JP2003076007A - Positive type photosensitive resin precursor composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali-developable positive type photosensitive resin precursor composition. SOLUTION: The positive type photosensitive resin precursor composition is characterized in that it contains (a) a polymer based on structural units of formula (1) (where R<1> is a di-to octavalent >=2C organic group; R<2> is a di-to hexavalent >=2C organic group, R<1> and/or R<2> has an alicyclic substituent; R<3> is H or a 1-20C organic group; (n) is an integer of 10-100,000; (m) is an integer of 0-2; and (p) and (q) are each an integer of 0-4 but p+q>0), (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, 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. In addition, in the case of adding a soluble polyimide resin having a hydroxyl group, the problems as described above are lessened, but the structure is limited to make it soluble, and the solvent resistance of the obtained polyimide resin is poor. The point was a problem. A polyamide resin having a hydroxyl group, to which quinonediazide is added, has a problem that the structure is limited in order to obtain solubility, and thus the solvent resistance of the resin obtained after heat treatment is poor. Further, when they are applied to devices, they also have a problem that electrodes such as aluminum are contaminated during dry etching and heat treatment.

[0004]

In consideration of the above drawbacks,
The present invention, a polyimide precursor having a specific structure introduced into the main chain, a resin composition obtained by adding a compound having a phenolic hydroxyl group and a naphthoquinonediazide compound, high transparency to the exposure wavelength is high. The inventors have found that patterning with high sensitivity is possible and that the contamination of the electrodes during curing is significantly reduced, and the invention has been completed.

[0005]

The present invention comprises (a) a polymer containing a structural unit represented by the general formula (1) 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.

[0006]

[Chemical 6]

(Wherein R ¹ is a divalent to octavalent organic group having 2 or more carbon atoms, R ² is a divalent to hexavalent organic group having 2 or more carbon atoms, and R ^{1 is} And / or R ² has an aliphatic cyclic substituent, R ³ is hydrogen or an organic group having 1 to 20 carbon atoms, and n is 10 to 10
An integer from 0000, m is an integer from 0 to 2, p, q
Represents an integer from 0 to 4. However, p + q> 0. )

[0008]

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

The above general formula (1) represents a polyamic acid having a hydroxyl group, and due to the presence of the hydroxyl group, the solubility in an alkaline aqueous solution is better than that of a polyamic acid having no hydroxyl group. Particularly, among the hydroxyl groups, phenolic hydroxyl groups are more preferable than the solubility in the alkaline aqueous solution. Further, by having 10 wt% or more of a fluorine atom in the general formula (1), when developing with an alkaline aqueous solution,
Since water repellency is appropriately exerted at the interface of the film, bleeding at the interface 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 ^{1 in the} above general formula (1) represents a structural component of an acid dianhydride, and this acid dianhydride contains an aliphatic ring and is divalent to at least 2 carbon atoms. It is preferably an octavalent organic group, and more preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms.

Specifically, those having a structure represented by the general formula (2) are preferable, and in this case, R ⁴ and R ⁶ 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. R ⁵ represents an aliphatic cyclic substituent,

[0012]

[Chemical 7]

It is represented by R ⁹ to R ²⁰ are hydrogen or an alkyl group, and t, u, and v each represent an integer of 1 to 6.
If a fluorine component such as fluorine or a fluoroalkyl group is introduced into R ⁹ to R ²⁰ , it becomes a contamination source of the electrode due to the annealing treatment, which is not preferable. As an example of such R ⁵ ,
Examples thereof include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. From the viewpoint of heat resistance, 5- to 8-membered rings are preferable, and 5- or 6-membered rings are particularly preferable. From this point t is 2
Alternatively, 3 is particularly preferable, and u and v are particularly preferably 3 ≦ u + v ≦ 4. In addition, the compound can be modified with a compound having an aromatic ring as long as the transparency of the polymer is not impaired. Specifically, hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group,
It represents a substituent such as a bis (hydroxyphenyl) sulfone group, a hydroxydiphenyl ether group, and a dihydroxydiphenyl ether group.

