JP5241142B2 - Positive photosensitive resin composition - Google Patents

Description

  The present invention provides a positive photosensitive resin composition that is a precursor of a heat resistant resin used as a surface protective film and an interlayer insulating film of a semiconductor device, and has heat resistance using the positive photosensitive resin composition. The present invention relates to a method for producing a cured relief pattern, and a semiconductor device having the cured relief pattern.

  Polyimide resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like are widely used for surface protection films and interlayer insulating films of semiconductor devices. This polyimide resin is currently often provided in the form of a photosensitive polyimide precursor composition. In the process of manufacturing a semiconductor device, the precursor composition is applied to a substrate such as a silicon wafer, patterned with actinic rays, developed, and subjected to a thermal imidization treatment to become a part of the semiconductor device. A surface protective film, an interlayer insulating film, or the like can be easily formed. Therefore, the manufacturing process of a semiconductor device using a photosensitive polyimide precursor composition is a manufacturing process using a conventional non-photosensitive polyimide precursor composition that needs to be patterned by a lithography method after forming a surface protective film or the like. Compared with the process, it has the feature that the process can be greatly shortened.

By the way, this photosensitive polyimide precursor composition requires the use of an organic solvent such as N-methyl-2-pyrrolidone as a developing solution in the development process. Countermeasures are being sought. In response to this, recently, various proposals have been made on heat-resistant photosensitive resin materials that can be developed with an alkaline aqueous solution, as with photoresists.
Among them, an alkaline aqueous solution-soluble hydroxypolyamide, such as polybenzoxazole (hereinafter also referred to as “PBO”) precursor, which becomes a heat-resistant resin after curing, is converted into a photoacid generator (hereinafter “PAC”) such as a photosensitive diazoquinone compound. The method of using the PBO precursor composition mixed with the above as a positive photosensitive resin composition is disclosed in Patent Documents 1 and 2, and has attracted attention in recent years.

The development mechanism of this positive photosensitive resin composition is such that the photosensitive diazoquinone compound and the PBO precursor in the unexposed area have a low dissolution rate in an alkaline aqueous solution, whereas the photosensitive diazoquinone compound is converted to indenecarboxylic by exposure. This is based on the fact that the dissolution rate in the alkaline aqueous solution of the exposed portion is increased by chemically changing to an acid compound. By utilizing the difference in the dissolution rate with respect to the developer between the exposed portion and the unexposed portion, a relief pattern composed of the unexposed portion can be created.
The PBO precursor composition described above can form a positive relief pattern by exposure and development with an alkaline aqueous solution. Further, heat generates an oxazole ring, and the cured PBO film has the same thermosetting film characteristics as a polyimide film. Therefore, the PBO precursor composition is a promising organic solvent development type polyimide precursor composition. Has attracted attention as an alternative material.

However, the PBO precursor composition has a problem that the sensitivity is lower than that of the photosensitive polyimide precursor composition, and there is a demand for a more sensitive composition.
By using a composition containing an organic acid such as formic acid or acetic acid as an essential component, it has excellent storage stability, stable photosensitivity, good heat resistance, and high sensitivity photopolymer composition. A thing is proposed by patent document 3 grade | etc.,. Further, Patent Document 4 proposes a positive photoresist composition containing a resin selected from the group consisting of a polyimide precursor and polyimide, an acid generator, a dissolution accelerator, and a solvent as essential components.
Japanese Examined Patent Publication No. 1-46862 JP-A-63-96162 JP 2004-029712 A Japanese Patent Publication No. 7-500932

  The present invention relates to a positive photosensitive resin composition having excellent positive lithography performance such as high sensitivity and high resolution and adhesion to a silicon substrate, a method for producing a cured relief pattern using the composition, and the curing An object is to provide a semiconductor device having a relief pattern.

The inventor has found that a positive photosensitive resin composition that solves the above problems can be obtained by combining a specific aromatic carboxylic acid with a hydroxypolyamide having a specific structure, and has led to the present invention. It was.
That is, the first of the present invention is (A) 100 parts by mass of hydroxypolyamide having a repeating unit represented by the following general formula (1), (B) 1 to 50 parts by mass of a photoacid generator, (C ) A positive photosensitive resin composition comprising 0.01 to 70 parts by mass of an aromatic carboxylic acid compound having 7 to 15 carbon atoms.

Wherein X ₁ is a tetravalent organic group having at least 2 or more carbon atoms, and X ₂ , Y ₁ and Y ₂ are each independently a divalent organic having at least 2 carbon atoms. M is an integer of 2 to 1000, n is an integer of 0 to 500, and m / (m + n)> 0.5, where m dihydroxys including X ₁ and Y ₁ The arrangement order of the diamide unit and n diamide units including X ₂ and Y ₂ is not limited.)
The aromatic carboxylic acid compound is preferably a compound represented by the following general formula (2), and more preferably the aromatic carboxylic acid compound is a compound represented by the following general formula (3). .
Among these, in the composition of the present invention, the photoacid generator is preferably a compound having a naphthoquinonediazide structure.

(In the formula, R ₁ is a monovalent or divalent organic group having a substituent and having 6 to 14 carbon atoms, and p is an integer of 1 to 2).

(In the formula, R ₃ is a monovalent organic group having a substituent and having 6 to 14 carbon atoms.)
The second aspect of the present invention is that (1) the positive photosensitive resin composition described above is formed on a substrate in the form of a layer or film, and (2) exposure with actinic radiation through a mask, A method for producing a cured relief pattern, comprising directly irradiating an electron beam or an ion beam, (3) eluting or removing an exposed portion or an irradiated portion, and (4) subjecting the obtained relief pattern to heat treatment. .
Furthermore, a third aspect of the present invention is a semiconductor device having a cured relief pattern layer obtained by the above-described manufacturing method.

