JP5072462B2 - 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 manufacturing 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 the positive photosensitive resin composition is that the PAC and PBO precursor in the unexposed area have a low dissolution rate in an alkaline aqueous solution, but the PAC chemically changes to an indenecarboxylic acid compound by exposure. This utilizes the fact that the dissolution rate of the exposed portion in the alkaline aqueous solution increases. 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. This photosensitive PBO precursor composition is easy to form a relief pattern and has good storage stability. Further, an oxazole ring is generated by heat, and the cured PBO film is a thermosetting film equivalent to a polyimide film. Since the characteristics are obtained, it attracts attention as a promising alternative material for the organic solvent development type polyimide precursor composition.

However, the photosensitive 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. This is because if the photosensitive resin composition has low sensitivity, the exposure time required for forming the relief pattern becomes long, leading to high cost of the exposure process. Therefore, although it is necessary to improve the photosensitivity of the photosensitive resin composition, Patent Document 3 proposes to add at least one selected from an onium salt, a diaryl compound, and a tetraalkylammonium salt as a dissolution inhibitor. Yes. In addition, Patent Document 4 proposes to add a compound having a sulfone group in order to adjust the dissolution rate and to improve the adhesion to the substrate.
Furthermore, in order to improve the storage stability of the photosensitive resin composition, it is proposed in Patent Document 5 that an organic acid such as fumaric acid or acetic acid is an essential component.

Japanese Examined Patent Publication No. 01-046862 JP 63-096162 A Japanese Patent No. 3509612 JP 2000-241974 A JP 2004-029712 A

  It is an object of the present invention to provide a high-sensitivity positive photosensitive resin composition, a method for producing a cured relief pattern using the composition, and a semiconductor device having the cured relief pattern.

The polyimide having a phenolic hydroxyl group and the PBO precursor composition have a problem that the sensitivity is lower than that of the photosensitive polyimide precursor composition.
Therefore, the inventor of the present invention has known in the art a resin having at least one group selected from the group consisting of a phenolic hydroxyl group and a carboxyl group in the molecular structure and soluble in an alkaline aqueous solution, or a precursor thereof. It was found that a positive photosensitive resin composition that solves the above problems can be obtained by combining a sulfonic acid anhydride and a cross-linking agent shown below with a photosensitive resin composition comprising PAC and an organic solvent. Invented the invention.
That is, the first of the present invention is (B) 1 to 50 parts by weight of a photoacid generator and (C) 0.01 to 30 parts by weight of a sulfonic anhydride with respect to 100 parts by weight of (A) an aqueous alkaline solution-soluble polymer. Part and (D) 0.1-70 mass parts of crosslinking agents, It is a positive photosensitive resin composition characterized by the above-mentioned. Furthermore, the positive photosensitive resin composition containing 0.01-50 mass parts of (E) alkoxybenzene represented by the following general formula (1) is preferable, and 0.01-50 mass parts of (F) carboxylic acid compounds are included. A positive photosensitive resin composition is more preferable.
(In the formula, Q is a group having at least one carbon atom. Q is an integer of 1 to 3. Z is a hydrogen atom or a monovalent organic group.)
In the composition of the present invention, the photoacid generator is preferably a compound having a naphthoquinonediazide structure.

Further, (A) a positive photosensitive polymer composition in which the aqueous alkali-soluble polymer is a polycondensate having a repeating unit represented by the following general formula (2) and containing a hydroxypolyamide structure in the molecule. Preferably there is.
(Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, X ₂ is a divalent organic group having at least 2 carbon atoms, and Y ₁ and Y ₂ are Each independently represents a divalent to tetravalent organic group having at least 2 carbon atoms, t and u are each independently an integer of 0 to 2, r is an integer of 2 to 1000, and s Is an integer from 0 to 500, where 0.5 <r / (r + s) ≦ 1.0, including r dihydroxydiamide units including X ₁ and Y ₁ , and X ₂ and Y ₂ . (The order of arrangement of s diamide units is not limited.)

Further, (A) the aqueous alkali solution-soluble polymer is dehydrated by one or two or more tetracarboxylic dianhydrides and one or two or more aromatic diamines having an amino group and a phenolic hydroxyl group which are ortho to each other. A polycondensate having a condensed structure is preferred.
Among them, (A) an aqueous alkali-soluble polymer is a bicyclo (2,2,2) -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and bis (3-amino It is more preferable that it is a polycondensate having a structure obtained by dehydrating condensation of -4-hydroxyphenyl) sulfone.

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, which comprises direct irradiation with an electron beam or ion beam, (3) elution removal of an exposed portion or irradiated portion with a developer, and (4) heat treatment of the obtained relief pattern. is there.
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.

  The positive photosensitive resin composition of the present invention has characteristics excellent in positive lithography performance such as high sensitivity and high resolution, and a method for producing a cured relief pattern using the positive 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) Alkaline aqueous solution-soluble polymer The (A) alkaline aqueous solution-soluble polymer used in the present composition has at least one group selected from the group consisting of a phenolic hydroxyl group and a carboxyl group in the molecular structure, and is an alkaline aqueous solution. Specific polycondensates or precursors thereof, specifically, (i) a hydropolyoxyamide that is a PBO precursor, (ii) an alkali-soluble polyimide having a phenolic hydroxyl group, (iii) ) Polyamide that is derived from tetracarboxylic acid and diamine and is a polyimide precursor having a carboxyl group at the ortho position of the amide bond, and a polycondensate having a structure obtained by copolymerizing these polycondensates in the molecule.