The hydroxyl group of the general formula (2) is preferably located adjacent to the amide bond. a and b represent an integer of 1 or 2, and when a and b are 3 or more,
The characteristics of the obtained heat resistant resin film deteriorate.

Further, R ⁷ and R ^{8 in} the general formula (2) are preferably hydrogen and / or an organic group having 1 to 20 carbon atoms. When the carbon number is 20 or more, the solubility in an alkali developing solution is lowered.

In the general formula (2), o and s represent integers of 0 to 2, and when o and s are 0, they are ring-closed by heat treatment to form a benzoxazole ring and when 1 or 2, they are imide rings. It is preferable to have a structure capable of forming

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

[0018]

[Chemical 8]

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 having two carboxyl groups as 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 ² in the above general formula (1) represents a structural component of diamine. Among these, as a preferable example of R ² , a divalent to hexavalent organic group having an aliphatic ring and having at least two carbon atoms having a hydroxyl group is preferable, and a carbon number of 6 to 30 trivalent or tetravalent organic groups are more preferred. Specific examples include those having the structures represented by the general formulas (3), (4), and (5).

Among them, R ^{22 in} the general formula (3), R ^{25 in} the general formula (4) and R ²⁸ in the general formula (5) are the general formula (2).
The same organic group as R ^{5 in the above} is shown, and an aliphatic cyclic substituent is shown. R ²¹ and R ²³ in the general formula (3) are preferably an organic group having an aromatic ring or a hydroxyl group in view of heat resistance of the obtained polymer. R ²⁴ and R ²⁶ in the general formula (4), the general formula (5)
R ²⁷ in the above is preferably an organic group having an aromatic ring in view of the heat resistance of the obtained polymer. Also, in general formula (3), c, d,
“E” and “f” in the general formula (4) and “g” in the general formula (5) each represent an integer of 1 or 2, and “h” in the general formula (5) represents an integer from 0 to 2.

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

[0023]

[Chemical 9]

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

[0025]

[Chemical 10]

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

[0027]

[Chemical 11]

In the general formula (3), R ²¹ and R ^{23 each} represent a trivalent to tetravalent organic group selected from 2 to 20 carbon atoms and have an aromatic ring due to the heat resistance of the resulting polymer. Those 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 is 2 having 2 to 30 carbon atoms
Represents a valent organic group. 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 (4), R ²⁴ and R ²⁶ 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.

In the general formula (5), R ²⁷ 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.

It is also possible to modify with another diamine component in the range of 1 to 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) represents hydrogen or an organic group having 1 to 20 carbon atoms. From the viewpoint of stability of the resulting positive photosensitive resin precursor solution, R ³ is preferably an organic group, but hydrogen is preferable in view of the solubility of the 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, it is preferable that R ³ contains at least one hydrocarbon group having 1 to 16 carbon atoms and the other is a hydrogen atom.

Further, m in the general formula (1) represents the number of carboxyl groups, which is an integer from 0 to 2. N in the general formula (1) 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, R ¹ and R ² 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)
Examples thereof include those obtained by copolymerizing tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane and the like in an amount of 1 to 10 mol%.

The positive photosensitive resin composition of the present invention may consist of only the structural unit represented by the general formula (1), or may be a copolymer or blend with other structural units. May be. At that time, it is preferable that the structural unit represented by the general formula (1) 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 utilizing a known method. 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.