  According to the present invention, a positive-type photosensitive resin composition having high-sensitivity and high-resolution positive-type lithography performance and excellent adhesion to a silicon substrate, and a cured relief pattern using the positive-type photosensitive resin composition And a semiconductor device having the cured relief pattern.

<Positive photosensitive resin composition>
Each component constituting the positive photosensitive resin composition of the present invention will be specifically described below.
(A) Hydroxypolyamide Hydroxypolyamide, which is the base polymer of the positive photosensitive resin composition of the present invention, has m dihydroxydiamide units of the following general formula (1). The dihydroxydiamide unit has a structure obtained by polycondensing a dicarboxylic acid having a Y ₁ (COOH) ₂ structure and a bisaminophenol having a X ₁ (NH ₂ ) ₂ (OH) ₂ structure. The two amino groups and hydroxy groups of the bisaminophenol are each in the ortho position, and the hydroxypolyamide is closed by heating to about 280 to 400 ° C. to form a polybenz which is a heat resistant resin. Change to oxazole. m is preferably in the range of 2 to 1000, more preferably in the range of 3 to 50, and most preferably in the range of 3 to 30.

The hydroxy polyamide may have n diamide units of the above general formula (1) as necessary. The diamide unit has a structure obtained by polycondensing a diamine having a structure of X ₂ (NH ₂ ) ₂ and a dicarboxylic acid having a structure of Y ₂ (COOH) ₂ . n is preferably in the range of 0 to 500, and more preferably in the range of 0 to 10.
The higher the proportion of the above-mentioned dihydroxydiamide units in the hydroxypolyamide, the better the solubility in an alkaline aqueous solution used as a developer. Therefore, the value of m / (m + n) is preferably 0.5 or more. It is more preferably 7 or more, and most preferably 0.8 or more.

Examples of the bisaminophenol having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, and 4,4 ′. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino- 4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis -(4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis -(4-amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino- 3,3′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and Examples include 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.
Of these bisaminophenols having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ , X ₁ is preferably an aromatic group selected from the following.

In addition, as a compound having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ , two pairs of diamines having an amide bond and a phenolic hydroxyl group in the ortho position relative to each other (hereinafter referred to as “PBO precursor structure in the molecule”). Can also be used. Examples thereof include diamines represented by the following general formula, which are obtained by reacting bisaminophenol having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ with two molecules of nitrobenzoic acid for reduction. .

(In the formula, X ₃ is a tetravalent organic group having at least 2 carbon atoms, and is at least one organic group selected from the group consisting of preferable organic groups represented by X ₁ described above. Is preferred.)
As another method for obtaining a diamine having a PBO precursor structure in the molecule, the dicarboxylic acid dichloride having the structure of Y ₃ (COCl) ₂ is reacted with two molecules of nitroaminophenol for reduction. There are also ways to obtain the indicated diamines.

(In the formula, Y ₃ is a divalent organic group having at least 2 carbon atoms, and is at least one organic group selected from the group consisting of preferable organic groups represented by Y ₁ described later. Is preferred.)
Examples of the diamine having the structure of X ₂ (NH ₂ ) ₂ include aromatic diamine and silicon diamine.
Among these, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl ether, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′- Diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2′-bis (4-aminophenyl) ) Propane, 2,2'-bis (4-aminophenyl) hexa Fluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2,4-bis (4-aminophenyl) -1-pentene, 4-methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-4-aminobenzyl) benzene, Imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6) -amino-1- (4-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4,4′-diaminoazobenzene, 4,4′-diamino Phenylurea, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 4,4'-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, 4,4′-diaminobiphenyl, 4,4 '-Diaminobenzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-di Aminobiphenyl, o-toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-amino) Phenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-di- (3-aminophenoxy) diphenylsulfone, and 4, 4′-diaminobenzanilide and the like, and the hydrogen atom of the aromatic nucleus of these aromatic diamines is at least selected from the group consisting of a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, and a phenyl group A compound substituted by a kind of group or atom is mentioned.

Moreover, in order to improve adhesiveness with a base material, silicon diamine can be selected as a part or all of the diamine having the structure of X ₂ (NH ₂ ) ₂ , and examples thereof include bis (4-amino Phenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (4-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyl) Dimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, and the like.
Examples of the dicarboxylic acid having Y ₁ (COOH) ₂ and Y ₂ (COOH) ₂ structures include dicarboxylic acids in which Y ₁ and Y ₂ are each an aromatic group or an aliphatic group selected from the following.

