a desired pattern. The actinic rays used for exposure include ultraviolet rays, visible rays, electron rays, and X-rays. In the present invention, i rays (365 nm), h rays (405 nm), g
It is preferred to use the line (436 nm).

The pattern of the heat-resistant resin is formed by removing the exposed portion with a developing solution after the exposure. As the developing solution, an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl Aqueous solutions of compounds showing alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine are preferred. In some cases, a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolaclone, dimethylacrylamide, methanol, ethanol, etc. Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added alone or in combination of several kinds. Good. After development, rinse with water. Also here, rinse treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.

After development, a temperature of 200 to 500 ° C. is applied to convert into a heat resistant resin film. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and gradually increasing the temperature or by 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 a passivation film for semiconductors, a protective film for semiconductor elements, an interlayer insulating film for multi-layer wiring for high-density packaging, and the like. .

[0057]

The present invention will be described below with reference to examples and techniques, but the present invention is not limited to these examples. The photosensitive heat-resistant resin precursor compositions in the examples were evaluated by the following methods.

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

Method for measuring film thickness Lambda Ace STM-6 manufactured by Dainippon Screen Mfg. Co., Ltd.
02 was used and the measurement was performed at a refractive index of 1.64.

Exposure exposure machine (i-line stepper NSR-175 manufactured by Nikon Corporation)
5-i7A), a reticle with a cut pattern was set, and the exposure time was changed to perform i-line exposure (intensity of 365 nm).

Development Using a developing device SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd., a 2.38% aqueous solution of tetramethylammonium hydroxide was sprayed at 50 rpm for 10 seconds. After this, leave at 0 rpm for 60 seconds, rinse with water at 400 rpm,
It was shaken off at 3000 rpm for 10 seconds and dried.

Calculation of residual film rate The residual film rate was calculated according to the following formula. Residual film ratio (%) = film thickness after development / film thickness after prebaking × 1
00 Sensitivity Calculation After exposure and development, an exposure time for forming a 50 μm line-and-space pattern (1 L / 1S) in a width of 1: 1 (hereinafter referred to as an optimum exposure time) was determined.

Calculation of resolution After exposure and development, the minimum pattern size in the optimum exposure time for forming a 50 μm line-and-space pattern (1 L / 1 S) in a width of 1: 1 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 allyl glycidyl ether 34.2 g (0.3 mol) were added to gamma butyrolactone 1
It was dissolved in 00 g and cooled to -15 ° C. 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of gamma-butyrolactone was added dropwise thereto so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, 4 at 0 ℃
Reacted for hours. The solution was concentrated with a rotary evaporator and poured into 1 l of toluene to obtain an acid anhydride (a).

[0065]

[Chemical 12]

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (b) 18.3 g (0.05 mol) of BAHF was added to 100 parts of acetone.
The solution was dissolved in 1 ml of 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 the dropping is completed,
The reaction was carried out at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and dried in vacuum at 50 ° C.

30 g of the solid was placed in a 300 ml stainless autoclave, dispersed in 250 ml of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here by a balloon to carry out the reduction reaction at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloon did not deflate any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and the mixture was concentrated with a rotary evaporator to obtain a diamine compound (b). The obtained solid was used for the reaction as it was.

[0068]

[Chemical 13]

Synthesis Example 3 Synthesis of hydroxyl group-containing diamine (c) 2-amino-4-nitrophenol 15.4 g (0.1
50 ml of acetone, 30 g of propylene oxide
It was dissolved in (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. After the dropping was completed, the reaction was carried out at -15 ° C for 4 hours. Then, 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 to this, and stirring was continued at room temperature until the hydrogen gas balloon did not shrink further, and the mixture was further stirred for 2 hours with the hydrogen gas balloon attached. After the stirring was completed, the palladium compound was removed by filtration, and the solution was concentrated by a rotary evaporator until the volume became half. Ethanol is added here to perform recrystallization,
Crystals of the desired compound were obtained.

[0071]

[Chemical 14]

Synthesis Example 4 Synthesis of hydroxyl group-containing diamine (d) 2-amino-4-nitrophenol 15.4 g (0.1
Mol) acetone 100 ml, propylene oxide 1
It was dissolved in 7.4 g (0.3 mol) and cooled to -15 ° C. 20.4 g of 4-nitrobenzoyl chloride here
A solution of (0.11 mol) in 100 ml of acetone was gradually added dropwise. After the dropping was completed, the reaction was carried out at -15 ° C for 4 hours. Then, the temperature was returned to room temperature and the generated precipitate was collected by filtration. Then, crystals of the target compound were obtained in the same manner as in Synthesis Example 2.

[0073]

[Chemical 15]

Synthesis Example 5 Synthesis of quinonediazide compound (1) Under a dry nitrogen stream, 7.21 g (0.05
Mol) and 13.43 g (0.05 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane, and the mixture was brought to room temperature. Here, triethylamine 5.06 mixed with 50 g of 1,4-dioxane
Using g, a quinonediazide compound (1) was obtained in the same manner as in Synthesis Example 5.

