JP4721845B2 - Positive photosensitive resin composition - Google Patents

Description

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

Conventionally, polyimide resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been widely used for surface protective films and interlayer insulating films of semiconductor devices. 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, recently, various heat-resistant photosensitive resin materials that can be developed with an alkaline aqueous solution have been proposed in the same manner as photoresists.

Among them, a PBO precursor composition obtained by mixing an alkaline aqueous solution-soluble hydroxypolyamide, such as a 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. In recent years, attention has been paid to a method of using the product (see, for example, Patent Document 1).
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, and the cured PBO film has the same thermosetting film characteristics as a polyimide film. It attracts attention as a promising alternative material for solvent-developed polyimide precursors. However, the PBO precursor composition obtained by the methods disclosed so far still has many problems.

For example, in recent years, semiconductor devices that are inferior in heat resistance compared to conventional products have been developed, and there is a demand for lowering the thermosetting temperature as a surface protective film or interlayer insulating film, especially for thermosetting at 280 ° C. or lower. There are many things that can be done. However, in the conventional PBO precursor composition, the ring closure reaction from the PBO precursor to PBO (ring closure reaction to the oxazole ring) does not proceed sufficiently in the region of 280 ° C. or lower. The film obtained by curing did not have the excellent heat resistance, electrical properties, mechanical properties and the like expected for PBO.
Conventionally, it has been known that the use of a dehydrating agent such as concentrated sulfuric acid, phosphorus oxychloride, polyphosphoric acid or the like is effective for proceeding the ring-closing reaction to the oxazole ring at a low temperature (for example, see Non-Patent Document 1) . However, it is very difficult to add these dehydrating agents to the photosensitive PBO precursor composition in view of the stability of the composition, the lithography performance, etc., and no satisfactory one has been proposed yet.

JP 63-096162 A The Chemical Society of Japan "Experimental Chemistry Course 4th Edition Vol. 24 Organic Synthesis VI" published by Maruzen Co., Ltd., p525

  The present invention is a novel positive photosensitive resin that has excellent stability and exhibits excellent heat resistance, electrical properties, mechanical properties, etc. by sufficiently proceeding with the ring closure reaction of PBO even when used at a low thermosetting temperature. An object is to provide a composition, a method for producing a cured relief pattern using the composition, and a semiconductor device having the cured relief pattern.

（式中、Ｘ₁ は少なくとも２個以上の炭素原子を有する４価の有機基を示し、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価の有機基を示す。また、ｍは２〜１０００の整数を示し、ｎは０〜５００の整数を示し、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。） As a result of intensive research to solve the above-mentioned problems, the present inventors have established a positive photosensitive resin that solves the above-mentioned problems by combining an ester compound having a specific structure with a hydroxypolyamide and a photosensitive diazoquinone compound. The present inventors have found that a functional resin composition can be obtained and have made the present invention.
That is, one aspect of the present invention is 100 parts by mass of a hydroxypolyamide having a repeating unit represented by the following general formula (1) and at least one ester compound represented by the following general formula (3 ) or the following general formula (5). It is a positive photosensitive resin composition characterized by containing 0.1-30 mass parts of at least 1 compound represented, and 1-100 mass parts of photosensitive diazoquinone compounds.

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

（式中、Ｒ₅ は、ハロゲン原子、ニトロ基、シアノ基、アルキルカルボニル基、アミド基、イミド基、若しくはエステル基の少なくとも１つで置換されていてもよい炭素数１〜８の一価の有機基、または水素原子を示す。Ｒ₆ は、アルコキシル基、アルキルカルボニルオキシ基、水酸基、アミド基、アミノ基、またはイミノ基の少なくとも１つで置換されていてもよい炭素数１〜１０の一価の有機基を示す。Ｒ₇ は、ハロゲン原子、ニトロ基、シアノ基、アルコキシル基、アミノ基、またはイミノ基の少なくとも１つで置換されていてもよい、炭素数３〜８の二価の有機基を示す。Ｒ₈ は、ハロゲン原子、または水酸基で置換されていてもよい炭素数６〜１０の一価の有機基を示す。）

(In the formula, R ₅ is a monovalent monovalent alkyl having 1 to 8 carbon atoms which may be substituted with at least one of a halogen atom, a nitro group, a cyano group, an alkylcarbonyl group, an amide group, an imide group, or an ester group. R ₆ represents an organic group or a hydrogen atom, and R ₆ is an alkyl group, an alkylcarbonyloxy group, a hydroxyl group, an amide group, an amino group, or an imino group. R ₇ represents a divalent organic group having 3 to 8 carbon atoms, which may be substituted with at least one of a halogen atom, a nitro group, a cyano group, an alkoxyl group, an amino group, or an imino group. R ₈ represents an organic group, and R ₈ represents a monovalent organic group having 6 to 10 carbon atoms which may be substituted with a halogen atom or a hydroxyl group.