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, BisP-RS, Bis
PG-26X, BisRS-3P, BisOC-OCH
P, BisPC-OCHP, Bis25X-OCHP,
Bis26X-OCHP, BisOCHP-OC, Bi
s236T-OCHP, methylenetris-FR-CR,
BisRS-26X, BisRS-OCHP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP
-PC, BIR-PC, BIR-PTBP, BIR-P
CHP, BIP-BIOC-F, 4PC, BIR-BI
PC-F and TEP-BIP-A (above, a brand name, the Asahi organic material industry Co., Ltd. product) are 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, BisP-RS, B
isRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X, BIP-PC, B
IR-PC, BIR-PTBP, BIR-BIPC-F
Etc. Of these, particularly preferred compounds having a phenolic hydroxyl group include, for example, Bis
-Z, TekP-4HBPA, TrisP-HAP, T
risP-PA, BisP-RS, BIR-PC, BI
R-PTBP and BIR-BIPC-F. The structures of compounds having a particularly preferred phenolic hydroxyl group are shown below.

[0041]

[Chemical 12]

The resin composition obtained by adding the compound having a phenolic hydroxyl group is hardly dissolved in an alkali developing solution before exposure, and is easily dissolved in an alkali developing solution after exposure, so that the resin composition is developed. Little film loss and easy development in a short time.

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, BisP-RS, B
isRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (these product names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, B
IR-PC, BIR-PTBP, BIR-PCHP, B
IP-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, methylenebisphenol, BisP-AP (trade name, Honshu Chemical Industry Co., Ltd. Compounds in which 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid is introduced into the compound) 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 Heat-Resistant Resin Precursor Film A 6-inch silicon wafer was coated with a photosensitive heat-resistant resin precursor composition (hereinafter referred to as varnish) so that the film thickness after prebaking would be 7 μm, Then, using a hot plate (Mark-7 manufactured by Tokyo Electron Ltd.), 12
By prebaking at 0 ° C. for 3 minutes, a photosensitive polyimide precursor film was obtained.

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 (GCA i-line stepper DSW-8000)
Then, a reticle with a cut pattern was set, and the exposure time was changed (intensity of 365 nm) to perform i-line exposure. Development 2. Using a developing device of Mark-7 manufactured by Tokyo Electron Ltd., tetramethylammonium hydroxide 2.
A 38% aqueous solution was sprayed for 10 seconds. After this, 6 in 0 rotations
Let stand for 0 seconds, rinse with water at 400 rpm, 300
It was shaken off at 0 rotation for 10 seconds and dried.

The cured photosensitive polyimide precursor film was heated to 140 at a nitrogen stream (oxygen concentration of 20 ppm or less) using an inert oven INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.
30 minutes at ℃, then heat up to 350 ℃ in 1 hour 35
A heat treatment was performed at 0 ° C. for 1 hour to form a cured film.

Measurement of Transmittance of Heat-Resistant Resin Precursor Composition A heat-resistant resin precursor composition was applied on a glass substrate so that the film thickness after prebaking was about 10 μm, and UV-visible spectroscopy manufactured by Shimadzu Corporation. Photometer MultiSpec-150
0 was used to measure the transmittance at a wavelength of 365 nm.

Substrate surface analysis during heat treatment (X-ray photoelectron spectroscopy (XPS)) A varnish was applied on a 4-inch silicon wafer on which Al was vapor-deposited so that the film thickness after curing was 5 μm, and exposure, development and curing were performed. After that, the opening (1
The chemical state of the surface at (00 × 100 μm) was measured using SSX-100 manufactured by SSI. Further, in order to investigate the degree of contamination by the carbon component (organic matter) in the Al part, Ar
Depth profile analysis by ion etching was performed to measure the depth at which the carbon component was not detected.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride (1) 1,1-bis (3-amino-4-hydroxyphenyl) cyclohexane (ABCH) 14.9 under a stream of dry nitrogen.
g (0.05 mol) and allyl glycidyl ether 34.
2 g (0.3 mol) was dissolved in 100 g of gamma-butyrolactone 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 the dropping was completed, the reaction was carried out at 0 ° C. for 4 hours. The solution was concentrated with a rotary evaporator and poured into 1 l of toluene to obtain an acid anhydride (1).