Wherein A is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, and a single bond. R represents a group selected from the group consisting of a hydrogen atom, an alkyl group, an unsaturated group, and a halogen atom, and k represents an integer of 0 to 4. )
In addition, a derivative of 5-aminoisophthalic acid can be used for a part or all of the dicarboxylic acid having the Y ₁ (COOH) ₂ and Y ₂ (COOH) ₂ structures. Specific compounds to be reacted with 5-aminoisophthalic acid to obtain the derivative include 5-norbornene-2,3-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3, 6-tetrahydrophthalic anhydride, 3-ethynyl-1,2-phthalic anhydride, 4-ethynyl-1,2-phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 1 -Cyclohexene-1,2-dicarboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, allyl succinic anhydride , Isocyanate ethyl methacrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate 3-cyclohexene-1-carboxylic acid chloride, 2-furancarboxylic acid chloride, crotonic acid chloride, cinnamic acid chloride, methacrylic acid chloride, acrylic acid chloride, propiolic acid chloride, tetrolic acid chloride, thiophene 2-acetyl chloride, p -Styrenesulfonyl chloride, glycidyl methacrylate, allyl glycidyl ether, chloroformate methyl ester, chloroformate ethyl ester, chloroformate n-propyl ester, chloroformate isopropyl ester, chloroformate isobutyl ester, 2-ethoxy chloroformate Ester, chloroformate-sec-butyl ester, chloroformate benzyl ester, chloroformate 2-ethylhexyl ester, chloroformate allyl ester, chloroformate phenyl ester, chloro Acid 2,2,2-trichloroethyl ester, chloroformate-2-butoxyethyl ester, chloroformate-p-nitrobenzyl ester, chloroformate-p-methoxybenzyl ester, isobornylbenzyl chloroformate, Chloroformic acid-p-biphenylisopropylbenzyl ester, 2-t-butyloxycarbonyl-oxyimino-2-phenylacetonitrile, St-butyloxycarbonyl-4,6-dimethyl-thiopyrimidine, di-tert-butyl-dicarbonate N-ethoxycarbonylphthalimide, ethyldithiocarbonyl chloride, formic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, methanesulfonic acid chloride, acetyl chloride, trityl chloride, trimethylchlorosilane, hexamethyldisila N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (dimethylamino) trimethylsilane, trimethylsilyldiphenylurea, bis (trimethylsilyl) urea, isocyanic acid And phenyl, n-butyl isocyanate, n-octadecyl isocyanate, o-tolyl isocyanate, 1,2-phthalic anhydride, and cis-1,2-cyclohexanedicarboxylic anhydride, and glutaric anhydride. .

Furthermore, as a dicarboxylic acid having a Y ₁ (COOH) _{2 or} Y ₂ (COOH) ₂ structure, a dicarboxylic acid obtained by ring-opening a tetracarboxylic dianhydride with a monoalcohol or a monoamine can also be used. Examples of monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, and benzyl alcohol. Examples of monoamine include butylamine and aniline. As an example of said tetracarboxylic dianhydride, the compound shown by following Chemical formula is mentioned.

Wherein B is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ —. Means a valent group.)
Alternatively, tetracarboxylic dianhydride can be reacted with bisaminophenol or diamine, and the resulting carboxylic acid residue can be esterified or amidated with a monoalcohol or monoamine.
Also, trimellitic acid chloride is reacted with bisaminophenol to produce tetracarboxylic dianhydride, and ring-opened in the same manner as the above tetracarboxylic dianhydride and used as dicarboxylic acid You can also. Examples of the tetracarboxylic dianhydride obtained here include chemical formulas shown below.

(Wherein, X ₄ represents a divalent organic group represented by X ₁ (OH) ₂ (NH—) ₂ )
As a method of polycondensation of dicarboxylic acid and bisaminophenol (diamine) to synthesize hydroxypolyamide, dicarboxylic acid and thionyl chloride are used to form diacid chloride, and then bisaminophenol (diamine) acts. Or a method of polycondensation of dicarboxylic acid and bisaminophenol (diamine) with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be allowed to act simultaneously.

In the hydroxy polyamide having the repeating unit represented by the general formula (1), it is also preferable to use the terminal group after being sealed with an organic group (hereinafter referred to as “sealing group”). In the polycondensation of hydroxypolyamide, when the dicarboxylic acid component is used in an excess number of moles compared to the sum of the bisaminophenol component and the diamine component, an amino group or a compound having a hydroxyl group is used as the sealing group. Is preferred. Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, and hydroxyethyl acrylate.
Conversely, when the sum of the bisaminophenol component and the diamine component is used in an excessive number of moles compared to the dicarboxylic acid component, the sealing group has an acid anhydride, carboxylic acid, acid chloride, isocyanate group, etc. It is preferable to use a compound. Examples of the compound include benzoyl chloride, norbornene dicarboxylic anhydride, norbornene carboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, methylcyclohexane dicarboxylic anhydride Products, cyclohexene dicarboxylic acid anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, tosyl chloride and the like.

(B) Photoacid generator As the photoacid generator contained in the positive photosensitive resin composition of the present invention, a photosensitive diazoquinone compound, an onium salt, a halogen-containing compound, and the like can be used, and a naphthoquinonediazide structure is used. A compound having is preferred.
Examples of the onium salts include iodonium salts, sulfonium salts, fosiphonium salts, phosphonium salts, ammonium salts, and diazonium salts. An onium selected from the group consisting of diaryl iodonium salts, triaryl sulfonium salts, and trialkyl sulfonium salts. Salts are preferred.
Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds, and trichloromethyltriazine is preferable.

  The compound having the naphthoquinone diazide structure is a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure. US Pat. No. 2,772,972, US Pat. No. 2,797,213 And U.S. Pat. No. 3,669,658. A compound having a naphthoquinonediazide structure is preferred, and the naphthoquinonediazide structure is a 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and 1,2 of the polyhydroxy compound. -At least one compound selected from the group consisting of naphthoquinonediazide-5-sulfonic acid ester (hereinafter also referred to as "NQD compound").

