JP4726730B2 - Positive photosensitive resin composition - Google Patents

Description

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

Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor device. This polyimide resin is generally provided in the form of a photosensitive polyimide precursor composition. By applying, patterning with actinic rays, development, thermal imidization treatment, etc., a surface protective film and interlayer insulation are formed on a semiconductor device. A film or the like can be easily formed, and the process can be significantly shortened as compared with the conventional non-photosensitive polyimide precursor composition.
However, the photosensitive polyimide precursor composition needs to use a large amount of an organic solvent such as N-methyl-2-pyrrolidone as a developing solution in the development process. Solvent measures have been demanded. 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.

In particular, a PBO precursor composition obtained by mixing an alkaline aqueous solution-soluble hydroxypolyamide, such as polybenzoxazole (hereinafter also referred to as “PBO”) precursor, with a photoactive component such as a photosensitive diazoquinone compound is used as a positive photosensitive resin composition. A method used as a product is disclosed, for example, in Patent Document 1 and has attracted attention in recent years.
The development mechanism of this positive photosensitive resin is that the photosensitive diazoquinone compound in the unexposed area is insoluble in the alkaline aqueous solution, but the photosensitive diazoquinone compound undergoes a chemical change upon exposure to become an indenecarboxylic acid compound. It makes use of being soluble in an alkaline aqueous solution. By using the difference in dissolution rate with respect to the developer between the exposed portion and the unexposed portion, a relief pattern of only 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 thermosetting film characteristics equivalent to those of a polyimide film, and thus has attracted attention as a promising alternative material for an organic solvent development type polyimide precursor.

In recent years, the transition of packaging methods for semiconductor devices using the above-mentioned materials has been remarkable, and the conventional lead frame has been changed to a LOC package in which a gold wire is connected to the semiconductor device. From the viewpoint of improving the degree of integration and reducing the chip size, Tends to be multilayered. As a result, the conditions under which the polyimide coating and the PBO coating are exposed in the process of forming the structure are also complicated. For example, a higher chemical resistance against a photoresist stripping solution containing a strong acid or a strong base (such as ethanolamine or tetramethylammonium hydride) has been required.
The mounting method of semiconductor devices on printed wiring boards is not limited to the conventional mounting method using metal pins and lead-tin eutectic solder, but also high-density BGA (ball grid array) aiming at chip size package, polyimide coating and PBO coating Has changed to a structure that directly contacts solder bumps. Also, the solder used is being replaced by lead-free high melting point solder for the purpose of reducing environmental impact. As described above, the polyimide coating and PBO coating used in the reflow process have a technical background that requires more excellent heat resistance, chemical resistance, and reflow resistance.

When the PBO precursor composition is actually used in the above-described process, relatively high chemical resistance and reflow resistance are exhibited when a high molecular weight polymer of a certain degree or more is used as the base PBO precursor resin. Since the solubility of the resin in an alkaline aqueous solution is lowered, there is a problem that the development time becomes long. For example, Patent Document 2 proposes a technique for adding a low-molecular compound having a heat-reactive functional group typified by an epoxy group and crosslinking the polymer by heat treatment to increase physical properties. This can be expected to improve reflow resistance, but due to its reactivity, there are problems in the stability of the composition such as changes in viscosity and development time over time (see Comparative Example 3 described later).
Further, for example, Patent Document 3 proposes a technique for increasing a physical property by adding a compound having an organic group containing an amide bond as a compound having a substituent derived from an amine functional group. Thereby, although improvement of mechanical properties such as elongation can be expected, the obtained reflow resistance is not sufficient, and it is difficult to say that the material is practical for the above-described process (see Comparative Example 2 described later). . As described above, a positive photosensitive resin that has both excellent lithography characteristics necessary for use in the above-described processes, heat resistance, and reflow resistance and has no practical problems has not yet been obtained. It was.

JP 63-096162 A JP 2000-039714 A WO05 / 101125 pamphlet

  The present invention relates to a novel positive photosensitive resin composition capable of obtaining a cured film having excellent storage stability and reflow resistance without impairing positive lithography performance, and a cured relief using the composition. It is an object of the present invention to provide a pattern manufacturing method and a semiconductor device having the cured relief pattern.

  As a result of intensive studies to solve the above problems, the present inventor combines a polybenzoxazole resin precursor with a thermally crosslinkable low molecular weight compound having a specific structure, without impairing lithography performance, The inventors have found that a positive photosensitive resin composition exhibiting excellent reflow resistance even under low heat treatment temperature conditions and having good storage stability can be obtained, and the present invention has been made.