（式中、Ｒ₁₀は、ハロゲン原子、ニトロ基、シアノ基、アルコキシル基、アミノ基、またはイミノ基の少なくとも１つで置換されていてもよい二価の有機基を示す。）
但し、Ｒ¹Ｒ²Ｃ＝Ｎ−Ｏ−ＳＯ₂−Ｒ（式中、Ｒはアリール基、アルキル基、パーフル
オロアルキル基であり、Ｒ¹はシアノ基であり、Ｒ²はメトキシフェニル基、フェニル基を示す。）で示される化合物、下記式Ｃ１８、下記式Ｃ３で表される化合物、１，３−ブタンスルトン、メタンスルホン酸メチルエステル、メタンスルホン酸エチルエステル、メタンスルホン酸フェニルエステル、およびメタンスルホン酸２−イソプロピルエチルエステルで表される化合物を除く。

さらにアクリレート系化合物１〜１００質量部を含むことが好ましい。

(In the formula, R ₁₀ represents a divalent organic group which may be substituted with at least one of a halogen atom, a nitro group, a cyano group, an alkoxyl group, an amino group, or an imino group.)
Provided that R ¹ R ² C═N—O—SO ₂ —R (wherein R is an aryl group, alkyl group, perfluoroalkyl group, R ¹ is a cyano group, R ² is a methoxyphenyl group, A compound represented by the following formula C18 , a compound represented by the following formula C3, 1,3-butane sultone, methanesulfonic acid methyl ester, methanesulfonic acid ethyl ester, methanesulfonic acid phenyl ester, and methane Excludes compounds represented by 2-isopropylethyl sulfonic acid .

Furthermore, it is preferable that 1-100 mass parts of acrylate-type compounds are included.

In the second aspect of the present invention, (1) the positive photosensitive resin composition according to one aspect 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, A method for producing a cured relief pattern, which comprises directly irradiating light, an electron beam or an ion beam, (3) eluting and removing the exposed portion or irradiated portion, and (4) heat-treating the obtained relief pattern. is there.
A third aspect of the present invention is a semiconductor device having a cured relief pattern layer obtained by the second production method of the present invention.

  The positive photosensitive resin composition of the present invention has good stability, and exhibits excellent heat resistance, electrical properties, and mechanical properties due to sufficient progress of the ring closure reaction of PBO even when used at a low thermosetting temperature. To do. Moreover, the manufacturing method of the cured relief pattern using this positive photosensitive resin composition and the semiconductor device which has this cured relief pattern are provided.

<Positive photosensitive resin composition>
Each component constituting the positive photosensitive resin composition of the present invention will be specifically described below. (1) Hydroxypolyamide Hydroxypolyamide, which is the base polymer of the positive photosensitive resin composition of the present invention, is a polymer containing m dihydroxydiamide units of the following general formula (1). The dihydroxydiamide unit has a structure obtained by condensing a bisaminophenol having a X ₁ (NH ₂ ) ₂ (OH) ₂ structure and a dicarboxylic acid having a Y ₁ (COOH) ₂ structure. Here, the two amino groups and the hydroxy group of the bisaminophenol are each in the ortho position. When a compound having a catalytic action is not added, the hydroxypolyamide is usually heated to about 300 to 400 ° C. to cyclize and change to polybenzoxazole 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 following general formula (1). The diamide unit has a structure obtained by condensing a diamine having a X ₂ (NH ₂ ) ₂ structure and a dicarboxylic acid having a Y ₂ (COOH) ₂ structure. n is preferably in the range of 0 to 500, and more preferably in the range of 0 to 10. If the ratio of the diamide units in the hydroxypolyamide is too high, the solubility in an alkaline aqueous solution used as a developer is lowered. Therefore, the value of m / (m + n) is preferably more than 0.5. 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, 1,3- And diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.