The NQD compound can be obtained by subjecting the naphthoquinonediazide sulfonic acid compound to sulfonyl chloride with chlorosulfonic acid or thionyl chloride and subjecting the resulting naphthoquinone diazide sulfonyl chloride to a polyhydroxy compound according to a conventional method. For example, a predetermined amount of a polyhydroxy compound and 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride in a solvent such as dioxane, acetone, or tetrahydrofuran, and basic such as triethylamine It can be obtained by reacting in the presence of a catalyst for esterification and washing the resulting product with water and drying.
Specific examples of the compound include NQD compounds of polyhydroxy compounds described below, but are not limited thereto.

(Wherein p is an integer from 0 to 9)

  In the present composition, as the naphthoquinone diazide sulfonyl group in the NQD compound, both a 5-naphthoquinone diazide sulfonyl group and a 4-naphthoquinone diazide sulfonyl group are preferably used. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. In addition, a naphthoquinone diazide sulfonyl ester compound in which 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, or 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester compound. Can also be used in combination. In the present composition, the blending amount of the photoacid generator with respect to the hydroxy polyamide is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the hydroxy polyamide. When the blending amount of the photosensitive diazoquinone compound is 1 part by mass or more, the patterning property of the resin is good, and when it is 50 parts by mass or less, the tensile elongation of the cured film is good and the development residue (scum) of the exposed part is Few.

(C) Aromatic carboxylic acid compound The aromatic carboxylic acid compound used in the present invention is an aromatic carboxylic acid having 7 to 15 carbon atoms. Specifically, o-toluic acid, m-toluic acid, p-toluic acid, o-anisic acid, m-anisic acid, p-anisic acid, benzoic acid, 2,4-dihydroxybenzoic acid, 3,5- Examples include dihydroxybenzoic acid, salicylic acid, methylene disalicylic acid, 2,2′-biphenyldicarboxylic acid, and the like.
Among these, an aromatic carboxylic acid compound having a structure represented by the following general formula (2) is preferable.

(In the formula, R ₁ is a monovalent or divalent organic group having 6 to 14 carbon atoms, and p is an integer of 1 to 2).
Furthermore, the carboxylic acid compound which has a structure represented by (3) is more preferable.

(In the formula, R ₃ is a monovalent aromatic group having a substituent and having 6 to 14 carbon atoms.)
Among these, the substituent for R ₃ is preferably an electron donating group, and more preferably at least one group selected from the group consisting of an alkyl group, an alkoxyl group, and a hydroxyl group.
Specifically, o-toluic acid, m-toluic acid, p-toluic acid, o-anisic acid, m-anisic acid, p-anisic acid, salicylic acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxy Examples include benzoic acid.
Furthermore, among the aromatic carboxylic acid compounds having the structure represented by the general formula (3), an aromatic carboxylic acid compound having a substituent is preferable from the viewpoint of solvent solubility and sensitivity, and is in the ortho position or the meta position. An aromatic carboxylic acid compound having a substituent at is more preferable, and an aromatic carboxylic acid compound having a substituent at the meta position is most preferable. These aromatic carboxylic acid compounds may be used alone or in combination of two or more.
The blending amount of the aromatic carboxylic acid compound with respect to the hydroxypolyamide is preferably 0.01 to 70 parts by mass, more preferably 0.1 to 50 parts by mass, and 1 to 40 parts by mass with respect to 100 parts by mass of the hydroxypolyamide. Is more preferable, and 5 to 20 parts by mass is particularly preferable. When the compounding amount of the carboxylic acid compound is 0.01 parts by mass or more, the development residue in the exposed part is reduced and the adhesion to the silicon substrate is good. When it is 70 parts by mass or less, the tensile elongation of the film after curing is good.

(D) Other additives In the positive photosensitive resin composition of the present invention, if necessary, a hydroxyl group-containing compound (excluding a phenol compound that appears later), a positive photosensitive resin composition, It is possible to add phenol compounds, dyes, surfactants, stabilizers and at least one adhesion aid for improving adhesion to a silicon wafer, which are known as additives.
More specifically describing the additive, the hydroxyl group-containing compound preferably has 4 to 14 carbon atoms. When a hydroxyl group-containing compound is added to the positive photosensitive resin composition of the present invention, sensitivity, resolution, and adhesion to a substrate are improved. Specific examples of the hydroxyl group-containing compound include cyclopropylcarbinol, 2-cyclohexen-1-ol, cyclohexanemethanol, 4-methyl-1-cyclohexanemethanol, 3,4-dimethylcyclohexanol, 4-ethylcyclohexanol, 4-t-butyrocyclohexanol, cyclohexaneethanol, 3-cyclohexyl-1-propanol, 1-cyclohexyl-1-pentanol, 3,3,5-trimethylcyclohexanol, norbornane-2-methanol, cyclooctanol, 2, 3,4-trimethyl-3-pentanol, 2,4-hexadien-1-ol, cis-2-hexen-1-ol, trans-2-hepten-1-ol, cis-4-hepten-1-ol Cis-3-octen-1-ol 4-ethyl-1-octin-3-ol, 2,7-octadienol, 3,6-dimethyl-1-heptin-3-ol, 3-ethyl-2-methyl-3-pentanol, 2-ethyl -1-hexanol, 2,3-dimethyl-2-hexanol, 2,5-dimethyl-2-hexanol, trans, cis-2,6-nonadien-1-ol, 1-nonen-3-ol, cis-2 -Butene-1,4-diol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,5-hexadiene-3,4-diol, 2,5 -Dimethyl-3-hexyne-2,5-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,2,4,4-tetramethyl-1,3-cyclobutane Diol, 1,2-cyclohe Sanji ol, trans-p-menthane-3,8-diol, 2,4-dimethoxybenzyl alcohol, butyroin, and the like.
Among these, a hydroxyl group-containing compound having a structure represented by the following general formula (4) is preferable.