（式中、Ｘ₁は少なくとも２個以上の炭素原子を有する４価の有機基、Ｘ₂、Ｙ₁およびＹ₂はそれぞれ独立に少なくとも２個以上の炭素原子を有する２価の有機基、ｍは２〜１０００の整数、ｎは０〜５００の整数であって、ｍ／（ｍ＋ｎ）＞０．５である。なお、Ｘ₁およびＹ₁を含むｍ個のジヒドロキシジアミド単位、並びにＸ₂およびＹ₂を含むｎ個のジアミド単位の配列順序は問わない。）

（式中、Ｒ₁、Ｒ₂は、１〜２０個の炭素原子を有する１価の有機基を表す。） That is, the first of the present invention is (A) 100 parts by mass of a hydroxypolyamide having a repeating unit represented by the following general formula (1), (B) a urethane group containing the following general formula (2) A positive photosensitive resin composition comprising 0.01 to 30 parts by mass of a compound and 1 to 100 parts by mass of (C) a photosensitive diazoquinone compound.

Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, X ₂ , Y ₁ and Y ₂ are each independently a divalent organic group having at least 2 carbon atoms, m Is an integer from 2 to 1000, n is an integer from 0 to 500, and m / (m + n)> 0.5, where m dihydroxydiamide units including X ₁ and Y ₁ , and X ₂ and (The order of arrangement of n diamide units including Y ₂ is not limited.)

(In the formula, R ₁ and R ₂ represent a monovalent organic group having 1 to 20 carbon atoms.)

In the second aspect of the present invention, (1) the positive photosensitive resin composition of the present invention is formed on a substrate in the form of a layer or a film, and (2) exposure with actinic radiation through a mask or light rays. , Directly irradiating with 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, It is.
Furthermore, a third aspect of the present invention is a semiconductor device having a cured relief pattern layer obtained by the production method of the present invention.

  According to the present invention, a positive photosensitive resin composition having excellent reflow resistance and good storage stability without impairing positive lithography performance, and production of a cured relief pattern using the positive photosensitive resin composition A method and a semiconductor device having the cured relief pattern are provided.

（式中、Ｘ₁は少なくとも２個以上の炭素原子を有する４価の有機基、Ｘ₂，Ｙ₁およびＹ₂はそれぞれ独立に少なくとも２個以上の炭素原子を有する２価の有機基、ｍは２〜１０００の整数、ｎは０〜５００の整数であって、ｍ／（ｍ＋ｎ）＞０．５である。なお、Ｘ₁およびＹ₁を含むｍ個のジヒドロキシジアミド単位、並びにＸ₂およびＹ₂を含むｎ個のジアミド単位の配列順序は問わない。） <Positive photosensitive resin composition>
Each component which comprises the positive photosensitive resin composition of this invention is demonstrated concretely below.
(A) Hydroxypolyamide Hydroxypolyamide, which is the base polymer of the positive photosensitive resin composition of the present invention, has a repeating unit represented by the following general formula (1).

Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, X ₂ , Y ₁ and Y ₂ are each independently a divalent organic group having at least 2 carbon atoms, m Is an integer from 2 to 1000, n is an integer from 0 to 500, and m / (m + n)> 0.5, where m dihydroxydiamide units including X ₁ and Y ₁ , and X ₂ and (The order of arrangement of n diamide units including Y ₂ is not limited.)

The dihydroxydiamide unit of the hydroxypolyamide has a structure in which a dicarboxylic acid having a Y ₁ (COOH) ₂ structure and a bisaminophenol having a X ₁ (NH ₂ ) ₂ (OH) ₂ structure are polycondensed. Here, the two amino groups and the hydroxy group of the bisaminophenol are each in the ortho position, and heating the hydroxypolyamide at about 280 to 400 ° C. closes the dihydroxydiamide unit, It changes to the benzoxazole unit which is a heat resistant resin. 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 20.
If necessary, the hydroxypolyamide may be condensed with n diamide units of the general formula (1). The diamide unit has a structure in which a diamine having a structure of X ₂ (NH ₂ ) ₂ and a dicarboxylic having a structure of Y ₂ (COOH) ₂ are polycondensed. n is preferably in the range of 0 to 500, and more preferably in the range of 0 to 10. The higher the ratio of hydroxypolyamide units in the hydroxypolyamide, the higher the solubility in an alkaline aqueous solution used as a developer, and the shorter the time required for development, so the value of m / (m + n) is 0.5 or more. It is preferable that it is 0.7, more preferably 0.7 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, 1,3- And diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.