[0064]

[Chemical 13]

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (1) 14.9 g (0.05 mol) of ABCH was dissolved in 100 ml of N, N-dimethylacetamide (DMAc) and 30.3 g (0.3 mol) of triethylamine. , -15 ° C. 4-nitrobenzoyl chloride 20.
A solution prepared by dissolving 4 g (0.11 mol) in 100 ml of DMAc was added dropwise. After the dropping was completed, the reaction was carried out at -15 ° C for 2 hours, and the temperature was returned to room temperature. The triethylamine salt was filtered off, the filtrate was poured into water, and the deposited precipitate was collected by filtration,
It was vacuum dried 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 the reaction was completed, the palladium compound as a catalyst was removed by filtration and the mixture was concentrated with a rotary evaporator to obtain a diamine compound (1). The obtained solid was used for the reaction as it was.

[0067]

[Chemical 14]

Synthetic Example 3 Synthesis of hydroxyl group-containing diamine (2) 1,3-cyclohexanedicarboxylic acid 17.2 g (0.
1 mol) was dissolved in 100 ml of thionyl chloride and 1 ml of dry dimethylformamide (DMF), and the mixture was stirred at 60 ° C. for 2 minutes.
Reacted for hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure, and the precipitate was recrystallized from hexane to obtain dicarboxylic acid chloride. 2-amino-4-nitrophenol 15.
4 g (0.1 mol) was dissolved in 50 ml of acetone and 30 g (0.34 mol) of propylene oxide, and cooled to -15 ° C. A solution of 11.5 g (0.055 mol) of 1,3-cyclohexanedicarboxylic acid chloride obtained above in 60 ml of acetone was gradually added dropwise thereto.
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.

[0070]

[Chemical 15]

Synthesis Example 4 Synthesis of hydroxyl group-containing diamine (3) 1,2-cyclopentanedicarboxylic acid 15.8 g (0.
1 mol) was dissolved in 100 ml of thionyl chloride and 1 ml of dry dimethylformamide (DMF), and the mixture was stirred at 60 ° C. for 2 minutes.
Reacted for hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure, and the precipitate was recrystallized from hexane to obtain dicarboxylic acid chloride. 2-amino-4-nitrophenol 15.
4 g (0.1 mol) was dissolved in 50 ml of acetone and 30 g (0.34 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 12.5 g (0.055 mol) of 1,2-cyclopentanedicarboxylic acid chloride obtained above in 60 ml of acetone was gradually added dropwise thereto.
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.

[0073]

[Chemical 16]

Synthesis Example 5 Synthesis of hydroxyl group-containing diamine (4) 1,1-cyclobutanedicarboxylic acid 14.4 g (0.1
Was dissolved in 100 ml of thionyl chloride and 1 ml of dry dimethylformamide (DMF), and the mixture was reacted at 60 ° C. for 2 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure, and the precipitate was recrystallized from hexane to obtain dicarboxylic acid chloride. 2-amino-4-nitrophenol 15.
4 g (0.1 mol) was dissolved in 50 ml of acetone and 30 g (0.34 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 11.7 g (0.055 mol) of 1,1-cyclobutanedicarboxylic acid chloride obtained above in 60 ml of acetone was gradually added dropwise thereto. 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.

[0076]

[Chemical 17]

Synthesis Example 6 Synthesis of hydroxyl group-containing diamine (5) 29.8 g (0.1 mol) of ABCH was dissolved in 100 ml of N, N-dimethylacetamide (DMAc) and 30.3 g (0.3 mol) of triethylamine, Cooled to -15 ° C. 3-nitrobenzoyl chloride 18.5
A solution prepared by dissolving g (0.1 mol) in 100 ml of DMAc was added dropwise over 1 hour. After dripping, 2 at -15 ℃
After reacting for a time, the temperature was returned to room temperature. The triethylamine salt was filtered off, the filtrate was poured into water, and the deposited precipitates were collected by filtration and vacuum dried at 50 ° C. The crude product was dissolved in ethanol and recrystallized.