また、Ｘ₂ （ＮＨ₂ ）₂ の構造を有するジアミンとしては、芳香族ジアミン、シリコンジアミンなどが挙げられる。 Particularly preferred among these bisaminophenols is when X ₁ is an aromatic group selected from the following.

As the diamine having a structure of X ₂ (NH _{2) 2,} an aromatic diamine, such as 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-a Nophenyl) hexafluoropropane, 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-amino) Benzyl) 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'-diaminobipheny 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) diphenylsulfone, 4,4′-diaminobenzanilide and the like, and the hydrogen atom of the aromatic nucleus of these aromatic diamines are a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group And a compound substituted with at least one group or atom selected from the group consisting of a group and a phenyl group. It is.

  In addition, silicon diamine can be selected in order to improve the adhesion to the substrate. Examples of this include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, and bis (p -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 −からなる群から選択される２価の基を意味する。）
前述の一般式（１）で示される繰り返し単位を有するヒドロキシポリアミドにおいて、その末端基を特定の有機基で封止することも本発明の範囲に含まれる。 Moreover, as a preferable dicarboxylic acid having a structure of Y ₁ (COOH) ₂ or Y ₂ (COOH) ₂ , a case where Y ₁ and Y ₂ are aromatic groups selected from the following can be mentioned.

Wherein A is a divalent group selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —. Means a group.)
In the hydroxypolyamide having the repeating unit represented by the general formula (1), it is also within the scope of the present invention to seal the terminal group with a specific organic group.

Examples of such a sealing group include groups having an unsaturated bond as described in JP-A-5-197153. When these groups are sealed, the coating film after heat curing is used. It is expected that the mechanical properties (especially elongation) and the cured relief pattern shape will be good. The following are mentioned as a suitable example of such a sealing group.

（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。） (2) Photosensitive diazoquinone compound The photosensitive diazoquinone compound used in the present invention is a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure. US Pat. No. 2,772,972, No. 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への配合量は、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質量部以上だと樹脂のパターニング性が発現し、１００質量部以内だと硬化後の膜の引張り伸び率、及び露光部の現像残さ（スカム）が良好になる。 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 to the hydroxy polyamide of a 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 exhibited, and when it is within 100 parts by mass, the tensile elongation rate of the cured film and the development residue (scum) of the exposed part are improved. .

（式中、Ｒ₁ は、ハロゲン原子、ニトロ基、シアノ基、アルキルカルボニル基、アミド基、イミド基、若しくはエステル基の少なくとも１つで置換されていてもよい炭素数１〜８の一価の有機基、または水素原子を示す。Ｒ₂ は、アルコキシル基、アルキルカルボニルオキシ基、水酸基、アミド基、アミノ基、またはイミノ基の少なくとも１つで置換されていてもよい炭素数１〜１０の一価の有機基を示す。Ｒ₃ は、ハロゲン原子、ニトロ基、シアノ基、アルコキシル基、アミノ基、またはイミノ基の少なくとも１つで置換されていてもよい、炭素数３〜８の二価の有機基を示す。Ｒ₄ は、ハロゲン原子、または水酸基で置換されていてもよい炭素数６〜１０の一価の有機基を示す。Ａは以下から選ばれる二価の基を示す。）

(3) Ester Compound In the positive photosensitive resin composition of the present invention, it is important to further contain at least one ester compound represented by the general formula (2) or the general formula (4). In the following, the C1-C8 organic group means an organic group having 1 to 8 carbon atoms, and the C1-C10 organic group means an organic group having 1 to 10 carbon atoms.

(In the formula, R ₁ is a monovalent monovalent carbon atom having 1 to 8 carbon atoms which may be substituted with at least _one of a halogen atom, a nitro group, a cyano group, an alkylcarbonyl group, an amide group, an imide group, or an ester group. R ₂ represents an organic group or a hydrogen atom, and R ₂ is an alkyl group, an alkylcarbonyloxy group, a hydroxyl group, an amide group, an amino group, or an imino group, which is optionally substituted with 1 to 10 carbon atoms. R ₃ represents a divalent organic group having 3 to 8 carbon atoms which may be substituted with at least one of a halogen atom, a nitro group, a cyano group, an alkoxyl group, an amino group, or an imino group. R ₄ represents an organic group, R ₄ represents a monovalent organic group having 6 to 10 carbon atoms which may be substituted with a halogen atom or a hydroxyl group, and A represents a divalent group selected from the following.