The above (i) hydroxypolyamide which is a PBO precursor is represented by a dihydroxydiamide unit of the following general formula (2). The dihydroxydiamide unit has a structure obtained by polycondensation of 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. r 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.
(Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, X ₂ is a divalent organic group having at least 2 carbon atoms, and Y ₁ and Y ₂ are Each independently represents a divalent to tetravalent organic group having at least 2 carbon atoms, t and u are each independently an integer of 0 to 2, r is an integer of 2 to 1000, and s Is an integer from 0 to 500, where 0.5 <r / (r + s) ≦ 1.0, including r dihydroxydiamide units including X ₁ and Y ₁ , and X ₂ and Y ₂ . (The order of arrangement of s diamide units is not limited.)

The hydroxy polyamide may have a diamide unit of the above general formula (2) 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 . s 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 r / (r + s) 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- ( -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 1,3 -Diamino-4,6-dihydroxybenzene and the like. 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.

Further, 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 in the molecule”). It is also possible to use a "diamine having a structure"). For example, the diamine represented by the following general formula obtained by reacting bisaminophenol having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ with two molecules of nitrobenzoic acid and reducing it may be mentioned. .
(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 Ruoropuropan, 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'-diaminodiphenylurea, 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′-diaminobiphenyl, o-toluidine sulfone, 2,2 -Bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4 -Aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-di- (3-aminophenoxy) diphenyl sulfone, 4,4'-diaminobenzanilide, and the like Of aromatic nuclei of aromatic diamines are chlorine, fluorine, bromine, methyl , A methoxy group, a cyano group, and a compound substituted by at least one group or atom selected from the group consisting of phenyl group.

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 aliphatic group, and a halogen atom, and k is an integer of 0 to 4 Is shown.)

A derivative of 5-aminoisophthalic acid can also 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, chloroformate 2-ethoxy ester, chloroformate-sec-butyl ester, Benzyl chloroformate, 2-ethylhexyl chloroformate, allyl ester chloroformate, phenyl ester chloroformate, 2,2,2-trichloroethyl ester chloroformate, chloro Acid 2-butoxyethyl ester, chloroformate -p- nitrobenzyl ester, chloroformate -p- methoxybenzyl ester, chloroformate isobornyl benzyl ester, chloroformate -p- biphenyl isopropyl benzyl ester,

2-t-butyloxycarbonyl-oxyimino-2-phenylacetonitrile, S-t-butyloxycarbonyl-4,6-dimethyl-thiopyrimidine, di-t-butyl-dicarbonate, N-ethoxycarbonylphthalimide, ethyldithiocarbonyl chloride , Formic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, methanesulfonic acid chloride, acetyl chloride, trityl chloride, trimethylchlorosilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoro Acetamide, (N, N-dimethylamino) trimethylsilane, (dimethylamino) trimethylsilane, trimethylsilyldiphenylurea, bis (trimethylsilyl) urea, isocyanate , 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 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.
(In the formula, 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 end group sealed with an organic group (hereinafter referred to as a 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, and tosyl chloride.

  Specific examples of the above-mentioned (ii) alkali-soluble polyimide having a phenolic hydroxyl group include one or two or more tetracarboxylic dianhydrides, and one or two or more having an amino group and a phenolic hydroxyl group that are ortho to each other. Is a polycondensate having a dehydration-condensed structure (hereinafter also simply referred to as “polycondensate A”), and tetracarboxylic dianhydride is an aromatic having 10 to 36 carbon atoms. It is preferably at least one compound selected from the group consisting of an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride having 8 to 34 carbon atoms.

  Specifically, 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4 ′ -Benzophenone tetracarboxylic dianhydride, bicyclo (2,2,2) -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-di Carboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, cyclobutanetetracarboxylic dianhydride, and 2,2 -Bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride can be mentioned. These tetracarboxylic dianhydrides can be used alone or in combination of two or more. Among the above tetracarboxylic dianhydrides, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, bicyclo (2,2,2) -oct-7-ene-2, 3,5,6-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride is the solubility of polycondensate A in organic solvents, and i-line commonly used as an exposure light source It is particularly preferable because of its high transparency with respect to.

  The above-mentioned aromatic diamine having an amino group and a phenolic hydroxyl group (hereinafter also referred to as “phenolic diamine”), that is, the phenolic diamine used herein, has one hydroxyl group (that is, Phenolic hydroxyl group), one phenolic hydroxyl group and one amino group at the ortho position, and another amino group at another position, preferably an amino group in the ortho position relative to each other, and It is an aromatic diamine having 6 to 30 carbon atoms and having at least two pairs of phenolic hydroxyl groups.

  Specifically, 3,5-diamino-1-hydroxybenzene, 4,6-diamino-1,3-dihydroxybenzene, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 4,4′-dihydroxy -3,3'-diaminobiphenyl, 3,4-dihydroxy-3 ', 4'-diaminobiphenyl, 2,2-bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxy Phenyl) sulfide, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) methane, 2,2-bis (4 -Amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropyl Bread, 2- (3hydroxy-4-aminophenyl) -2- (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3) -Hydroxyphenyl) sulfone. These phenolic diamines can be used alone or in combination of two or more. Among the above phenolic diamines, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3′-dihydroxy-4,4′-diaminobiphenyl, and bis (3-amino- 4-Hydroxyphenyl) sulfone is particularly preferred because of the high solubility of polycondensate A in an alkaline developer.

  As polycondensate A used in the present composition, tetracarboxylic dianhydride is bicyclo (2,2,2) -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. Yes, the polycondensate having a polycondensation structure in which the phenolic diamine is bis (3-amino-4-hydroxyphenyl) sulfone is highly soluble in organic solvents and highly transparent to the exposure light source. This is most preferable because it has a low coefficient of thermal expansion, high solubility in an alkali developer, and good resolution pattern resolution.