Particularly preferred among these bisaminophenols is when X ₁ is an aromatic group selected from the following.

Preferred examples of the diamine having the X ₂ (NH ₂ ) ₂ structure include aromatic diamines and silicon diamines.
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′-diaminodiphenyl Urea, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-a Minophenoxy) 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-amino Phenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-amino) Phenyl) fluorene, 4,4′-di- (3-aminophenoxy) diphenylsulfone, and 4, 4′-diaminobenzanilide, and at least one selected from the group consisting of a hydrogen atom of an aromatic nucleus of these aromatic diamines consisting of a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, and a phenyl group And a compound substituted by a group or an atom.

  Further, silicon diamine can be selected in order to enhance the adhesion to the substrate. Examples of this include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, and bis (4 -Aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis ( γ-aminopropyl) tetraphenyldisiloxane and the like.

（式中、Ａは、−ＣＨ₂−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ₃）₂−、及び単結合からなる群から選択される２価の基を示し、Ｒは、それぞれ独立に、水素原子、アルキル基、アルケニル基、及びハロゲン原子からなる群から選択される基を示し、ｋは０〜４の整数を示す。） Preferred examples of the dicarboxylic acid having a Y ₁ (COOH) ₂ or Y ₂ (COOH) ₂ structure include those in which Y ₁ and Y ₂ are aromatic groups 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 alkenyl group, and a halogen atom, and k represents an integer of 0 to 4.)

It is also preferable to use a derivative of 5-aminoisophthalic acid for a part or all of the dicarboxylic acid having the Y ₁ (COOH) ₂ or Y ₂ (COOH) ₂ structure.
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 Chloroformic acid methyl ester, chloroformic acid ethyl ester, chloroformic acid n-propyl ester, chloroformic acid isopropyl ester, chloroformic acid isobutyl ester, chloroformic acid 2-ethoxy ester, chloroformic acid-sec-butyl ester, Benzyl chloroformate, 2-ethylhexyl chloroformate, allyl ester chloroformate, phenyl ester chloroformate, 2,2,2-trichloroethyl ester chloroformate, chloroformate 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. .

（式中、Ｂは−ＣＨ₂−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＮＨＣＯ−、及び−Ｃ（ＣＦ₃）₂−からなる群から選択される２価の基を意味する。） Furthermore, as a dicarboxylic acid having a Y ₁ (COOH) ₂ or Y ₂ (COOH) ₂ structure, a compound obtained by ring-opening a tetracarboxylic dianhydride with a monoalcohol or a monoamine can also be used. Examples of the monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, and benzyl alcohol. Examples of the monoamine include butylamine and aniline. Examples of the tetracarboxylic dianhydride include the following.

Wherein B is a divalent group selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ —. Means a group of

（式中、Ｘ₃はＸ₁（ＯＨ）₂（ＮＨ−）₂を表す。） Further, trimellitic acid chloride is reacted with the above-mentioned bisaminophenol to produce tetracarboxylic dianhydride, and ring opening is performed in the same manner to produce Y ₁ (COOH) ₂ or Y ₂ (COOH) _2. It can also be used as a dicarboxylic acid having a structure. Examples of the tetracarboxylic dianhydride obtained here include the following.

(In the formula, X ₃ represents X ₁ (OH) ₂ (NH—) _2. )

Alternatively, the tetracarboxylic dianhydride can be reacted with the bisaminophenol, and the resulting carboxylic acid residue can be esterified or amidated with a monoalcohol or monoamine.
As a method for producing a dihydroxydiamide unit 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, a dicarboxylic acid may be used. And thionyl chloride to form diacid chloride and then react with bisaminophenol, and dicarboxylic acid and bisaminophenol are polycondensed with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be allowed to act simultaneously.

In the hydroxypolyamide 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 “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.