（式中、Ｒ₉ は、ハロゲン原子、ニトロ基、シアノ基、アルコキシル基、アミノ基、またはイミノ基の少なくとも１つで置換されていてもよい二価の有機基を示す。Ｚ₁ 、及びＺ₂ は、それぞれ独立に以下から選ばれる二価の基を示す。）

(In the formula, R ₉ represents a divalent organic group which may be substituted with at least one of a halogen atom, a nitro group, a cyano group, an alkoxyl group, an amino group, or an imino group. Z ₁ and Z ₂ represents a divalent group independently selected from the following:

（式中、Ｒ₅ は、ハロゲン原子、ニトロ基、シアノ基、アルキルカルボニル基、アミド基、イミド基、若しくはエステル基の少なくとも１つで置換されていてもよい炭素数１〜８の一価の有機基、または水素原子を示す。Ｒ₆ は、アルコキシル基、アルキルカルボニルオキシ基、水酸基、アミド基、アミノ基、またはイミノ基の少なくとも１つで置換されていてもよい炭素数１〜１０の一価の有機基を示す。Ｒ₇ は、ハロゲン原子、ニトロ基、シアノ基、アルコキシル基、アミノ基、またはイミノ基の少なくとも１つで置換されていてもよい、炭素数３〜８の二価の有機基を示す。Ｒ₈ は、ハロゲン原子、または水酸基で置換されていてもよい炭素数６〜１０の一価の有機基を示す。） The ester compound is more preferably at least one compound represented by general formula (3) or general formula (5), and more preferably at least one compound represented by general formula (3).

(In the formula, R ₅ is a monovalent monovalent alkyl having 1 to 8 carbon atoms which may be substituted with at least one of a halogen atom, a nitro group, a cyano group, an alkylcarbonyl group, an amide group, an imide group, or an ester group. R ₆ represents an organic group or a hydrogen atom, and R ₆ is an alkyl group, an alkylcarbonyloxy group, a hydroxyl group, an amide group, an amino group, or an imino group. R ₇ represents a divalent organic group having 3 to 8 carbon atoms, which may be substituted with at least one of a halogen atom, a nitro group, a cyano group, an alkoxyl group, an amino group, or an imino group. R ₈ represents an organic group, and R ₈ represents a monovalent organic group having 6 to 10 carbon atoms which may be substituted with a halogen atom or a hydroxyl group.

（式中、Ｒ₁₀はハロゲン原子、ニトロ基、シアノ基、アルコキシル基、アミノ基、またはイミノ基の少なくとも１つで置換されていてもよい二価の有機基を示す。）

(Wherein R ₁₀ represents a divalent organic group which may be substituted with at least one of a halogen atom, a nitro group, a cyano group, an alkoxyl group, an amino group, or an imino group.)

  When the ester compound represented by the general formula (2) to the general formula (5) is added to the positive photosensitive resin composition composed of the hydroxy polyamide and the photosensitive diazoquinone compound, the thermosetting temperature is, for example, 280. Even at a low temperature of ℃ or lower, the ring closure reaction of PBO proceeds sufficiently, and a final cured film having excellent heat resistance, electrical properties, mechanical properties and the like can be obtained. And the ester compound represented by General formula (2)-General formula (5) does not impair the stability of a composition by adding. In addition, the ester compound can be added together with a thermal base generator such as an amine imide compound for the purpose of facilitating the generation of acid.