The obtained crystal 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.

[0079]

[Chemical 18]

Synthesis Example 7 Synthesis of hydroxyl group-containing diamine (6) 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.

[0082]

[Chemical 19]

Synthesis Example 8 Synthesis of hydroxyl group-containing diamine (7) 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 7.

[0084]

[Chemical 20]

Synthesis Example 9 Synthesis of quinonediazide compound (1) 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,
Triethylamine (10.12 g) mixed with 1,4-dioxane (50 g) was added dropwise so that the temperature of the system did not exceed 35 ° C. After dropping, the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Then, the deposited precipitate was collected by filtration. The precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (1).

[0086]

[Chemical 21]

Synthesis Example 10 Quinonediazide compound (2)
Synthetic dry nitrogen stream, TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 15.31 g (0.05 mol) and 4
-Naphthoquinone diazide sulfonyl acid chloride 13.4
3 g (0.05 mol) and 5-naphthoquinonediazide sulfonyl acid chloride 17.46 g (0.065 mol) were dissolved in 450 g of 1,4-dioxane, and the mixture was brought to room temperature.
Using 11.64 g of triethylamine mixed with 50 g of 1,4-dioxane, a quinonediazide compound (2) was obtained in the same manner as in Synthesis Example 5.

[0088]

[Chemical formula 22]

Synthesis Example 11 Quinonediazide compound (3)
Under a synthetic dry nitrogen stream of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 21.22 g (0.05 mol) and 4-
Naphthoquinone diazide sulfonyl acid chloride 13.43
g (0.05 mol), 5-naphthoquinone diazide sulfonyl chloride 20.15 g (0.075 mol)
It was dissolved in 450 g of 4-dioxane and brought to room temperature. A quinonediazide compound (3) was obtained in the same manner as in Synthesis Example 5 by using 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane.

[0090]

[Chemical formula 23]

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

[0092]

[Chemical formula 24]

Example 1 5.01 g (0.025 mol) of 4,4'-diaminophenyl ether and 1.24 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane under a stream of dry nitrogen.
(0.005 mol) of N-methyl-2-pyrrolidone (N
MP) was dissolved in 50 g. Hydroxy group-containing acid anhydride (1) (19.4 g, 0.03 mol) was added to NMP14.
g, and reacted at 20 ° C. for 1 hour, then 5
The reaction was carried out at 0 ° 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.

The obtained polymer solution was coated on a glass substrate, and the polymer transmittance was measured as described above. Further, 40 g of the obtained polymer solution was added with 2 g of the quinonediazide compound (1) shown above and Bis-Z (trade name, Honshu Chemical Industry Co., Ltd.) as a compound having a phenolic hydroxyl group.
1 g) to obtain a varnish A of the photosensitive polyimide precursor composition. Using the obtained varnish, as described above, a photosensitive polyimide precursor film was prepared, exposed, developed and cured on a silicon wafer on which aluminum was vapor deposited, and XPS measurement was performed on the opening.

Example 2 Under a dry nitrogen stream, 13.4 g (0.025 mol) of the hydroxyl group-containing diamine (1) obtained in Synthesis Example 2 was added to N-.
It was dissolved in 50 g of methyl-2-pyrrolidone (NMP). 16.1 g (0.025 mol) of the hydroxy group-containing acid anhydride obtained in Synthesis Example 1 was added thereto together with 30 g of pyridine, and the mixture was reacted at 60 ° C. for 6 hours. After the reaction,
The solution was poured into 2 l of water, and the 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 the polymer solid thus obtained
Was measured, and the polymer solution obtained by dissolving in 18.6 g of NMP was applied on a glass substrate, and the transmittance of the polymer was measured as described above.