（式中、Ｒ₁、Ｒ₂は、１〜２０個の炭素原子を有する１価の有機基を表す。）
本発明者は、該ウレタン基含有化合物をヒドロキシポリアミドを含むポジ型感光性樹脂組成物に添加することにより、保存時の粘度上昇を防ぎ、リソグラフィー性能を損なうことがなく、硬化膜の耐リフロー性を高める効果を奏することを見出した。この理由は、ウレタン結合自体は常温では反応性が低く構造的に安定である一方、熱処理を行うことにより効率的に分解しイソシアネート基やアミノ基といった反応性の高い基を生成しヒドロキシポリアミドの分子鎖間架橋を起こすことが可能となるためと考えられる。 (B) Urethane group containing compound The positive photosensitive resin composition of this invention contains a urethane group containing compound, More preferably, the urethane group containing compound represented by following General formula (2) is included.

(In the formula, R ₁ and R ₂ represent a monovalent organic group having 1 to 20 carbon atoms.)
By adding the urethane group-containing compound to a positive photosensitive resin composition containing hydroxypolyamide, the present inventor prevents an increase in viscosity during storage, does not impair lithography performance, and reflow resistance of the cured film. It has been found that there is an effect of enhancing the effect. The reason for this is that the urethane bond itself has low reactivity and is structurally stable at room temperature, but it is efficiently decomposed by heat treatment to generate highly reactive groups such as isocyanate groups and amino groups, thereby producing hydroxypolyamide molecules. This is thought to be because interchain crosslinking can occur.

The isocyanate compound or amine compound used for the production of the urethane group-containing compound preferably does not contain an acidic organic group such as a hydroxyl group or a carboxyl group. It is considered that by using the organic group, an isocyanate group or an amino group generated from the urethane compound by heat treatment is not deactivated in the molecule and is used for crosslinking between the molecular chains of the hydroxy polyamide with high efficiency. The urethane group-containing compound is easily produced by, for example, a method of reacting a monohydric alcohol with the isocyanate compound listed below, or a method of reacting a chloroformate ester or dicarbonate ester with the amine compound listed below. be able to.

The monohydric alcohol to be reacted with the isocyanate compound is preferably an aliphatic or aromatic monoalcohol having 1 to 20 carbon atoms. For example, methanol, ethanol, isopropanol, n-butanol, t-butanol, phenol and the like can be mentioned. In consideration of decomposability during heat treatment, methanol, ethanol, and t-butanol are more preferable. These monohydric alcohols may be used alone or in combination.
Examples of the chloroformate to be reacted with the amine compound include chloroformate methyl ester, chloroformate ethyl ester, chloroformate n-propyl ester, chloroformate isopropyl ester, chloroformate isobutyl ester, chloroformate 2 -Ethoxy ester, chloroformate-sec-butyl ester, chloroformate benzyl ester, chloroformate 2-ethylhexyl ester, chloroformate allyl ester, chloroformate phenyl ester, chloroformate 2,2,2-trichloroethyl Ester, chloroformate-2-butoxyethyl ester, chloroformate-p-nitrobenzyl ester, chloroformate-p-methoxybenzyl ester, chloroformate isobornylbenzyl ester, chloroformate-p-biphenylisopropylbenzyl Esters, The carbonate esters, di -t- butyl - dicarbonate and the like. Among these, chloroformate methyl ester, chloroformate ethyl ester, chloroformate n-propyl ester, chloroformate isopropyl ester, chloroformate isobutyl ester, chloroformate 2-ethoxy ester, chloroformate allyl ester, Preferred are chloroformic acid phenyl ester and di-t-butyl-dicarbonate. These chloroformate esters and dicarbonate esters may be used alone or in combination. These urethane group-containing compounds may be used alone or in combination of two or more.
0.01-30 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 urethane group containing compound, 0.1-15 mass parts is more preferable. When the compounding amount of the urethane group-containing compound is 0.1 parts by mass or more, chemical resistance and reflow resistance are good, and when it is 15 parts by mass or less, the tensile elongation rate of the cured film is good.

（式中、Ｑは水素原子または以下に示すナフトキノンジアジドスルホン酸エステル基であり、すべてのＱが同時に水素原子であることはない。） (C) Photosensitive diazoquinone compound The photosensitive diazoquinone compound used in the positive photosensitive resin composition of the present invention is a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure. No. 2,772,972, No. 2,797,213, No. 3,669,658 and the like. As an example of a preferable thing, the following are mentioned, for example.

(In the formula, Q is a hydrogen atom or a naphthoquinone diazide sulfonate group shown below, and all Qs are not hydrogen atoms at the same time.)