  Examples of the ester compound include ethyl acetate, methyl acetate, t-butyl acetate, t-butyl acetoacetate, t-butyl acrylate, allyl chloroacetate, n-butyl chloroacetate, t-butyl chloroacetate, and ethyl chloroacetate. , Methyl chloroacetate, benzyl chloroacetate, isopropyl chloroacetate, 2-methoxyethyl chloroacetate, methyl dichloroacetate, methyl trichloroacetate, ethyl trichloroacetate, 2-ethoxyethyl trichloroacetate, t-butyl cyanoacetate, t-butyl methacrylate , Ethyl trifluoroacetate, methyl trifluoroacetate, phenyl trifluoroacetate, vinyl trifluoroacetate, isopropyl trifluoroacetate, allyl trifluoroacetate, ethyl benzoate, methyl benzoate, t-butyl benzoate, 2-chlorobenzoic acid Methyl, 2-c Ethyl benzoate, ethyl 4-chlorobenzoate, ethyl 2,5-dichlorobenzoate, methyl 2,4-dichlorobenzoate, ethyl perfluorobenzoate, methyl perfluorobenzoate, t-butyl pentachlorophenylcarboxylate, Carboxylic acid esters such as methyl pentafluoropropionate, ethyl pentafluoropropionate and t-butyl crotonic acid, cyclic carboxylic acid esters such as phenolphthalein and thymolphthalein, ethyl methanesulfonate, methyl methanesulfonate, methane 2-methoxyethyl sulfonate, 2-isopropoxyethyl methanesulfonate, phenyl p-toluenesulfonate, ethyl p-toluenesulfonate, methyl p-toluenesulfonate, 2-phenylethyl p-toluenesulfonate, p-tolue N-propyl sulfonate, n-butyl p-toluenesulfonate, t-butyl p-toluenesulfonate, n-hexyl p-toluenesulfonate, n-heptyl p-toluenesulfonate, n-octyl p-toluenesulfonate , 2-methoxyethyl p-toluenesulfonate, propargyl p-toluenesulfonate, 3-butynyl p-toluenesulfonate, ethyl trifluoromethanesulfonate, n-butyl trifluoromethanesulfonate, ethyl perfluorobutanesulfonate, perfluoro Sulfonic esters such as methyl butane sulfonate and ethyl perfluorooctane sulfonate, 1,4-butane sultone, 2,4-butane sultone, 1,3-propane sultone, phenol red, bromophenol blue, bromocresol green, Examples thereof include cyclic sulfonic acid esters such as bromocresol purple, 2-sulfobenzoic acid anhydride, p-toluenesulfonic acid anhydride, and phthalic acid anhydride.

  Among these ester compounds, preferred are ethyl methanesulfonate, methyl methanesulfonate, 2-methoxyethyl methanesulfonate, 2-isopropoxyethyl methanesulfonate, phenyl p-toluenesulfonate, and ethyl p-toluenesulfonate. , Methyl p-toluenesulfonate, 2-methoxyethyl p-toluenesulfonate, ethyl trifluoromethanesulfonate, n-butyl trifluoromethanesulfonate, ethyl perfluorobutanesulfonate, methyl perfluorobutanesulfonate, perfluorooctanesulfone Examples include sulfonic acid esters such as ethyl acid, 1,4-butane sultone, 2,4-butane sultone, 2-sulfobenzoic acid anhydride, and p-toluenesulfonic acid anhydride.

Further, among the sulfonic acid esters, most preferred are ethyl methanesulfonate, methyl methanesulfonate, 2-methoxyethyl methanesulfonate, ethyl p-toluenesulfonate, methyl p-toluenesulfonate, p-toluenesulfone. Examples include acid 2-methoxyethyl, ethyl trifluoromethanesulfonate, n-butyl trifluoromethanesulfonate, 2,4-butane sultone, 2-sulfobenzoic anhydride, p-toluenesulfonic anhydride, and the like. These compounds may be used alone or in combination of two or more.
The addition amount of the ester compound is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the hydroxy polyamide. When the addition amount is 0.1 parts by mass or more, there is an effect of promoting the ring-closing reaction to PBO at the time of thermosetting at low temperature. On the other hand, if the addition amount is within 30 parts by mass, the composition has good stability. is there.

(4) Acrylate-based compound In the positive photosensitive resin composition of the present invention, it is preferable to contain an acrylate-based compound from the viewpoint of improving the mechanical properties of the final cured film. An acrylate compound refers to a compound selected from the group consisting of acrylic acid ester, methacrylic acid ester, acrylamide, and methacrylamide.
Examples of the acrylate compound include NK-ester series manufactured by Shin-Nakamura Chemical Co., Ltd .; M-20G, M-40G, M-90G, M-230G, CB-1, SA, S, AMP-10G, AMP-20G AMP-60G, AM-90G, A-SA, LA, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, HD, NPG, 9PG, 701, BPE-100, BPE-200, BPE-500 , BPE-1300, A-200, A-400, A-600, A-HD, A-NPG, APG-200, APG-400, APG-700, A-BPE-4, 701A, TMPT, A-TMPT , A-TMM-3, A-TMM-3L, A-TMMT, and the like.