Further, 2 g of the naphthoquinonediazide compound (2) shown above, 2 g of BisP-RS (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a compound having a phenolic hydroxyl group, and 1 g of vinyltrimethoxysilane were added to 10 g of the polymer solid. And gamma-butyrolactone were dissolved in 30 g to obtain a varnish B of a photosensitive polyimide precursor composition. Using the obtained varnish, as described above, a photosensitive polyimide precursor film was prepared, exposed, developed and cured on a silicon wafer on which aluminum was vapor deposited, and XPS measurement was performed on the opening.

Example 3 Under a dry nitrogen stream, 17.3 g (0.045 mol) of the hydroxyl group-containing diamine compound (2) obtained in Synthesis Example 3 and 1,3-bis (3-aminopropyl) tetramethyldi NMP containing 1.24 g (0.005 mol) of siloxane
It was dissolved in 50 g. 12.4 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid anhydride
(0.04 mol) together with 21 g of NMP, add 20
The reaction was carried out at 0 ° C for 1 hour and then at 50 ° C for 2 hours. 0.98 g (0.01 mol) of maleic anhydride here
Was added and stirred at 50 ° C. for 2 hours, and then 14.7 g (0.1 mol) of N, N-dimethylformamide diethyl acetal.
Was diluted with 5 g of NMP and added dropwise over 10 minutes.
After the dropping, the mixture was stirred at 50 ° C. for 3 hours.

The obtained polymer solution was coated on a glass substrate and the transmittance of the polymer was measured as described above. Further, 1.6 g of the quinonediazide compound (3) shown above and 0.8 g of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a compound having a phenolic hydroxyl group were dissolved in 30 g of the obtained polymer solution. Varnish C of a photosensitive polyimide precursor composition was obtained. Using the obtained varnish, as described above, a photosensitive polyimide precursor film was prepared, exposed, developed and cured on a silicon wafer on which aluminum was vapor deposited, and XPS measurement was performed on the opening.

Example 4 Under a dry nitrogen stream, 9.26 g (0.025 mol) of the hydroxyl group-containing diamine compound (3) obtained in Synthesis Example 4 was obtained.
And 4,4'-diaminodiphenyl ether 4.51g
(0.0225 mol) and 1,3-bis (3-aminopropyl) tetramethyldisiloxane 0.62 g (0.00
25 mol) was dissolved in 70 g of NMP. 22.63 g (0.035 mol) of the hydroxyl group-containing acid anhydride (1) and 4.41 g (0.015 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride were stored at room temperature for NM.
P25 g was added together, and the mixture was stirred at room temperature for 1 hour and then at 50 ° C. for 2 hours. Then, a solution prepared by diluting 17.6 g (0.2 mol) of glycidyl methyl ether with 10 g of NMP was added, and the mixture was stirred at 70 ° C. for 6 hours.

The obtained polymer solution was applied onto a glass substrate, and the polymer transmittance was measured as described above. Furthermore, 2.5 g of the quinonediazide compound (3) shown above and 2 g of BIR-PC (trade name, manufactured by Asahi Organic Materials Co., Ltd.) as a compound having a phenolic hydroxyl group were dissolved in 40 g of this polymer solution to prepare a photosensitive polyimide. Varnish D of the precursor composition was obtained. Using the obtained varnish, as described above, a photosensitive polyimide precursor film was prepared, exposed, developed and cured on a silicon wafer on which aluminum was vapor deposited, and XPS measurement was performed on the opening.

Example 5 In place of the hydroxyl group-containing diamine compound (2) of Example 3, 16.03 g (0.045 mol) of the hydroxyl group-containing diamine compound (4) obtained in Synthesis Example 5 was used. Polymerization was performed in the same manner as in Example 3. The obtained polymer solution was applied onto a glass substrate, and the polymer transmittance was measured as described above. Further, in the same manner as in Example 3, a varnish E of the photosensitive polyimide precursor composition was obtained. Using the obtained varnish, as described above, a photosensitive polyimide precursor film was prepared, exposed, developed and cured on a silicon wafer on which aluminum was vapor deposited, and XPS measurement was performed on the opening.