感光性ジアゾキノン化合物のヒドロキシポリアミドに対する配合量は、該ヒドロキシポリアミド１００質量部に対し、１〜１００質量部が好ましく、１０〜３０質量部がより好ましい。感光性ジアゾキノン化合物の配合量が１質量部以上で樹脂のパターニング性が良好であり、１００質量部以下では硬化後の膜の引張り伸び率が良好かつ、露光部の現像残さ（スカム）が少ない。 Among these, the following are particularly preferable.

1-100 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 the photosensitive diazoquinone compound, 10-30 mass parts is more preferable. 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 100 parts by mass or less, the tensile elongation of the cured film is good and the development residue (scum) in the exposed part is small.

(D) Other additives A thermal radical generator may be added to the positive photosensitive resin composition of the present invention. The radical generator used here is preferably one that generates radicals under heat treatment conditions, and examples of preferable ones include organic peroxides such as dicumyl peroxide and organic non-peroxides such as dimethyldiphenylbutane.
When the thermal radical generator is added, the addition amount is preferably 0 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the hydroxy polyamide. If the addition amount is within 20 parts by mass, the storage stability is good.
In the positive photosensitive resin composition of the present invention, the phenol compound, the dye, the surfactant, and the substrate, which are conventionally used as additives for the photosensitive resin composition, if necessary, for enhancing the adhesion to the substrate. It is also possible to add adhesion aids, stabilizers and the like.

More specifically, the above additives include ballast agents, paracumylphenol, bisaminophenol, resorcinol and the like. 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. Examples of the dye include methyl violet, crystal violet, and malachite green.
When adding a phenol compound, 0-50 mass parts is preferable with respect to 100 mass parts of hydroxy polyamide, and 1-30 mass parts is preferable. If the addition amount is within 50 parts by mass, the tensile elongation of the film after thermosetting is good.

Examples of the surfactant include non-ionic surfactants made of polyglycols such as polypropylene glycol or polyoxyethylene lauryl ether, or derivatives thereof, such as Fluorard (trade name, manufactured by Sumitomo 3M), Megafuck ( Fluorosurfactants such as trade name, Dainippon Ink & Chemicals, Inc. or Sulflon (trade name, manufactured by Asahi Glass), such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corporation ) And granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
When the surfactant is added, the addition amount is preferably 0 to 10 parts by mass and more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the hydroxy polyamide. If the addition amount is within 10 parts by mass, the tensile elongation of the film after thermosetting is good. 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.
Examples of the adhesion assistant include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, epoxy polymer, and various silane coupling agents.

Specific preferred examples of the silane coupling agent include, for example, N-phenyl-3-aminopropyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 2- (trialkoxysilylethyl) pyridine, and 3-methacryloxypropyl. Trialkoxysilane, 3-methacryloxypropyl dialkoxyalkylsilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkyl Silane and acid anhydride or acid dianhydride reactant, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane amino group converted to urethane group or urea group And the like of. In this case, methyl group, ethyl group, butyl group, etc. as the alkyl group, maleic anhydride, phthalic anhydride, etc. as the acid anhydride, pyromellitic dianhydride as the acid dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, etc., t-butoxycarbonylamino group as a urethane group, phenylamino as a urea group Examples thereof include a carbonylamino group.
The addition amount in the case of adding an adhesion assistant is preferably 0 to 30 parts by mass and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the hydroxy polyamide. If the addition amount is within 30 parts by mass, the tensile elongation of the film after thermosetting 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 a solvent include N-methyl-2-pyrrolidone, γ-butyrolactone (hereinafter also referred to as “GBL”), isophorone, N, N-dimethylacetamide (hereinafter also referred to as “DMAc”), dimethylimidazo. Linone, 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 acetate, 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. Among these solvents, non-amide solvents are preferable because they have little influence on photoresists, and specifically, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate. And so on.
The addition amount of the solvent is preferably 50 to 1000 parts by mass with respect to 100 parts by mass of the hydroxy polyamide. 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, a method for producing a cured relief pattern by applying the positive photosensitive resin composition of the present invention to a substrate 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 roll coater. 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 irradiated portion is dissolved and removed with a developer, and then rinsed with a rinse solution to obtain a desired relief pattern. As a developing method, methods such as spray, paddle, dip, and ultrasonic can be used. Distilled water, deionized water, etc. can be used for the rinse liquid.

The developer used for developing the photosensitive resin film formed with the positive photosensitive resin composition of the present invention is an alkaline aqueous solution in which an alkali-soluble polymer is dissolved and removed, and an alkali compound is dissolved. is required. 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, ammonia and the like.