The dehydration condensation reaction can be performed by heating the tetracarboxylic dianhydride and the phenolic diamine to 30 ° C. to 220 ° C., preferably 170 ° C. to 200 ° C. in the presence of an acid or a base catalyst. . As the acid catalyst, it is possible to use an inorganic acid such as sulfuric acid or an organic acid such as p-toluenesulfonic acid, which is usually used in the production of polyimide. Since it remains in the condensate solution, it becomes a deterioration factor of the composition of the present invention, and it is necessary to remove these catalysts by precipitating and redissolving the polycondensate. For this reason, in producing the polycondensate A, an acid group that is generated in situ by performing the above dehydration condensation in the presence of a lactone-base catalyst is preferably used as the acid catalyst. That is, it is preferable to use a catalyst system utilizing the following equilibrium reaction of lactone, base and water as the acid catalyst.
{Lactone} + {base} + {water} = {acid group} ⁺ {base} ⁻
Dehydration condensation can be carried out using this {acid group} ⁺ {base} ⁻ system as a catalyst. The water produced is azeotroped with toluene and removed from the reaction system. When the reaction system imidization is completed, {acid} ⁺ {base} ^- it becomes lactone and base are removed from the reaction system together with the simultaneous toluene lose catalysis. The polycondensate A solution produced by this method can be industrially used as it is as a high-purity polycondensate solution because the catalyst material is not contained in the polyimide solution after the reaction.
As the lactone used here, γ-valerolactone is preferable, and as the base, it is preferable to use at least one of pyridine and methylmorpholine.

Furthermore, without adding a polycondensation catalyst or the like, the temperature of the reaction solution is maintained at a temperature higher than the temperature at which the imidization reaction occurs, and the water generated by the dehydration reaction is removed from the reaction system using an azeotropic solvent with water such as toluene. A method of completing the imidation dehydration condensation reaction is more preferable. The solution of polycondensate A produced by this method can also be used industrially as it is as a high-purity polycondensate solution because the catalyst substance is not contained in the polyimide solution after the reaction.
As a reaction solvent for performing the dehydration condensation reaction, it is preferable to use a polar organic solvent for dissolving the polycondensate A in addition to toluene which is a solvent for azeotropically distilling water. As these polar solvents, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, tetramethylurea, sulfolane and the like are used.

When the lactone-base catalyst is used, the concentration of tetracarboxylic dianhydride in the entire reaction mixture at the start of the reaction is preferably in the range of 4 to 25% by weight, and the concentration of lactone is 0 to 0.6% by weight. The base concentration is preferably 0 to 0.9% by weight.
In the polycondensate A, polycondensation obtained by copolycondensation of tetracarboxylic dianhydride, the above-mentioned phenolic diamine, and a diamine having no phenolic hydroxyl group (hereinafter referred to as “non-phenolic diamine”). By using a material, the physical properties can be controlled more freely. Non-phenolic diamines are aromatic diamines having 6 to 30 carbon atoms that do not have phenolic hydroxyl groups, and diaminopolysiloxanes.

  Specifically, 4,4 ′-(or 3,4′-, 3,3′-, 2,4 ′-) diaminodiphenyl ether, 4,4 ′-(or 3,3 ′-) diaminodiphenyl sulfone, 4,4 ′-(or 3,3 ′-) diaminodiphenyl sulfide, 4,4′-benzophenone diamine, 3,3′-benzophenone diamine, 4,4′-di (4-aminophenoxy) phenyl sulfone, 4, 4′-di (3-aminophenoxy) phenylsulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) ) Benzene, 2,2-bis {4- (4-aminophenoxy) phenyl} propane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 2, '- bis (4-aminophenyl) propane,

2,2′-trifluoromethyl-4,4′-diaminobiphenyl, 2,2 ′, 6,6′-tetramethyl-4,4′-diaminobiphenyl, 2,2 ′, 6,6′-tetratri Fluoromethyl-4,4′-diaminobiphenyl, bis {(4-aminophenyl) -2-propyl} 1,4-benzene, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4 -Aminophenoxyphenyl) fluorene, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, aromatic diamines such as 3,5-diaminobenzoic acid, 2,6-diaminopyridine, 2,4-diamino Examples include diamines such as pyridine, bis (4-aminophenyl-2-propyl) -1,4-benzene, and diaminopolysiloxane compounds. Non-phenolic diamine can be used individually or in combination of 2 or more types.

In general, a polyimide resin having a high elastic modulus is a linear, rigid polymer that has low solubility in a solvent and low transparency to i-line. Therefore, it is important to design a polymer with a molecular arrangement that meets the conflicting requirements of solvent solubility and high modulus. Therefore, the polycondensate A is a block having a defined molecular sequence comprising a block obtained by polycondensation of phenolic diamine and tetracarboxylic dianhydride and a block obtained by polycondensation of non-phenolic diamine and tetracarboxylic dianhydride. A copolycondensate is preferred.
When the block copolycondensate is used, in the block obtained by polycondensation of non-phenolic diamine and tetracarboxylic dianhydride, aromatic tetracarboxylic acid is preferable from the viewpoint of obtaining a highly elastic polymer, and aliphatic tetracarboxylic acid is From the viewpoint of solubility in a solvent and transparency to i-line, bicyclo (2,2,2) -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride is particularly preferable. Non-phenolic diamines are preferred from the viewpoint of obtaining a polymer having a high elastic modulus as an aromatic diamine.

  The block obtained by polycondensation of phenolic diamine and tetracarboxylic dianhydride has a tetracarboxylic dianhydride of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, bicyclo ( 2,2,2) -Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, at least one selected from the group consisting of bis (3,4-dicarboxyphenyl) ether dianhydride Certain compounds and phenolic diamines are 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3′-dihydroxy-4,4′-diaminobiphenyl, and bis (3-amino A block having a structure in which at least one compound selected from the group consisting of -4-hydroxyphenyl) sulfone is polycondensed is against an aqueous alkaline solution. From the viewpoints of solubility, i-line transparency, and solvent solubility.