(In the formula, R ₂ is a monovalent or divalent organic group having a branched structure, a ring structure, or an unsaturated double bond, and having 4 to 14 carbon atoms, and q is 1 to 2). Is an integer.)
Specifically, cyclopropylcarbinol, 2-cyclohexen-1-ol, cyclohexanemethanol, 4-methyl-1-cyclohexanemethanol, 3,4-dimethylcyclohexanol, 4-ethylcyclohexanol, 4-t-butyro Cyclohexanol, cyclohexaneethanol, 3-cyclohexyl-1-propanol, 1-cyclohexyl-1-pentanol, 3,3,5-trimethylcyclohexanol, norbornane-2-methanol, cyclooctanol, 2,3,4-trimethyl- 3-pentanol, 2,4-hexadien-1-ol, cis-2-hexen-1-ol, trans-2-hepten-1-ol, cis-4-hepten-1-ol, cis-3-octene -1-ol, 4-ethyl-1-octyne-3-o 2,7-octadienol, 3,6-dimethyl-1-heptin-3-ol, 3-ethyl-2-methyl-3-pentanol, 2-ethyl-1-hexanol, 2,3-dimethyl 2-hexanol, 2,5-dimethyl-2-hexanol, trans, cis-2,6-nonadien-1-ol, 1-nonen-3-ol, cis-2-butene-1,4-diol, 2 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,5-hexadiene-3,4-diol, 2,5-dimethyl-3-hexyne-2,5 -Diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanediol, trans -P- Pentane-3,8-diol, 2,4-dimethoxybenzyl alcohol, butyroin, and the like.
Furthermore, the hydroxyl group containing compound which has a structure represented by (5) is more preferable.

(Wherein R ₄ is a monovalent organic group having a branched structure, a ring structure, or an unsaturated double bond, and having 4 to 14 carbon atoms.)
Specifically, cyclopropylcarbinol, 2-cyclohexen-1-ol, cyclohexanemethanol, 4-methyl-1-cyclohexanemethanol, 3,4-dimethylcyclohexanol, 4-ethylcyclohexanol, 4-t-butyro Cyclohexanol, cyclohexaneethanol, 3-cyclohexyl-1-propanol, 1-cyclohexyl-1-pentanol, 3,3,5-trimethylcyclohexanol, norbornane-2-methanol, cyclooctanol, 2,3,4-trimethyl- 3-pentanol, 2,4-hexadien-1-ol, cis-2-hexen-1-ol, trans-2-hepten-1-ol, cis-4-hepten-1-ol, cis-3-octene -1-ol, 4-ethyl-1-octyne-3-o 2,7-octadienol, 3,6-dimethyl-1-heptin-3-ol, 3-ethyl-2-methyl-3-pentanol, 2-ethyl-1-hexanol, 2,3-dimethyl -2-hexanol, 2,5-dimethyl-2-hexanol, trans, cis-2,6-nonadien-1-ol, 1-nonen-3-ol, 2,4-dimethoxybenzyl alcohol and the like.
These hydroxyl group-containing compounds may be used alone or in combination of two or more.

The blending amount of the hydroxyl group-containing compound with respect to the hydroxypolyamide is preferably 0 to 70 parts by mass, more preferably 0.1 to 50 parts by mass, and further preferably 1 to 40 parts by mass with respect to 100 parts by mass of the hydroxypolyamide. 5 to 25 is particularly preferable. When the compounding amount of the hydroxyl group-containing compound is 0.01 parts by mass or more, the development residue in the exposed area decreases, and when it is 70 parts by mass or less, the tensile elongation of the film after curing is good.
The phenol compound is a ballast agent used in the photosensitive diazoquinone compound, and a linear phenol compound such as paracumylphenol, bisphenols, resorcinol, or MtrisPC, MtetraPC (made by Honshu Chemical Industry Co., Ltd .: trade name), Non-linear phenolic compounds such as TrisP-HAP, TrisP-PHBA, TrisP-PA (made by Honshu Chemical Industry Co., Ltd .: trade name), compounds in which 2-5 hydrogen atoms of the phenyl group of diphenylmethane are substituted with hydroxyl groups, 2, The compound etc. which substituted the 1-5 hydrogen atom of the phenyl group of 2-diphenylpropane by the hydroxyl group are mentioned. By adding the phenol compound, the adhesion of the relief pattern during development can be improved and the generation of residues can be suppressed. In addition, a ballast agent means the phenol compound currently used as a raw material for the above-mentioned photosensitive diazoquinone compound which is a phenol compound in which a part of the phenolic hydrogen atom is converted to naphthoquinonediazide sulfonic acid ester.