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 and the like.
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, a resin dissolution inhibitor, or the like can be added to the alkaline aqueous solution.
Finally, the obtained relief pattern can be heat-treated to form a heat-resistant cured relief pattern having a polybenzoxazole structure.
The cured relief pattern created by the above-described manufacturing method is used to manufacture a known semiconductor device as a surface protective film, an interlayer insulating film, a rewiring insulating film, a flip chip device protective film, or a protective film for a device having a bump structure. A semiconductor device can be manufactured by combining with the method. It is also useful as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films, and the like.

The present invention will be described more specifically based on reference examples and examples, but the present invention is not limited to these examples.
<Synthesis of hydroxy polyamide>
[Reference Example 1]
In a 1-liter three-necked flask, 18.12 g (0.1 mol) of 5-aminoisophthalic acid was dissolved in 200 g of N-methyl-2-pyrrolidone and 15.8 g (0.2 mol) of pyridine, and dissolved in 36 g of γ-butyrolactone. 11.94 g (0.105 mol) of ethyl chloroformate was added dropwise. This was ice-cooled to 0 ° C., and 35.69 g of thionyl chloride (0.3 mol) dissolved in 105 g of γ-butyrolactone was added dropwise so as not to exceed 10 ° C. over 30 minutes. After stirring for 1 hour while cooling with ice so as not to exceed 10 ° C., the temperature was returned to room temperature, and unreacted thionyl chloride and by-product sulfurous acid gas were distilled off using a vacuum pump. This solution is designated as reaction solution 1.
Next, 90 g of γ-butyrolactone was dissolved in 29.512 g (0.1 mol) of 4,4′-oxybisbenzoic acid dichloride in a 0.5 liter Erlenmeyer flask. This solution is designated as reaction solution 2.

In a 2-liter separable flask, 283 g of N-methyl-2-pyrrolidone obtained by drying 80.58 g (0.22 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 31.6 g of pyridine ( 0.4 mol), and then cooled to 0 ° C., the reaction solution 1 and the reaction solution 2 were mixed, and added dropwise using a dropping funnel. The time required for the dropping was 40 minutes, and the maximum reaction temperature was 10 ° C. It stirred for 2 hours after completion | finish of dripping. Thereafter, the reaction solution was transferred to a 10 liter beaker, and 5 liters of distilled water was added to the reaction solution to precipitate the produced polymer. The supernatant solution was removed, and 1.5 liters of tetrahydrofuran was added to redissolve. Further, 5 liters of distilled water was added to precipitate the produced polymer. The supernatant solution was removed, and 1.5 liters of tetrahydrofuran added and re-dissolved were passed through a column filled with anion exchange resin and cation exchange resin substituted with tetrahydrofuran, and the reaction solution was further added to 12 liters of water. The polymer was dispersed and precipitated by dropwise addition under high-speed stirring. This was recovered, washed appropriately with water and dehydrated, and then vacuum dried to obtain hydroxypolyamide (P-1). The weight average molecular weight of the thus synthesized hydroxypolyamide by GPC was 22000 (Mw) in terms of polystyrene. The analysis conditions for GPC are described below.
Column: Showa Denko Co., Ltd. Trade name: Shodex 805/804/803 in series Separation: Tetrahydrofuran 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko brand name Shodex RI SE-61

[Reference Example 2]
Reference Example 1 is the same as Reference Example 1 except that 17.24 g (0.105 mol) of 5-norbornene 2,3-dicarboxylic acid anhydride was used instead of 11.94 g (0.105 mol) of ethyl chloroformate. Similarly, a polybenzoxazole resin precursor was obtained (P-2). However, the reaction of 5-aminoisophthalic acid and 5-norbornene 2,3-dicarboxylic anhydride took 15 hours at room temperature after completion of the dropping. The polystyrene equivalent weight average molecular weight of this resin was 17000 (Mw).