  Among them, bicyclo (2,2,2) -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and bis (3-amino-4-hydroxyphenyl) sulfone have a dehydration condensation structure. A polycondensate having bis (3-amino-4-hydroxyphenyl) sulfone in the range of 20 mol% to 60 mol% in all the raw material monomers for obtaining polycondensate A. , Solubility in organic solvents, transparency to i-line, high developability using 2.38% tetramethylammonium hydroxide aqueous solution, which is a developer usually used in the manufacturing process of semiconductor devices, and the relief pattern This is preferable because the resolution performance is high and the thermal expansion coefficient of the cured film is low.

  The polycondensate A is made into a block copolycondensate in the condensation reaction described above to obtain a block in which tetracarboxylic dianhydride is excessively reacted with a phenolic diamine, and then a non-phenolic diamine is added ( The molar ratio of the sum of the phenolic diamine and non-phenolic diamine and the tetracarboxylic dianhydride is 1: 1.5 to 0.7). In this case, the order of adding the non-phenolic diamine and the phenolic diamine may be changed. This technique is specifically described in various examples below. When the copolycondensate having four or more components is used, the number of times each monomer is sequentially added may be increased accordingly.

Needless to say, a block copolycondensate can be formed using two or more tetracarboxylic dianhydrides or two or more phenolic diamines. Moreover, this invention is not limited to the block copolycondensate using a sequential reaction, When preparing a raw material of 3 or more components, it is possible to prepare a random copolycondensate by simultaneously charging the raw materials into the reaction system.
Furthermore, the terminal of the polycondensate A may be modified with an organic group having an unsaturated bond. As methods for modifying the terminal of the polycondensate A, maleic anhydride, succinic anhydride, cinnamic anhydride, norbornene anhydride, 4-ethynylphthalic anhydride, phenylethynylphthalic anhydride, 4 An appropriate amount of aminostyrene, 4-ethynylaniline, 3-ethynylaniline or the like may be added during the synthesis of the polycondensate A.

  Regarding the weight average molecular weight of polycondensate A and the developer, the weight average molecular weight in terms of polystyrene is 3000 to 70000, an ethanolamine aqueous solution, a 5% tetramethylammonium hydroxide aqueous solution, or a 2.38% tetramethylammonium hydroxide. Polycondensates that can be developed with an aqueous solution are preferred. Bicyclo (2,2,2) -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and bis (3-amino-4-hydroxyphenyl) sulfone have a dehydration condensation structure. When the polycondensate is a polycondensate in which bis (3-amino-4-hydroxyphenyl) sulfone is in the range of 20 mol% to 60 mol% in the total raw material monomers for obtaining the polycondensate A, The weight average molecular weight in terms of polystyrene is more preferably 5000 to 17000, the mechanical properties are improved when the weight average molecular weight is 5000 or more, and the dispersibility in the 2.38% tetramethylammonium hydroxide aqueous solution is improved at 17000 or less. The resolution performance of the relief pattern is improved. In order to control the weight average molecular weight, the molar ratio of the sum of all tetracarboxylic dianhydrides, phenolic diamine and non-phenolic diamine is 1: 0.75 to 0.87 or 0.75 to 0.87: It is preferable to make it react by ratio of 1, and it is more preferable to make it react by ratio of 1: 0.75-0.87 especially. As described above, it is possible to control the molecular weight by adding 1: 1 and shortening the reaction time, but in this case, the storage stability of the composition at room temperature is not good.

The polycondensate A produced by the above method can be obtained in the form of a solution dissolved in an organic solvent (hereinafter also referred to as “polycondensate solution” or “polymer solution”). The composition of the present invention can also be obtained by adding a functional diazonaphthoquinone compound. The concentration of the polycondensate A in the polycondensate solution is preferably in the range of 5 to 50% by weight. If desired, the solution can be further diluted with the diluent solvents listed below.
Examples of the diluting solvent include polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, morpholine, and the like. In addition to this polar solvent, ketones, esters, lactones, ethers, halogenated hydrocarbons and hydrocarbons which are general organic solvents may be mixed, for example, acetone, methyl ethyl ketone, methyl isobutyl. Ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, hept Emissions, benzene, may be toluene, xylene, and mesitylene used.

  In addition, instead of using the produced polycondensate solution as it is, the polycondensate may be isolated through a purification step and redissolved in the dilution solvent before use. As a specific purification step, first, a polycondensate is precipitated by adding a poor solvent such as methanol, ethanol, isopropanol, or water to the polycondensate solution obtained by the above production method. Next, it is dissolved again in a good solvent such as γ-butyrolactone or N-methylpyrrolidone, and the solution is passed through a column filled with an ion exchange resin to remove ionic impurities. Finally, it is a purification step in which the solution is dropped into pure water, the precipitate is filtered off and vacuum dried. Thereby, a low molecular weight component, an ionic impurity, etc. can also be removed.

  (Iii) Polyamide, which is a polyimide precursor derived from tetracarboxylic acid and diamine and having a carboxyl group at the ortho position of the amide bond, is obtained by combining the above tetracarboxylic acid anhydride and non-phenolic diamine with γ-butyrolactone, N-methyl It can be obtained by an addition condensation reaction in a polar organic solvent such as pyrrolidone, dimethylformamide, dimethylacetamide, tetramethylurea, or sulfolane at room temperature using a catalyst such as pyridine or triethylamine as necessary. The weight average molecular weight is preferably in the range of 8000 to 70000, and when adjusting the molecular weight, it is preferable from the standpoint of storage stability at room temperature that a large amount of tetracarboxylic acid is added to form a carboxylic acid terminal. The reaction solution may be used as a composition as it is, or may be subjected to a purification step as described above.

(B) Photoacid generator As the photoacid generator contained in the positive photosensitive resin composition of the present invention, a compound having a naphthoquinonediazide structure, an onium salt, a halogen-containing compound, and the like can be used. A diazoquinone compound is preferred.
Examples of the onium salt 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 preferred.