0-50 mass parts is preferable with respect to 100 mass parts of this hydroxy polyamide, and, as for the compounding quantity with respect to hydroxy polyamide of a phenolic compound, 1-30 mass parts is preferable. When the addition amount is within 50 parts by mass, the heat resistance of the film after thermosetting is good.
Examples of the dye include methyl violet, crystal violet, and malachite green. As for the compounding quantity with respect to the hydroxy polyamide of dye, 0.1-10 mass parts is preferable with respect to 100 mass parts of this hydroxy polyamide. When the addition amount is 10 parts by mass or less, the heat resistance of the film after thermosetting is good.
Examples of the surfactant include polypropylene glycol, polyglycols such as polyoxyethylene lauryl ether, and nonionic surfactants composed of derivatives thereof. Further, fluorine-based surfactants such as Fluorard (manufactured by Sumitomo 3M: trade name), Mega-Fac (manufactured by Dainippon Ink & Chemicals, Inc .: trade name), or Sulflon (made by Asahi Glass Co., Ltd .: trade name) are listed. Furthermore, organosiloxane surfactants such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name), DBE (manufactured by Chisso Corporation: trade name), or granol (manufactured by Kyoeisha Chemical Co., Ltd .: trade name) are listed. By adding the surfactant, it is possible to make it more difficult for the coating film to be repelled at the wafer edge during coating.

0-10 mass parts is preferable with respect to 100 mass parts of this hydroxy polyamide, and, as for the compounding quantity with respect to hydroxy polyamide of surfactant, 0.01-1 mass part is more preferable. If the addition amount is within 10 parts by mass, the heat resistance of the film after thermosetting is good.
Examples of the adhesion aid include various silane coupling agents such as alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy polymer, and epoxy silane.
Specific preferred examples of the silane coupling agent include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Corporation: trade name: Syra Ace S810), 3-mercaptopropyltriethoxysilane. (Manufactured by Azmax Co., Ltd .: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS1375, product of Azmax Co., Ltd .: trade name SIM6474.0), mercaptomethyltrimethoxysilane ( Azmax Co., Ltd .: Trade name SIM6473.5C), Mercaptomethylmethyldimethoxysilane (Azmax Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercap Topropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2 -Mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2 -Mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethyl Xisilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS3610, manufactured by Asmax Co., Ltd .: trade name SIU9055. 0), N- (3-trimethoxysilylpropyl) urea (manufactured by Azmax Co., Ltd .: trade name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- (3-ethoxydimethoxysilylpropyl) Urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea Urea, N- (3-Met Sidipropoxysilylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3-tripropoxy) Silylethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- (3-trimethoxy Silylbutyl) urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0598 .0), m-aminophenyltrimethoxysilane (as Product name: SLA0599.0), p-aminophenyltrimethoxysilane (product name: SLA0599.1) Aminophenyltrimethoxysilane (product name: SLA0599.2), 2 -(Trimethoxysilylethyl) pyridine (manufactured by Azmax Co., Ltd .: Trade name SIT83396), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) Examples thereof include pyridine, (3-triethoxysilylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, and the like. Particularly preferable examples include, but are not limited to, the following structures.

The blending amount of the adhesion aid with respect to hydroxypolyamide is preferably 0 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, further preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the hydroxypolyamide. 1 to 5 parts by mass is particularly preferable. When the compounding amount of the silicon-based coupling agent is 0.01 parts by mass or more, there is no development residue in the exposed area, and adhesion with the silicon substrate is good. When it is 20 parts by mass or less, the temporal stability in adhesion is good.
In the present invention, these components are preferably dissolved in a solvent to form a varnish and used as a positive photosensitive resin composition. Examples of such solvents include N-methyl-2-pyrrolidone, γ-butyrolactone (hereinafter also referred to as “GBL”), cyclopentanone, cyclohexanone, isophorone, N, N-dimethylacetamide (hereinafter also referred to as “DMAc”). ), Dimethylimidazolinone, tetramethylurea, dimethyl sulfoxide, diethylene glycol dimethyl ether (hereinafter also referred to as “DMDG”), diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol Monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol Seteto, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, may be used alone or as a mixture of methyl 3-methoxy propionate or the like. Of these solvents, non-amide solvents are preferred because they have little influence on the photoresist. Specific more preferable examples include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate and the like.
The blending amount of the solvent with respect to hydroxypolyamide is preferably 50 to 1000 parts by mass with respect to 100 parts by mass of the hydroxypolyamide. The addition amount of the solvent is preferably set to a viscosity suitable for the coating apparatus and the coating thickness within the above range, because the production of the cured relief pattern can be facilitated.

<Curing relief pattern and method for manufacturing semiconductor device>
Next, the manufacturing method of the cured relief pattern of the present invention will be specifically described below.
First, the positive photosensitive resin composition of the present invention is applied to a substrate such as a silicon wafer, a ceramic substrate, or an aluminum substrate by spin coating using a spinner, or a coater such as a die coater or a roll coater. To do. This is dried at 50 to 140 ° C. using an oven or a hot plate to remove the solvent.
Second, exposure with actinic radiation is performed through a mask using a contact aligner or a stepper, or light, electron beam, or ion beam is directly irradiated.
Third, the exposed portion or the irradiated portion is dissolved and removed with a developing solution, followed by rinsing with a rinsing solution to obtain a desired relief pattern. As a developing method, a spray, paddle, dip, or ultrasonic method can be used. As the rinsing liquid, distilled water, deionized water or the like can be used.
The developer used for developing the film formed from the positive photosensitive resin composition of the present invention is for dissolving and removing the alkali-soluble polymer and needs to be an alkaline aqueous solution in which an alkali compound is dissolved. is there. The alkali compound dissolved in the developer may be either an inorganic alkali compound or an organic alkali compound.

Examples of the inorganic alkali compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate. , Lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, and ammonia.
Examples of the organic alkali compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, diethylamine. -N-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, triethanolamine, etc. are mentioned.