[Reference Example 3]
In a 1-liter 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 of pyridine (0.6 mol) ), And 98.5 g (0.6 mol) of 5-norbornene-2,3-dicarboxylic acid 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 liter of ion-exchanged water with stirring, and the precipitate was filtered off, and then 500 ml of THF was added thereto and dissolved by stirring. This homogeneous solution was added to a glass column packed with a cation-exchange resin. The remaining pyridine was removed through Next, this solution was dropped into 3 liters 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 liters of a 0.5 wt% 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 liters 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 4]
102.4 g (0.92 mol) of resorcinol and 92.0 g (0.92 mol) of hexanal were dissolved in 920 ml of ethanol. This was cooled to 0 ° C. and 148 ml of 12N hydrochloric acid was added dropwise and stirred. The mixture was then stirred at 70 ° C. for 10 hours under a nitrogen atmosphere. After reaching room temperature, the precipitate was removed by filtration. The solid obtained by washing the filtrate with water at 80 ° C. and drying was recrystallized with a mixed solvent of methanol, hexane and acetone. Thereafter, vacuum drying was performed to obtain a resorcin cyclic tetramer with a yield of 50%.
Next, 76.9 g (0.1 mol) of the resorcin cyclic tetramer synthesized earlier, 134.3 g (0.5 mol of naphthoquinone diazide sulfonic acid esterification rate of 62. 1-naphthoquinone diazide-4-sulfonyl chloride). 5%) and 1057 g of tetrahydrofuran were added and dissolved by stirring at 20 ° C. A solution prepared by diluting 53.1 g (0.525 mol) of triethylamine with 266 g of tetrahydrofuran 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. After completion of the dropwise addition, the mixture was left to stir at 20 ° C. for another 30 minutes, and then 6.8 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 10 liters of a 0.5 wt% 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 liters 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 the desired photosensitive diazoquinone compound (Q-2).

[Reference Example 5]
In a separable flask having a capacity of 500 ml, 33.4 g (0.1 mol) of 2,2-bis (4-aminophenyl) -hexafluoropropane, 110 g of GBL, and 15.8 g (0.2 mol) of pyridine were dissolved in 86.8 g of GBL. 21.7 g (0.2 mol) of ethyl chloroformate was added dropwise. At this time, the temperature of the reaction solution was controlled in the range of 10 to 30 ° C. using an ice-water bath, and the reaction was stirred for 2 hours, and then the reaction was confirmed by HPLC. A single peak was detected with a purity of 99%. This 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 GBL was added and dissolved by stirring, and this homogeneous solution was mixed with cation-exchange resin and anion-exchange resin. The remaining chlorine ions and pyridine were removed through a packed glass column. Next, this solution was dropped into 3 liters of ion-exchanged water under high-speed stirring to precipitate a product, which was separated by filtration and vacuum-dried to obtain a urethane group-containing compound (C-1).

[Reference Example 6]
In Reference Example 5, the same procedure as in Reference Example 5 was conducted except that 43.7 g (0.2 mol) of di-t-butyl-dicarbonate was used instead of 21.7 g (0.2 mol) of ethyl chloroformate. A urethane group-containing compound was obtained (C-2). However, the reaction of 2,2-bis (4-aminophenyl) -hexafluoropropane and di-t-butyl-dicarbonate required 10 hours at room temperature after completion of the dropping. When the reaction was confirmed by HPLC, no starting material was detected, and the product was detected as a single peak with a purity of 99%.

[Reference Example 7]
In Reference Example 5, 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoro was used instead of 33.4 g (0.1 mol) of 2,2-bis (4-aminophenyl) -hexafluoropropane. A urethane group-containing compound was obtained in the same manner as in Reference Example 5 except that 36.6 g (0.1 mol) of propane was used (C-3). When the reaction was confirmed by HPLC, no starting material was detected, and the product was detected as a single peak with a purity of 99%.

[Examples 1-4, Comparative Examples 1-3]
The photosensitive diazoquinone compound (Q-1 or Q-1) obtained in Reference Example 3 or 4 is used with respect to 100 parts by mass of the hydroxypolyamide (P-1 or P-2) obtained in Reference Example 1 or 2. -2) 20 parts by mass, the C-1 to C-3 urethane group-containing compound obtained in Reference Examples 5 to 7 above, or the following C-4 thermally crosslinkable compound (collectively referred to as "crosslinking agent") 10) parts by weight in a solvent of 170 parts by weight, and then filtered through a 0.2 μm filter, and the positive photosensitive resins of Examples 1 to 4 and Comparative Examples 1 to 3 described in Table 1 A composition was prepared.
(C-4) Epolite 3002 (manufactured by Kyoeisha Chemical)