[0075]

[Chemical 16]

Synthesis Example 6 Synthesis of quinonediazide compound (2) TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 15.31 g (0.05 mol) and 5 under a dry nitrogen stream.
-Naphthoquinone diazide sulfonyl 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
Using 15.18 g of triethylamine mixed with 0 g of quinonediazide compound (2) in the same manner as in Synthesis Example 5.
Got

[0077]

[Chemical 17]

Synthesis Example 7 Synthesis of quinonediazide compound (3) 4-isopropylphenol 6.81 under a stream of dry nitrogen.
g (0.05 mol) and 5-naphthoquinone diazide sulfonyl chloride 13.43 g (0.05 mol) 1,4
-Dissolved in 450 g dioxane and brought to room temperature. Here, 5.06 g of triethylamine mixed with 50 g of 1,4-dioxane was used, and was used in the same manner as in Synthesis Example 5 to obtain a quinonediazide compound (3).

[0079]

[Chemical 18]

Synthesis Example 8 Synthesis of quinonediazide compound (4) 11.41 g of bisphenol A under a stream of dry nitrogen
(0.05 mol) and 5-naphthoquinone diazide sulfonyl chloride (26.86 g, 0.1 mol) 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]

[Chemical 19]

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

[0083]

[Chemical 20]

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), 4-allylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.20 g (0.00
9 mol) to N-methyl-2-pyrrolidone (NMP) 50
g. 21.4 g (0.03 mol) of the hydroxy group-containing acid anhydride (a) was added together with 14 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour and then at 50 ° C. for 4 hours. Then, 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 dropping, the mixture was stirred at 50 ° C. for 3 hours.

2.0 g of the naphthoquinonediazide compound (1) shown above was added to 40.0 g of the obtained solution, 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 the photosensitive polyimide precursor composition. Using the obtained varnish, a photosensitive polyimide precursor film was prepared, exposed and developed on a silicon wafer as described above, and the sensitivity, residual film rate and resolution of the varnish were evaluated.

Example 2 Diamine (b) 1 obtained in Synthesis Example 2 under a stream of dry nitrogen
3.6 g (0.0225 mol), 4 as an end-capping agent
-Ethynylaniline (manufactured by Fuji Photo Film Co., Ltd.) 0.
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 acid anhydride (a) was added thereto 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 l 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 polymer solid 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 prepared, exposed and developed on a silicon wafer as described above, and the sensitivity, residual film rate and resolution of the varnish were evaluated.

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 (manufactured by Tokyo Chemical Industry Co., Ltd.) as a terminal blocking agent Made)
0.3 g (0.025 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 1.24 g
(0.005 mol) was dissolved in 50 g of NMP. Here, 12.4 g (0.04 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid anhydride was added to NMP21.
g, and reacted at 20 ° C. for 1 hour, then 5
The reaction was carried out at 0 ° C for 2 hours. 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 prepared by diluting 4.7 g (0.1 mol) with 5 g of NMP was added dropwise over 10 minutes. After the dropping, the mixture was stirred at 50 ° C. for 3 hours.

In 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 prepared, exposed and developed on a silicon wafer as described above, and the sensitivity, residual film rate and resolution of the varnish were evaluated.

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 dry nitrogen stream. 0.62 g (0.0025 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 0.21 g of 3-nitroaniline (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a terminal blocking agent. 0015 mol) to NMP7
It was dissolved in 0 g. Hydroxyl group-containing acid anhydride (a)
24.99 g (0.035 mol), 3,3 ', 4,4'
-Biphenyl tetracarboxylic acid 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 was added,
The mixture was 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 as a compound having a phenolic hydroxyl group, BIR-PC (trade name,
2.0 g of Asahi Organic Materials 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 prepared, exposed and developed on a silicon wafer as described above, and the sensitivity, residual film rate and resolution of the varnish were evaluated.

Example 5 15.56 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane under a stream of dry nitrogen
(0.0425 mol), 4-allylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.00 g (0.0
075 mol) to 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 gammabutyrolactone was added dropwise so that the internal temperature did not exceed 0 ° C. did. After the dropping was completed, stirring was continued for 6 hours at -15 ° C.

After 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 with water three times, and then dried in a vacuum dryer at 80 ° C. for 20 hours.

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

Example 6 Diamine (b) 1 obtained in Synthesis Example 2 under a stream of dry nitrogen
3.6 g (0.0225 mol), 4 as an end-capping agent
-(3-aminophenyl) -2-methyl-3-butyne-
2-Ol (trade name: M-APACB, manufactured by Fuji Photo Film Co., Ltd.) 0.44 g (0.0025 mol) was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP).
17.5 g of hydroxy group-containing acid anhydride (a)
(0.025 mol) with 30 g of pyridine,
The reaction was carried out at 60 ° C for 6 hours. After the reaction was completed, the solution was added with 2 l of water.
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 polymer solid thus obtained
2 g of the naphthoquinonediazide compound (2) shown above and BIR-PC (trade name, manufactured by Asahi Organic Materials 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 prepared, exposed and developed on a silicon wafer as described above, and the sensitivity, residual film rate and resolution of the varnish were evaluated.