Furthermore, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a storage stabilizer, and a resin dissolution inhibitor can be added to the alkaline aqueous solution. .
Finally, the obtained relief pattern is heat-treated to form a heat-resistant cured relief pattern made of a resin having a polybenzoxazole structure.
The semiconductor device of the present invention uses the cured relief pattern of the present invention as a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, or a protective film for a device having a bump structure. It can manufacture by combining with the manufacturing method of an apparatus.
The positive photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad plates, solder resist films, or liquid crystal alignment films.

The present invention will be described based on reference examples and examples.
[Reference Example 1]
<Synthesis of hydroxy polyamide>
In a 2 L separable flask, 197.8 g (0.54 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 75.9 g (0.96 mol) of pyridine, and 692 g of DMAc at room temperature. (25 ° C.) The mixture was stirred and dissolved. A solution obtained by dissolving 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic anhydride in 88 g of DMDG was added dropwise thereto from a dropping funnel. The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 28 ° C.

After completion of the dropwise addition, the mixture was heated to 50 ° C. with a hot water bath and stirred for 18 hours, and then the IR spectrum of the reaction solution was measured to confirm that characteristic absorption of imide groups at 1385 cm ⁻¹ and 1772 cm ⁻¹ appeared.
Next, this was cooled to 8 ° C. with a water bath, and a solution obtained by dissolving 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride in 398 g of DMDG was added dropwise thereto from a dropping funnel. The time required for the dropping was 80 minutes, and the maximum reaction solution temperature was 12 ° C. Three hours after the completion of the dropping, the above reaction solution was dropped into 12 liters of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, washed with water as appropriate, dehydrated and then vacuum-dried. ) The weight average molecular weight of the thus synthesized hydroxypolyamide by GPC was 14,000 in terms of polystyrene. The analysis conditions for GPC are described below.
Column: Showa Denko Co., Ltd. Trade name: Shodex 805/804/803 Series separation liquid: Tetrahydrofuran 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko brand name Shodex RI SE-61

[Reference Example 2]
<Synthesis of diazonaphthoquinone compound>
In a 1 L separable flask, 109.9 g (0.3 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 330 g of tetrahydrofuran (THF), 47.5 g (0.6 mol) of pyridine. Into this, 98.5 g (0.6 mol) of 5-norbornene-2,3-dicarboxylic anhydride was added in powder form at room temperature. After stirring for 3 days at room temperature, the reaction was confirmed by HPLC. As a result, no starting material was detected and the product was detected as a single peak with a purity of 99%. This reaction solution was dropped as it was into 1 l of ion-exchanged water with stirring, and the precipitate was filtered off, and then 500 ml of THF was added and dissolved by stirring. This homogeneous solution was dissolved in cation exchange resin: Amberlyst 15 (manufactured by Organo). ) The remaining pyridine was removed through a glass column packed with 100 g. Next, this solution was dropped into 3 l of ion-exchanged water under high-speed stirring to precipitate a product, which was filtered off and then vacuum-dried.
The product is imidized, it is not characteristic absorption of amide groups in the vicinity of 1540 cm ^-1 and 1650 cm ^-1 appear characteristic absorption of an imide group 1394Cm ^-1 and 1774 cm ^-1 in the IR spectrum is present, and NMR spectrum This was confirmed by the absence of amide and carboxylic acid proton peaks.

Next, 65.9 g (0.1 mol) of the product, 53.7 g (0.2 mol) of 1,2-naphthoquinonediazide-4-sulfonyl chloride and 560 g of acetone were added and dissolved by stirring at 20 ° C. A solution prepared by diluting 21.2 g (0.21 mol) of triethylamine with 106.2 g of acetone was added dropwise thereto at a constant rate over 30 minutes. At this time, the temperature of the reaction solution was controlled in the range of 20 to 30 ° C. using an ice water bath or the like.
After completion of the dropwise addition, the mixture was allowed to stir at 20 ° C. for another 30 minutes, and then 5.6 g of a 36 wt% hydrochloric acid aqueous solution was added at once. The reaction solution was then cooled in an ice water bath, and the precipitated solid was filtered off with suction. . The filtrate obtained at this time was added dropwise to 5 l of a 0.5% by weight aqueous hydrochloric acid solution over 1 hour with stirring to precipitate the desired product, which was collected by suction filtration. The obtained cake-like recovered material was again dispersed in 5 l of ion-exchanged water, stirred, washed, collected by filtration, and this water washing operation was repeated three times. Finally, the cake-like product obtained was vacuum-dried at 40 ° C. for 24 hours to obtain a photosensitive diazoquinone compound (Q-1).

[Reference Example 3]
<Synthesis of polyimide precursor composition>
In a separable flask with a volume of 2 liters, 87.2 g (0.4 mol) of pyromellitic dianhydride, 59.3 g (0.8 mol) of isobutyl alcohol and 320 g of GBL were mixed and stirred at room temperature (25 ° C.), and dissolved. While stirring under cooling, 63.3 g (0.8 mol) of pyridine was added. After completion of heat generation, the solution was cooled to room temperature and left for 16 hours.
Next, a solution of 165 g (0.8 mol) of dicyclohexylcarbodiimide dissolved in 120 g of GBL was added over 40 minutes with stirring under ice-cooling, and then 74.5 g (0.37 mol) of 4,4′-diaminodiphenyl ether was added to 150 g of GBL. The suspension was similarly added over 60 minutes with stirring under ice cooling. After stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour. After further addition of 250 ml of DMAc and 400 ml of THF, the precipitate was removed by suction filtration, and the resulting reaction solution was added to 15 l of ethyl alcohol. The resulting precipitate was filtered off and then vacuum dried to obtain a polyimide precursor (P-2).