<Evaluation of positive photosensitive resin composition>
(1) Evaluation of patterning characteristics The positive photosensitive resin composition is spin-coated on a 5-inch silicon wafer with a spin coater (Dspin 636) manufactured by Dainippon Screen Mfg. Co., Ltd., and pre-baked at 130 ° C. for 180 seconds on a hot plate. A film having a thickness of 7.5 μm was formed. The film thickness was measured with a film thickness measuring device (Lambda Ace) manufactured by Dainippon Screen Mfg.
This coating film was exposed through a reticle with a test pattern by using a Nikon stepper (NSR2005i8A) having an exposure wavelength of i-line (365 nm) while changing the exposure stepwise. This was developed using an alkali developer (AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide aqueous solution) manufactured by AZ Electric Materials Co., Ltd. under a condition of 23 ° C. so that the film thickness after development was 6.5 μm. Was developed and rinsed with pure water to form a positive relief pattern. The sensitivity and resolution of the positive photosensitive resin composition are shown in Table 2.
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.

(2) Reflow resistance evaluation The relief pattern obtained by the above method (1) was cured for 1 hour at 350 ° C. in a vertical curing furnace (manufactured by Koyo Lindberg) at 350 ° C. To give a cured relief pattern. Next, the silicon wafer on which the cured relief pattern was formed was cut into about 10 cm square, and a sample for a reflow resistance test was produced. On the cured relief pattern, a flux (trade name: SOLDERITE, product number BF-30, manufactured by Tamura Kaken) was spin-coated (20 seconds at 500 rpm). This was heated to a peak temperature of 360 ° C. in a nitrogen atmosphere under simulated solder reflow conditions using a mesh belt type continuous firing furnace (model name 6841-20AMC-36, manufactured by Koyo Thermo Systems Co., Ltd.). This is in conformity with the solder reflow conditions described in Section 7.6 of IPC / JEDEC: J-STD-020A, which is a standard of the US semiconductor industry association, regarding a semiconductor device evaluation method. This is a standardized test condition assuming ℃.
The sample after the above reflow treatment was immersed in xylene for 10 minutes, then immersed in 2-propanol for 10 minutes to remove the flux, dried, and then observed under an optical microscope to cause damage to the cured relief pattern. The presence or absence of the occurrence of cracks was evaluated.
Evaluation index of cracks ○: No crack ×: Crack generation Further, the film thickness before and after the reflow treatment was measured, and the rate of change (swell rate) was calculated.

(3) Storage Stability Evaluation After measuring the viscosity of the positive photosensitive resin composition at 23 ° C. using an E-type viscometer, after standing at room temperature for 2 weeks, the viscosity was measured again, and the rate of change (Thickening rate) was calculated.
Evaluation index of storage stability Good: within ± 5% Poor: ± 5% or more From Table 2, by using the positive photosensitive resin composition of the present invention, storage stability is good, high sensitivity, and high resolution. It can be seen that a thermosetting film having not only a relief pattern but also good reflow resistance was obtained. On the other hand, it can be seen that the compositions of Comparative Examples 1 to 3 that do not contain the urethane group-containing compound that satisfies the requirements of the present invention have a disadvantage that good reflow resistance cannot be obtained or the stability of the composition is poor. .

  The positive photosensitive resin composition of the present invention includes a surface protective film for a semiconductor device, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, a protective film for a device having a bump structure, and an interlayer of a multilayer circuit. 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 (3)

(A) 100 parts by mass of a hydroxypolyamide having a repeating unit represented by the following general formula (1), (B) 0.01 to 30 parts by mass of a urethane group-containing compound represented by the following general formula (2), And (C) 1 to 100 parts by mass of a photosensitive diazoquinone compound, a positive photosensitive resin composition.

Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, X ₂ , Y ₁ and Y ₂ are each independently a divalent organic group having at least 2 carbon atoms, m Is an integer from 2 to 1000, n is an integer from 0 to 500, and m / (m + n)> 0.5, where m dihydroxydiamide units including X ₁ and Y ₁ , and X ₂ and (The order of arrangement of n diamide units including Y ₂ is not limited.)

(In the formula, R ₁ and R ₂ represent a monovalent organic group having 1 to 20 carbon atoms.)   (1) The positive photosensitive resin composition according to claim 1 is formed on a substrate in the form of a layer or a film, and (2) it is exposed with actinic radiation through a mask, or a light beam, an electron beam or an ion beam. (3) The exposed portion or irradiated portion is eluted and removed with a developer, and (4) the resulting relief pattern is heat treated.   A semiconductor device comprising a cured relief pattern layer obtained by the method for producing a cured relief pattern according to claim 2.