  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 a known substance disclosed in US 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 composition of the present invention, 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 this composition, the blending amount of the photoacid generator with respect to the aqueous alkali-soluble polymer is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight with respect to 100 parts by weight of the aqueous alkali-soluble polymer. -30 mass parts is especially preferable. When the blending amount of the photoacid generator is 1 part by mass or more, the patterning property of the resin is good. Few.

(C) Sulfonic acid anhydride The sulfonic acid anhydride used in the present invention preferably has 2 to 14 carbon atoms. Specific examples include benzenesulfonic anhydride, p-toluenesulfonic anhydride, methanesulfonic anhydride, trifluoromethanesulfonic anhydride, and the like.
These sulfonic anhydrides may be used alone or in combination of two or more.
The blending amount of the sulfonic acid anhydride with respect to the aqueous alkali-soluble polymer is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 15 parts by weight with respect to 100 parts by weight of the aqueous alkali-soluble polymer. 0.1-10 mass parts is further more preferable, and 0.5-5 are especially preferable. When the blending amount of the sulfonic anhydride is 0.01 parts by mass or more, the patterning property of the resin is good, and when it is 30 parts by mass or less, the tensile elongation of the cured film is good.

(D) Crosslinking agent The crosslinking agent contained in the positive photosensitive resin composition of the present invention is preferably the following compound containing a methylol group or a methoxymethyl group.

Other than the above, as the compound containing a methylol group or a methoxymethyl group, Nicarak MX-270 (manufactured by Sanwa Chemical Co., Ltd .: trade name) and Nicalak MX-280 (manufactured by Sanwa Chemical Co., Ltd .: trade name) are preferable.
The blending amount of the crosslinking agent with respect to the aqueous alkali-soluble polymer is preferably 0.1 to 70 parts by weight, more preferably 1 to 50 parts by weight, and 5 to 30 parts by weight with respect to 100 parts by weight of the aqueous alkali-soluble polymer. Part is particularly preferred. When the blending amount of the crosslinking agent is 0.01 parts by mass or more, the heat resistance of the film after thermosetting is good, and when it is 70 parts by mass or less, the tensile elongation of the film after curing is good.
(E) Alkoxybenzene The alkoxybenzene used in the present invention is a compound represented by the following general formula (1), and among them, a compound having two or more alkoxyl groups is preferable.
(In the formula, Q is a group having at least one carbon atom. Q is an integer of 1 to 3. Z is a hydrogen atom or a monovalent organic group.)
Specifically, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, 2,5-dimethoxyacetanilide, 2,4-dimethoxyacetoacetanilide, 2,4-dimethoxyacetophenone, 2, 4-dimethoxybenzyl aldehyde, 2,3-dimethoxybenzylamide, 3,5-dimethoxybenzylamide, 2,3-dimethoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,5-dimethoxybenzoic acid, 2,6- Dimethoxybenzoic acid, 3,4-dimethoxybenzoic acid, 3,5-dimethoxybenzoic acid, methyl 3,5-dimethoxybenzoate, 2,3-dimethoxybenzyl alcohol, 2,4-dimethoxybenzyl alcohol, 3,4-dimethoxy Benzyl alcohol, 3,5-dimethoxybenzyl alcohol, 1 3,5-trimethoxybenzene, 1,3,5-triethoxybenzene, 1,3,5-triisopropoxybenzene, 1,3,5-trimethoxytoluene, 1,3,5-trimethoxybenzyl alcohol, 1,3,5-trimethoxybenzoic acid and the like.
These alkoxybenzenes may be used alone or in combination of two or more.
The blending amount of the alkoxybenzene with respect to the alkaline aqueous solution-soluble polymer is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the alkaline aqueous solution-soluble polymer. 20 mass parts is further more preferable, and 5-15 mass parts is especially preferable. When the compounding amount of alkoxybenzene is 0.01 parts by mass or more, the effect of removing residues in the exposed area is high. When it is 50 parts by mass or less, the heat resistance of the film after thermosetting is good.

(F) Carboxylic acid compound The carboxylic acid compound used in the present invention has a linear structure, a branched structure, and a cyclic structure, and preferably has 6 to 17 carbon atoms. Specifically, sorbic acid, lauric acid, myristic acid, adipic acid, 2-methyl-4-pentenoic acid, 4-methyl-2-pentenoic acid, 2-methyl-2-pentenoic acid, 2-methyl-n- Valeric acid, 3-methyl-n-valeric acid, 4-methyl-n-valeric acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, n-nonanoic acid, isononanoic acid, decanoic acid, DL-leucine acid, N- Acetyl-DL-methionine, 2-heptenoic acid, 2-octenoic acid, 2-nonenoic acid, 2-decenoic acid, 9-decenoic acid, 2-dodecenoic acid, 10-undecenoic acid, 3-cyclohexene-1-carboxylic acid, 1-cyclohexene-3-carboxylic acid, cyclohexanecarboxylic acid, cyclopentylacetic acid, cyclohexylacetic acid, cyclohexylpropionic acid, 4-cyclohexylbutyric acid, 5-norbornene-2 Carboxylic acid, o-tolylacetic acid, m-tolylacetic acid, p-tolylacetic acid, o-toluic acid, m-toluic acid, p-toluic acid, o-anisic acid, m-anisic acid, p-anisic acid, 2, Examples include 4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, diphenolic acid, 2,2′-biphenyldicarboxylic acid, and the like.

These carboxylic acid compounds may be used alone or in combination of two or more.
The blending amount of the carboxylic acid compound with respect to the alkaline aqueous solution-soluble polymer is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the alkaline aqueous solution-soluble polymer. -20 mass parts is further more preferable, and 5-15 mass parts is especially preferable. When the compounding amount of the carboxylic acid compound is 0.01 parts by mass or more, the resolution of the exposed part is high and the adhesion to the silicon substrate is also good. When it is 50 parts by mass or less, the tensile elongation of the film after curing is good.