Comparative Example 1 4,4′-diaminophenyl ether 3.2 of Example 1
g was changed to 5.01 g (0.025 mol), and the same procedure as in Example 1 was carried out except that the end-capping agent 4-allylaniline was not used to obtain a varnish G of a photosensitive polyimide precursor composition. . Using the obtained varnish, a photosensitive polyimide precursor film was prepared, exposed and developed on a silicon wafer as described above, and the sensitivity, residual film rate and resolution of the varnish were evaluated.

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 of Example 2 was not used. Using the obtained varnish, a photosensitive polyimide precursor film was prepared, exposed and developed on a silicon wafer as described above, and the sensitivity, residual film rate and resolution of the varnish were evaluated.

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

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 of Example 4 was not used. Using the obtained varnish, a photosensitive polyimide precursor film was prepared, exposed and developed on a silicon wafer as described above, and the sensitivity, residual film rate and resolution of the varnish were evaluated.

COMPARATIVE EXAMPLE 5 15.56 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane of Example 5 was used as 1 part.
The same procedure as in Example 5 was repeated except that the amount of the end-capping agent 4-allylaniline was changed to 8.3 g (0.05 mol).
Varnish K of photosensitive polybenzoxazole precursor composition
Got As described above using the obtained varnish, a photosensitive polyimide precursor film is produced on a silicon wafer, exposed,
After development, the varnish was evaluated for sensitivity, residual film rate, 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]

INDUSTRIAL APPLICABILITY According to the present invention, a positive photosensitive resin precursor composition which can be developed with an alkaline aqueous solution and is excellent in resolution, sensitivity and residual film rate can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI G03F 7/004 501 G03F 7/004 501 7/022 7/022 H01L 21/027 H01L 21/30 502R (56) Reference JP-A-11-109620 (JP, A) JP-A-11-143070 (JP, A) JP-A-11-249306 (JP, A) JP-A-11-106651 (JP, A) JP-A-8-82931 (JP , A) JP 9-258441 (JP, A) JP 11-279404 (JP, A) JP 9-258439 (JP, A) JP 2001-5179 (JP, A) JP 2001- 64507 (JP, A) Special table 7-5009332 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (6)

(57) [Claims] 1. A polymer comprising (a) a structural unit represented by the general formula (1) and / or the general formula (2) as a main component,
A positive photosensitive resin precursor composition comprising (b) a compound having a phenolic hydroxyl group and (C) an esterified quinonediazide compound. [Chemical 1] (In the formula, R ¹ is a divalent to octavalent organic group having at least 2 or more carbon atoms, R ² is a divalent to hexavalent organic group having at least 2 or more carbon atoms, and R ³ is hydrogen. or .R ⁵ organic groups having a carbon number of 1 to 20, R ⁴ is showing a hydrocarbon group of a hydrogen atom, a hydroxyl group, from 1 to 10 carbon atoms
Represents a hydrocarbon group having at least one unsaturated hydrocarbon group and having 1 to 10 carbon atoms, a nitro group, a methylol group, an ester group and a hydroxyalkynyl group. n is an integer from 10 to 100000, m is an integer from 0 to 2, and p and q are integers from 0 to 4. p + q> 0
Is. ) 2. R in the general formula (1) or the general formula (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). [Chemical 2] (R ^6, R ⁸ represents a divalent to tetravalent organic radical selected from 2 to 20 carbon atoms, R ⁷ is a trivalent to hexavalent organic group having a hydroxyl group selected from 3-20C R ⁹ and R ^{10 each} represent hydrogen and / or an organic group having 1 to 20 carbon atoms, o and s each represent an integer of 0 to 2, and r represents an integer of 1 to 4.) 3. R in 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). [Chemical 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.
A divalent organic group selected from the following is shown. t and u are integers of 1 or 2. ) 4. R in the general formula (1) or the general formula (2).
² (OH) q is represented by general formula (5), The positive type photosensitive resin precursor composition of Claim 1 characterized by the above-mentioned. [Chemical 4] (R ¹⁴ and R ¹⁶ 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. R in the general formula (1) or the general formula (2).
² (OH) q is represented by General formula (6), The positive photosensitive resin precursor composition of Claim 1 characterized by the above-mentioned. [Chemical 5] (R ¹⁷ represents a divalent organic group selected from 2 to 20 carbon atoms, and R ¹⁸ represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. W is 1 Indicates an integer of up to 4). 6. R in the general formula (1) or the general formula (2). ^Five But
Vinyl group, ethynyl group, propynyl group, allyl group, 3-
Hydroxy-3-methyl-1-butynyl group, 3-hydro
Xy-3-methyl-1-pentynyl group, 3-hydroxy
-3-Ethyl-1-pentynyl group, nitro group, methylo
Characterized by being a substituent selected from a vinyl group and an ester group
The positive photosensitive resin precursor composition according to claim 1.