In addition, Kyoeisha Chemical Light Ester Series; M, E, NB, IB, EH, ID, L, L-5, L-7, TD, L-8, S, MC, 130MA, 041MA, CH, THF, BZ , PO, IB-X, HO, HOP, HOA, HOP-A, HOB, A, HO-MS, HO-HH, HO-MPP, G, P-1M, P-2M, EG, 2EG, 1.4BG 1.6HX, 1.9ND, TMP, G-101P, G-201P, BP-2EM, TB, IS, MTG, BO, CL, 3EG, 4EG, 9EG, 14EG, NP, M-3F, M-4F , M-6F, FM-108, 1.3BG, and 1.10DC.
In addition, Kyoeisha Chemical Light Acrylate Series IAA, LA, SA, BO-A, EC-A, MTG-A, 130A, DPM-A, PO-A, P-200A, NP-4EA, NP- 8EA, THF-A, IB-XA, HOA, HOP-A, M-600A, HOA-MS, HOA-MPE, 3EG-A, 4EG-A, 9EG-A, 14EG-A, NP-A, 1. 6HX-A, 1.9ND-A, DCP-A, BP-4EA, BP-4PA, TMP-A, TMP-6EO-3A, PE-3A, PE-4A, DPE-6A, BA-104, BA- 134, G-201P, and the like.

Furthermore, Kyoeisha Chemical Epoxy Ester Series; M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M, 3002A, etc., Toa Gosei Co., Ltd. Aronix Series; M-101, M-102, M-110, M -111, M-113, M-117, M-120, M-208, M-210, M-211, M-215, M-220, M-225, M-233, M-240, M-245 M-260, M-270, M-305, M-309, M-310, M-315, M-320, M-350, M-360, M-400, M-408, M-450, M -5300, M-5400, M-5600, M-5700, etc., or DMAEA, DMAPAA, DMAA, ACMO, NIPAM, DEAA, etc. manufactured by Kojin Co., Ltd. It is.
Among these acrylate compounds, compounds having two or more thermopolymerizable functional groups are particularly preferable. These compounds may be used alone or in combination of two or more.
1-100 mass parts is preferable with respect to 100 mass parts of this hydroxy polyamide, and, as for the compounding quantity to the hydroxy polyamide of an acrylate type compound, 5-30 mass parts is more preferable. When the blending amount of the acrylate compound is 1 part by mass or more, there is an effect of improving the elongation of the film after thermosetting, and when it is within 100 parts by mass, the stability of the composition is good.

(5) Other components In the positive photosensitive resin composition of the present invention, if necessary, a dye, a surfactant, a stabilizer, and a substrate, which are conventionally used as additives for photosensitive resin compositions, are used. It is also possible to add an adhesion assistant, a crosslinking agent, a solvent or the like for improving the adhesion.
The additives will be described more specifically. Examples of the dye include methyl violet, crystal violet, and malachite green. Examples of the surfactant include nonionic 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. (Trade name, manufactured by Dainippon Ink & Chemicals, Inc.) or sulfuron (trade name, manufactured by Asahi Glass Co., Ltd.), for example, KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, Chisso) And organic siloxane surfactants such as Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). 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.

  Examples of the crosslinking agent include 1,1,2,2-tetra (p-hydroxyphenyl) ethane, tetraglycidyl ether, glycerol triglycidyl ether, ortho-secondary butylphenyl glycidyl ether, 1,6-bis (2,3-epoxypropoxy ) Epoxy compounds such as naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, acetylacetone aluminum (III) salt, acetylacetone titanium (IV) salt, acetylacetone chromium (III) salt, acetylacetone magnesium (II) salt, acetylacetone magnesium (II) ) Salt, trifluoroacetylacetone aluminum (III) salt, trifluoroacetylacetone titanium (IV) salt, trifluoroacetylacetone chromium (III) salt, Metal chelating agents such as fluoroacetylacetone magnesium (II) salt and trifluoroacetylacetone nickel (II) salt, Nicalak MW-30MH, MW-100LH (trade name, manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, Cymel 303 (trade name, There are alkylated melamine resins such as Mitsui Cytec.