(G) Other additives For the positive photosensitive resin composition of the present invention, phenol compounds, dyes, fragrances and surfactants known as additives for the positive photosensitive resin composition are optionally added. It is also possible to add an adhesion assistant and an allyl compound for enhancing the adhesion to the silicon wafer.
More specifically about the additive, 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. (Honshu Chemical Industry Co., Ltd .: trade name), non-linear phenol compounds such as TrisP-HAP, TrisP-PHBA, TrisP-PA (Honshu Chemical Industry Co., Ltd .: trade name), 2 to 2 hydrogen atoms of the phenyl group of diphenylmethane Examples include compounds in which 5 are substituted with hydroxyl groups, and compounds in which 1 to 5 hydrogen atoms of the phenyl group of 2,2-diphenylpropane are substituted with hydroxyl groups. 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 alkaline aqueous solution soluble polymer, and 1-30 mass parts is preferable with respect to 100 mass parts of this alkaline aqueous solution soluble polymer. If the addition amount is 50 parts by mass or less, the heat resistance of the film after thermosetting is good.

Examples of the dye include methyl violet, crystal violet, and malachite green.
The blending amount of the dye with respect to the aqueous alkali-soluble polymer is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the aqueous alkaline solution-soluble polymer. When the addition amount is 10 parts by mass or less, the heat resistance of the film after thermosetting is good.
As the fragrance, terpene compounds are preferable, and specifically, linalool, isophytol, dihydrolinalool, linalool acetate, linalool oxide, geranyl linalool, lavandulol, tetrahydrolavandulol, lavandulol acetate, nerol, nerol acetate , Geraniol, citral, geranyl acetate, geranyl acetone, geraniic acid, citral dimethyl acetal, citronellol, citronellal, hydroxycitronellal, dimethyloctanal, citronellyl acid, citronellyl acetate, tageton, artemisia ketone, pregol, isopulegol, menthol, Menthol acetate, isomenthol, neomenthol, menthanol, menthanetriol, menthanetetraol, carbomenthol, menthoxy Acid, perillyl alcohol, perilaldehyde, carbeol, piperitol, terpene-4-ol, terpineol, terpineol, dihydroterpineol, sobreol, thymol, borneol, bornyl acetate, isoborneol, isobornyl acetate, cineol, pinol, pinocarbeveol, mill Tenor, myrtenal, berbenol, pinocampheol, camphorsulfonic acid, nerolidol, terpinene, ionone, pinene, camphene, camphorene aldehyde, camphoronic acid, isocamphoronic acid, camphoric acid, abitienic acid, glycyrrhetinic acid, and the like. These terpene compounds may be used alone or in combination of two or more.
0-70 mass parts is preferable with respect to 100 mass parts of this alkaline aqueous solution soluble polymer, and, as for the compounding quantity with respect to the alkaline aqueous solution soluble polymer of a fragrance | flavor, 1-50 mass parts is more preferable. If the addition amount is 70 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 made 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 alkaline aqueous solution soluble polymer, and, as for the compounding quantity with respect to the alkaline aqueous solution soluble polymer of surfactant, 0.01-1 mass part is more preferable. When the addition amount is 10 parts by mass or less, 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: Silaace S810), 3-mercaptopropyltritri Ethoxysilane (manufactured by Azmax Co., Ltd., trade name: SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: LS1375, manufactured by Azmax Co., Ltd., trade name: SIM6474.0), mercapto Methyltrimethoxysilane (Azmax Co., Ltd., trade name: SIM6473.5C), mercaptomethylmethyldimethoxysilane (Azmax Co., Ltd., trade name: SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3 -Mercaptopropylethoxydimethoxysilane, 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-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: LS3) 10, manufactured by Azmax 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, N- (3-methoxydipropoxysilylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N -(3-tripropoxysilylethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N -(3-trimethoxysilylbutyl) urea, N- (3-trie Silyl butyl) urea, N-(3- tripropoxysilyl butyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (AZmax Co., Ltd., trade name: SLA0598.0),

m-aminophenyltrimethoxysilane (manufactured by AZMAX Co., Ltd., trade name: SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by AZMAX Co., Ltd., trade name: SLA0599.1) aminophenyltrimethoxysilane (AZMAX Co., Ltd.) Product name: SLA0599.2), 2- (trimethoxysilylethyl) pyridine (manufactured by Azmax Co., Ltd., product name: SIT8396.0), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) ) Pyridine, 2- (diethoxysilylmethylethyl) pyridine and the like.

Particularly preferred compounds include, but are not limited to, compounds represented by the following structural formula.
0.01-30 mass parts is preferable with respect to 100 mass parts of this alkaline aqueous solution soluble polymer, and, as for the compounding quantity with respect to the alkaline aqueous solution soluble polymer of the said adhesion assistant, 0.1-10 mass parts is more preferable. If the addition amount is 30 parts by mass or less, the heat resistance of the film after thermosetting is good.

As allyl compounds, allyl alcohol, allyl anisole, benzoic acid allyl ester, cinnamic acid allyl ester, N-allyloxyphthalimide, allylphenol, allyl phenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, maleic acid Diallyl, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimesate, triallyl trimellitic acid, tetraallyl trimellitic acid, triallyl phosphate, triallyl Examples include allyl phosphite and triallyl citrate.
As for the compounding quantity with respect to this alkaline aqueous solution soluble polymer of said allyl compound, 0.1-70 mass parts is preferable with respect to 100 mass parts of this alkaline aqueous solution soluble polymer. When the compounding amount of the allyl compound is 0.1 parts by mass or more, the heat resistance of the film after thermosetting is good, and when it is 70 parts by mass or less, the tensile elongation of the film after curing is good.