Example 6 18.78 g (0.045 mol) of the hydroxyl group-containing diamine compound (5) obtained in Synthesis Example 6 was used in place of the hydroxyl group-containing diamine compound (3) of Example 4.
Other than using 3,3 ', 4,4'-diphenyl ether tetracarboxylic anhydride 4.65 g (0.015 mol) instead of 3,3', 4,4'-biphenyltetracarboxylic dianhydride. Polymerization was carried out in the same manner as in Example 4. The obtained polymer solution was applied onto a glass substrate, and the polymer transmittance was measured as described above. Further, in the same manner as in Example 3, a varnish F of the photosensitive polyimide precursor composition was obtained. Using the obtained varnish, as described above, a photosensitive polyimide precursor film was prepared, exposed, developed and cured on a silicon wafer on which aluminum was vapor deposited, and XPS was applied to the opening.
The measurement was performed.

Example 7 14.9 g (0.05 mol) of ABCH under a stream of dry nitrogen
Was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP) and 26.4 g (0.3 mol) of glycidyl methyl ether, and the temperature of the solution was cooled to -15 ° C. 7.38 g of diphenyl ether dicarboxylic acid dichloride
(0.025 mol), isophthalic acid dichloride 5.08
A solution prepared by dissolving g (0.025 mol) in 25 g of gamma-butyrolactone was added dropwise so that the internal temperature did not exceed 0 ° C. After the dropping was completed, stirring was continued for 6 hours at -15 ° C.
After the reaction was completed, the solution was poured into 3 l of water to collect a white precipitate. This precipitate was collected by filtration, washed with water three times, and then
It was dried in a vacuum dryer at 0 ° C. for 20 hours.

10 g of the polymer solid thus obtained
Was measured, and the polymer solution obtained by dissolving in 18.6 g of NMP was applied on a glass substrate, and the transmittance of the polymer was measured as described above.

Further, 2 g of the naphthoquinonediazide compound (2) shown above and Bis were added to 10 g of this polymer powder.
-Z (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 1 g of NMP3
It was dissolved in 0 g to obtain a varnish G of a photosensitive polybenzoxazole precursor composition. As described above using the obtained varnish, a photosensitive polyimide precursor film is prepared, exposed, developed and cured on a silicon wafer on which aluminum is vapor-deposited.
XPS measurement was performed on the openings.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 2 except that the hydroxyl group-containing diamine (6) obtained in Synthesis Example 7 was used in place of the hydroxyl group-containing diamine (1) in Example 2. .
10 g of the obtained polymer solid was weighed, and NMP 18.6 g
The polymer solution obtained by dissolving in the above was coated on a glass substrate, and the transmittance of the polymer was measured as described above. Further, a varnish H of the photosensitive polyimide precursor composition was obtained in the same manner as in Example 2. Using the obtained varnish, as described above, a photosensitive polyimide precursor film was prepared, exposed, developed and cured on a silicon wafer on which aluminum was vapor deposited, and XPS measurement was performed on the opening.

Comparative Example 2 Polymerization was carried out in the same manner as in Example 3 except that the hydroxyl group-containing diamine (7) obtained in Synthesis Example 8 was used in place of the hydroxyl group-containing diamine (2) in Example 3. .
The obtained polymer solution was applied onto a glass substrate, and the polymer transmittance was measured as described above. Further, in the same manner as in Example 3, a varnish I of the photosensitive polyimide precursor composition was obtained. As described above, using the obtained varnish, a photosensitive polyimide precursor film was prepared, exposed, developed and cured on a silicon wafer on which aluminum was vapor-deposited, and XP was used for the opening.
S measurement was performed.