<Preparation of positive photosensitive resin composition>
[Examples 1-11, Comparative Examples 1-7]
The photosensitive diazoquinone compound (Q-1) obtained in Reference Example 2 above and 100 parts by mass of the hydroxypolyamide (P-1, P-2) obtained in Reference Examples 1 and 3 above, and C-1 to C-13 aromatic carboxylic acid compounds were dissolved in 170 parts by mass of GBL, then filtered through a 0.2 μm filter, and Examples 1 to 11 and Comparative Examples 1 to 1 described in Table 1 were used. 7 positive type photosensitive resin composition was prepared.
(C-1) o-anisic acid (C-2) m-anisic acid (C-3) p-anisic acid (C-4) o-toluic acid (C-5) m-toluic acid (C-6) p-toluic acid (C-7) salicylic acid (C-8) 2,4-dihydroxybenzoic acid (C-9) 3,5-dihydroxybenzoic acid (C-10) 2,2'-biphenyldicarboxylic acid (C- 11) Benzoic acid (C-12) acetic acid (C-13) tiglic acid

<Evaluation of positive photosensitive resin composition>
(1) Evaluation of patterning characteristics The positive photosensitive resin compositions of the above examples and comparative examples were spin-coated on a 5-inch silicon wafer with a spin coater (Dspin 636 manufactured by Dainippon Screen Mfg. Co., Ltd.), and 120 on a hot plate. Pre-baking was performed at 180 ° C. for 180 seconds to form a coating film having a thickness of 11.5 μm. The film thickness was measured with a film thickness measuring device (Lambda Ace manufactured by Dainippon Screen Mfg. Co., Ltd.).
This coating film was exposed through a reticle with a test pattern using a stepper (NSR2005i8A manufactured by Nikon Corporation) having an exposure wavelength of i-line (365 nm) while changing the exposure stepwise. Using an alkali developer (AZ300MIF developer manufactured by AZ Electronic Materials Co., Ltd., 2.38 mass% tetramethylammonium hydroxide aqueous solution), the development time is 23 ° C. so that the film thickness after development is 9.8 μm. Was developed and rinsed with pure water to form a positive relief pattern. The development time was about 40 seconds to 140 seconds. Table 2 shows the sensitivity, resolution, and adhesive state of the positive photosensitive resin composition.

In the comparative example using the polyamic acid ester, the solubility in an aqueous 2.38 mass% tetramethylammonium hydroxide solution was very low, and the formed 11.5 μm coating film was hardly dissolved within the development time. .
In addition, the sensitivity, resolution, and adhesiveness of the positive photosensitive resin composition were evaluated as follows.
[Sensitivity (mJ / cm ² )]
The minimum exposure amount that can completely dissolve and remove the exposed portion of the coating film during the development time.
[Resolution (μm)]
Minimum resolution pattern size at the above exposure.
[Adhesion]
What is the adhesion state of the pattern at the above exposure amount?

  The positive photosensitive resin composition of the present invention includes a surface protective film for semiconductor devices, an interlayer insulating film, an insulating film for rewiring, a protective film for flip chip devices, a protective film for devices having a bump structure, and an interlayer for multilayer circuits. It can be suitably used as an insulating film, a cover coat of a flexible copper clad plate, a solder resist film, a liquid crystal alignment film, and the like.

Claims (6)

(A) For 100 parts by mass of hydroxypolyamide having a repeating unit represented by the following general formula (1), (B) 1-50 parts by mass of a photoacid generator, (C) a fragrance having 7-15 carbon atoms. A positive photosensitive resin composition comprising 0.01 to 70 parts by mass of an aromatic carboxylic acid compound (excluding a heterocyclic ring-containing compound ).

Wherein X ₁ is a tetravalent organic group having at least 2 or more carbon atoms, and X ₂ , Y ₁ and Y ₂ are each independently a divalent organic having at least 2 carbon atoms. M is an integer of 2 to 1000, n is an integer of 0 to 500, and m / (m + n)> 0.5, where m dihydroxys including X ₁ and Y ₁ The arrangement order of the diamide unit and n diamide units including X ₂ and Y ₂ is not limited.)   (B) The positive photosensitive resin composition of Claim 1 whose photo-acid generator is a compound which has a naphthoquinone diazide structure. The positive carbon according to claim 1 or 2, wherein (C) the aromatic carboxylic acid compound having 7 to 15 carbon atoms (excluding the heterocyclic ring-containing compound ) is a compound having a structure represented by the following general formula (2). Type photosensitive resin composition.

(In the formula, R ₁ is a monovalent or divalent aromatic group having a substituent and having 6 to 14 carbon atoms, and p is an integer of 1 to 2). (C) The aromatic carboxylic acid compound having 7 to 15 carbon atoms (excluding the heterocyclic ring-containing compound ) is a compound having a structure represented by the following general formula (3). The positive photosensitive resin composition as described.

(In the formula, R ₃ is a monovalent aromatic group having a substituent and having 6 to 14 carbon atoms.)   (1) The positive photosensitive resin composition according to any one of claims 1 to 4 is formed on a substrate in the form of a layer or a film, and (2) is exposed with actinic radiation through a mask, A method for producing a cured relief pattern, which comprises directly irradiating a light beam, an electron beam or an ion beam, (3) eluting and removing an exposed portion or irradiated portion, and (4) heat-treating the obtained relief pattern.   A semiconductor device comprising a cured relief pattern layer obtained by the production method according to claim 5.