(H) Solvent 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 preferred examples include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate and the like.
As for the compounding quantity with respect to the alkaline aqueous solution soluble polymer of a solvent, 50-1000 mass parts is preferable with respect to 100 mass parts of this alkaline aqueous solution soluble polymer. 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, mirror projection, or stepper, or light, electron beam, or ion beam is directly irradiated. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable. From the viewpoint of pattern resolution and handleability, the light source wavelength is preferably g-line, h-line or i-line of a mercury lamp, which may be used alone or in combination.
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 polycondensate dissolution inhibitor is added to the alkaline aqueous solution. Can do.

Finally, a heating step for heating the relief pattern of the positive photosensitive resin composition thus obtained is performed. The heating temperature is preferably 150 ° C. or higher, and a cured relief pattern can be obtained by volatilizing the photosensitive diazonaphthoquinone compound and the diluting solvent. In the method of forming a cured relief pattern using a polyimide or polybenzoxazole precursor composition, it is necessary to convert it to polyimide or polybenzoxazole by heating to 250 ° C. or more to advance a dehydration cyclization reaction. . Such a heat treatment apparatus can be performed by using a hot plate, an oven, or a temperature rising oven capable of setting a temperature program. Air may be used as the atmospheric gas when performing the heat treatment, and an inert gas such as nitrogen or argon may be used. Further, when it is necessary to perform heat treatment at a lower temperature, heating may be performed under reduced pressure using a vacuum pump or the like.
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 more specifically based on reference examples, examples, and comparative examples, but the present invention is not limited to these examples.
<Synthesis of aqueous alkali-soluble polymer>
[Reference Example 1]
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 dropwise addition, the reaction solution was dropped into 12 liters of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, appropriately washed with water, dehydrated and then vacuum-dried. P-1) was obtained. The weight average molecular weight of the thus synthesized aqueous alkaline solution-soluble polymer by gel permeation chromatography (hereinafter also referred to as “GPC”) was 14,000 in terms of polystyrene.
The analysis conditions for GPC are described below.
Column: manufactured by Showa Denko KK, trade name: Shodex: 805/804/803 in series Separation: Tetrahydrofuran; 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko, trade name: Shodex: RI · SE-61

[Reference Example 2]
In a separable flask having a volume of 2 l, 183.1 g (0.50 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 71.2 g (0.90 mol) of pyridine, and 730 g of DMAc were added at room temperature. (25 ° C.) The mixture was stirred and dissolved. A solution obtained by dissolving 15.4 g (0.10 mol) of cyclohexanedicarboxylic anhydride in 45.0 g of DMDG was added dropwise thereto from a dropping funnel. The time required for the dropwise addition was 20 minutes, and the maximum reaction solution temperature was 28 ° C.
After completion of the dropwise addition, the mixture was stirred at room temperature for 8 hours, then cooled to 8 ° C. with a water bath, and separately, 121.0 g (0.41 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride and isophthaloyl chloride in 520 g of DMDG. A solution in which 1 g (0.04 mol) was dissolved was dropped from a dropping funnel. The time required for the dropping was 70 minutes, and the maximum reaction solution temperature was 14 ° C. Three hours after the completion of the dropwise addition, the reaction solution was dropped into 12 liters of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, appropriately washed with water, dehydrated and then vacuum-dried. P-2) was obtained. The weight average molecular weight by GPC of the aqueous alkali-soluble polymer synthesized in this manner was 19000 in terms of polystyrene.
The analysis conditions for GPC were the same as in Reference Example 1.

[Reference Example 3]
Bicyclo (2,2,2) -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (Aldrich) was added to a four-necked flask equipped with a stir bar, Dean-Stark trap and nitrogen inlet tube. 14.89 g (60 mmol), molecular weight: 248.19) manufactured by the company, and 6.01 g (30 mmol) of 4,4′-diaminodiphenyl ether (manufactured by Wakayama Seika Co., Ltd., molecular weight: 200.00) were charged. Furthermore, 93.5 g of GBL and 30 g of toluene were added to the system as a solvent. After stirring at 100 rpm for 20 minutes at room temperature in a nitrogen atmosphere, heating was started in an oil bath at 180 ° C., and the whole liquid was stirred at 180 rpm. During the reaction, water as a by-product was distilled azeotropically with toluene, and water accumulated at the bottom of the reflux tube was removed every 30 minutes. Two hours after heating, the second stage charge was started, and 16.82 g (60 mmol) of bis (3-amino-4-hydroxyphenyl) sulfone (manufactured by Konishi Chemical Industry Co., Ltd., molecular weight: 280.3) was added. The mixture was further stirred for 1 hour. Subsequently, 3.96 g (45 mmol) of bis (3,4-dicarboxyphenyl) ether dianhydride 1 was added to the system. After heating and stirring at 180 ° C. and 180 rpm for 3 hours, the oil bath was lowered and heating was stopped. During the reaction, distillates of water and toluene, which are by-products of the reaction, were removed. The weight average molecular weight in terms of polystyrene of the polymer thus produced was 12,000. Thus, a polymer solution (P-3) having a resin concentration of 35% by weight was obtained.

<Synthesis of diazonaphthoquinone compound>
[Reference Example 4]
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%. The reaction solution was added dropwise to 1 liter of ion-exchanged water with stirring, and the precipitate was separated by filtration. To this, 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, appear characteristic absorption of an imide group 1394Cm ^-1 and 1774 cm ^-1 in the IR spectrum, the absence of a characteristic absorption of amide groups in the vicinity of 1540 cm ^-1 and 1650 cm ^-1, and NMR The spectrum 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 5]
In a separable flask having a volume of 1 l, 4,4 ′-(1- (2- (4-hydroxyphenyl) -2-propyl) phenyl) ethylidene) bisphenol (manufactured by Honshu Chemical Industry Co., Ltd., trade name: Tris-) as a polyhydroxy compound PA) 30 g (0.0707 mol) of the compound was used, and 47.49 g (0.177 mol) of 1,2-naphthoquinonediazide-4-sulfonic acid chloride in an amount corresponding to 83.3 mol% of the OH group was added to acetone. After stirring and dissolving in 300 g, the flask was adjusted to 30 ° C. in a thermostatic bath. Next, 17.9 g of triethylamine was dissolved in 18 g of acetone, charged in a dropping funnel, and then dropped into the flask over 30 minutes. Stirring was continued for another 30 minutes after completion of dropping, and hydrochloric acid was then added dropwise, and stirring was further performed for 30 minutes to complete the reaction. Thereafter, filtration was performed to remove triethylamine hydrochloride. The filtrate obtained here was added dropwise with stirring to a 3 l beaker in which 1640 g of pure water and 30 g of hydrochloric acid were mixed and stirred to obtain a precipitate. The precipitate was washed with water and filtered, and then dried under reduced pressure at 40 ° C. for 48 hours to obtain a photosensitive diazoquinone compound (Q-2).