Comparative Example 3 Similar to Example 1 except that 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid anhydride was used in place of the hydroxyl group-containing acid dianhydride (1) of Example 1. Was polymerized. The obtained polymer solution was applied onto a glass substrate, and the polymer transmittance was measured as described above. Further, a varnish J of the photosensitive polyimide precursor composition was obtained in the same manner as in Example 1. Using the obtained varnish, as described above, a photosensitive polyimide precursor film was prepared, exposed, developed and cured on a silicon wafer on which aluminum was vapor deposited, and XPS measurement was performed on the opening.

[0110]

[Table 1]

[0111]

According to the present invention, it is possible to obtain a positive type photosensitive resin precursor composition which can be developed with an alkaline aqueous solution and is excellent in transparency and has less electrode contamination during curing.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H025 AA01 AA06 AA09 AA10 AA20                       AB16 AC01 AD03 BE01 CB25                       CB45 FA17                 4J043 PA02 PA04 PC065 QB15                       QB26 QB31 RA34 SA05 TA14                       TA22 UA021 UA031 UA042                       UA131 UA141 UA151 UA152                       UB221 UB222 ZB22                 5F058 AA10 AC02 AC07 AF04 AG01                       AH02 AH03

Claims (5)

[Claims] 1. A method comprising: (a) a polymer containing a structural unit represented by the general formula (1) as a main component; (b) a compound having a phenolic hydroxyl group; and (C) an esterified quinonediazide compound. A positive photosensitive resin precursor composition comprising: [Chemical 1] (Wherein R ¹ is a divalent to octavalent organic group having 2 or more carbon atoms, R ² is a divalent to hexavalent organic group having 2 or more carbon atoms, and R ¹ and / or R ² has an aliphatic cyclic substituent, R ³ is hydrogen, or has 1 to 2 carbon atoms.
The organic groups up to 0 are shown. 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. However, p + q> 0. ) 2. R ¹ (COOR ³ ) m (O of the general formula (1)
H) p is represented by General formula (2), The positive photosensitive resin precursor composition of Claim 1 characterized by the above-mentioned. [Chemical 2] (R ⁴ and R ^{6 each} represent a divalent to tetravalent organic group selected from the group consisting of 2 to 20 carbon atoms, and R ⁵ represents the substituent shown in Chemical Formula 2 above.
R ⁹ to R ²⁰ are hydrogen or an alkyl group, and are t, u,
v represents an integer of 1 to 6, and a and b represent an integer of 1 or 2. R ⁷ and R ⁸ are hydrogen, and / or have 1 to 2 carbon atoms.
The organic groups up to 0 are shown. o and s represent integers from 0 to 2. ) 3. The positive photosensitive resin precursor composition according to claim 1, wherein R ² (OH) q in the general formula (1) is represented by the general formula (3). [Chemical 3] (R ²¹ and R ²³ represent a trivalent to tetravalent organic group selected from 2 to 20 carbon atoms, and R ²² represents the same aliphatic cyclic substituent as R ^{5 in the} general formula (2). d represents an integer of 1 or 2.) 4. The positive photosensitive resin precursor composition according to claim 1, wherein R ² (OH) q in the general formula (1) is represented by the general formula (4). [Chemical 4] (R ²⁴ and R ²⁶ represent a divalent organic group having 2 to 20 carbon atoms, and R ²⁵ represents the same aliphatic cyclic substituent as R ^{5 in the} general formula (2). E and f are 1 or Indicates an integer of 2.) 5. The positive photosensitive resin precursor composition according to claim 1, wherein R2 (OH) q of the general formula (1) is represented by the general formula (5). [Chemical 5] (R ²⁷ represents a divalent organic group selected from 2 to 20 carbon atoms, R ²⁸ represents the same aliphatic cyclic substituent as R ^{5 in the} general formula (2). G represents an integer of 1 or 2 , H is 0 to 2
Indicates an integer up to. )