Next, examples in the present invention will be described.
<Preparation of positive photosensitive resin composition>
[Examples 1 to 24, Comparative Examples 1 to 11]
The aqueous alkali-soluble polymers (P-1 to P-2) obtained in Reference Examples 1 and 2 above were dissolved in a GBL solvent to give a polymer solution having a 35 wt% resin concentration, and the above Reference Example 3 Each polymer solution (P-3) having a resin concentration of 35% by weight obtained by the synthesis method was prepared. The photosensitive diazoquinone compound (Q-1, Q-) obtained in Reference Example 4 or Reference Example 5 above with respect to a polymer solution (P-1 to P-3) containing 100 parts by mass of an aqueous alkali-soluble polymer. 2), a sulfonic acid anhydride of any one of the following C-1 to C-3, a crosslinking agent of the following D-1 or D-2, an alkoxybenzene of the following E-1 or E-2, and the following F-1 to F −3 carboxylic acid compound was dissolved in a predetermined mass part, and then filtered through a 0.2 μm filter, and the positive photosensitive resin compositions of Examples 1 to 24 and Comparative Examples 1 to 11 described in Table 1 were used. Was prepared.
(C-1) p-toluenesulfonic anhydride (C-2) benzenesulfonic anhydride (C-3) methanesulfonic anhydride (D-1) Nicalak MX-270 (manufactured by Sanwa Chemical Co., Ltd.)
(D-2) Nikarac MX-280 (manufactured by Sanwa Chemical Co., Ltd.)
(E-1) 2,4-Dimethoxyacetoacetanilide (E-2) Trimethoxybenzene (F-1) Lauric acid (F-2) Isononanoic acid (F-3) 10-Undecenoic 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 (manufactured by Tokyo Electron Co., Ltd., Clean Track Mark 8), and then on a hot plate. Pre-baking was performed at 130 ° 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 by using a stepper (NSR2005i8A, manufactured by Nikon Corporation) having an exposure wavelength of i-line (365 nm) while changing the exposure stepwise. Using an alkaline developer (manufactured by AZ Electronic Materials, AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide aqueous solution) and using P-1 and P-2 under conditions of 23 ° C. In the comparative example, the film thickness after development was 9.8 μm, and in the example using P-3 and the comparative example, the development time was adjusted so that the film thickness after development was 9.0 μm, and developed, and rinsed with pure water And a positive relief pattern was formed. Table 2 shows the sensitivity, resolution, and adhesive state of the positive photosensitive resin composition.
The sensitivity and resolution 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.

  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) A polycondensate containing a hydroxypolyamide structure having a repeating unit represented by the following general formula (2) in the molecule, and one or more tetracarboxylic dianhydrides, and an amino group in an ortho position relative to each other And 100 parts by mass of at least one alkaline aqueous solution-soluble polymer selected from the group consisting of polycondensates having a structure in which one or two or more aromatic diamines having a phenolic hydroxyl group are dehydrated and condensed (B) It contains 1 to 50 parts by mass of a photoacid generator having a naphthoquinonediazide structure , (C) 0.01 to 30 parts by mass of a sulfonic anhydride, and (D) 0.1 to 70 parts by mass of a crosslinking agent. Positive photosensitive resin composition.
(Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, X ₂ is a divalent organic group having at least 2 carbon atoms, and Y ₁ and Y ₂ are Each independently represents a divalent to tetravalent organic group having at least 2 carbon atoms, t and u are each independently an integer of 0 to 2, r is an integer of 2 to 1000, and s Is an integer from 0 to 500, where 0.5 <r / (r + s) ≦ 1.0, including r dihydroxydiamide units including X ₁ and Y ₁ , and X ₂ and Y ₂ . (The order of arrangement of s diamide units is not limited.) 2. The positive photosensitive resin composition according to claim 1, wherein the positive photosensitive resin composition further comprises 0.01 to 50 parts by mass of (E) alkoxybenzene represented by the following general formula (1). Composition.
(In the formula, Q is a group having at least one carbon atom. Q is an integer of 1 to 3. Z is a hydrogen atom or a monovalent organic group.)   The positive photosensitive resin composition according to claim 1 or 2, wherein the positive photosensitive resin composition further comprises 0.01 to 50 parts by mass of (F) a carboxylic acid compound. (A) From a polycondensate having a structure in which one or two or more tetracarboxylic dianhydrides and one or two or more aromatic diamines having an amino group and a phenolic hydroxyl group that are ortho to each other are dehydrated and condensed. An aqueous alkali-soluble polymer comprising bicyclo (2,2,2) -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and bis (3-amino-4-hydroxyphenyl) sulfone There positive photosensitive resin composition according to claim 1, characterized in that the polycondensate having a structure in which dehydration condensation. (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, Directly irradiating with a light beam, an electron beam or an ion beam, (3) Elution and removal of the exposed portion or irradiated portion with a developer, and (4) Heat-treating the obtained relief pattern, thereby producing a cured relief pattern Method. A semiconductor device comprising a cured relief pattern layer obtained by the manufacturing method according to claim 5 .