  In the present invention, these components are 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, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl 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, methyl-3- Methoxypropionate or the like can be used alone or in combination. Of these solvents, non-amide solvents are preferable from the viewpoint of little influence on photoresists, and specific more preferable examples include γ-butyrolactone, cyclopentanone, cyclohexanone, and isophorone.

<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 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. As the rinsing liquid, distilled water, deionized water, or the like can be used.

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. In this heat treatment, a temperature of 180 ° C. or higher is applied for 5 minutes or more, and a certain constant temperature may be maintained, or the temperature may be continuously increased. Preferred heat treatment conditions are such that the maximum temperature is 200 ° C. or higher and the time of 200 ° C. or higher is 30 minutes or longer.

Specifically, when the composition of the present invention is used for the production of a semiconductor device having inferior heat resistance, such as MRAM, organic semiconductor, and CMOS having copper wiring, which cannot be heated at 300 ° C. or higher, the heat treatment temperature is set to 180 to It is preferable to set it as 290 degreeC, and it is more preferable to set it as 220-250 degreeC. On the other hand, when used for the manufacture of a semiconductor device which does not have a problem in heating to 300 ° C. or higher, it is more preferably 300 to 350 ° C.
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 based on reference examples and examples.
<Synthesis of hydroxy polyamide>
[Reference Example 1]
In a 3 L separable flask, 173.1 g (0.473 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 605.7 g of N, N-dimethylacetamide (DMAc) 71.2 g (0.9 mol) of pyridine was mixed and stirred at room temperature (25 ° C.) to obtain a uniform solution. A solution prepared by dissolving 132.80 g (0.45 mol) of 4,4′-diphenyl ether dicarbonyl chloride in 531.2 g of diethylene glycol dimethyl ether (DMDG) was added dropwise thereto from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20 ° C. The time required for the dropping was 60 minutes, and the temperature of the reaction solution was 30 ° C. at the maximum.

3 hours after the completion of dropping, 6.9 g (0.045 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction solution, and the mixture was left to stir at room temperature for 15 hours, and 99% of all amine end groups of the polymer chain were carboxylated. Sealed with a cyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of 1,2-cyclohexyldicarboxylic anhydride added by high performance liquid chromatography (HPLC). Thereafter, the reaction solution was dropped into 20 l of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, appropriately washed with water, dehydrated and then vacuum dried, and measured by gel permeation chromatography (GPC). Hydroxypolyamide P-1 having a weight average molecular weight of 30000 (polystyrene conversion) was obtained.
In addition, when further purification of the polymer is necessary, it can be carried out by the following method. That is, after redissolving the polymer obtained above in DMDG, this was treated with a cation exchange resin and an anion exchange resin, and the solution obtained thereby was poured into ion exchange water, and then the precipitated polymer was removed. A purified polymer can be obtained by filtration, washing with water, and vacuum drying.

[Reference Example 2]
In a separable flask having a volume of 3 l, 173.1 g (0.473 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 71.2 g (0.9 mol) of pyridine, 605.7 g of DMAc Was dissolved by mixing and stirring at room temperature (25 ° C.). Separately, 7.4 g (0.045 mol) of 5-norbornene-2,3-dicarboxylic anhydride in 30 g of DMDG was added dropwise from a dropping funnel. The time required for the dropwise addition was 7 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. Further, by reaction tracking by HPLC, the products of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane and 5-norbornene-2,3-dicarboxylic anhydride are all imides. It was confirmed.
Next, this was cooled to 0 ° C. with an ice bath, and 132.8 g (0.45 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride dissolved separately in 531.2 g of DMDG was added dropwise from the dropping funnel. . The time required for the dropwise addition was 120 minutes, and the maximum reaction solution temperature was 12 ° C. 3 hours after the completion of dropping, the above reaction solution was dropped into 20 l of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, washed with water and dehydrated appropriately, followed by vacuum drying to obtain hydroxypolyamide P-2. It was. The weight average molecular weight of the thus synthesized hydroxypolyamide by GPC was 31000 in terms of polystyrene.

[Reference Example 3]
In a 3 L separable flask, 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane 85.0 g (0.23 mol), pyridine 35.6 g (0.45 mol), DMAc 297.4 g Was dissolved by mixing and stirring at room temperature (25 ° C.). Separately, 2.3 g (0.014 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride dissolved in 9 g of DMDG was dropped from the dropping funnel. The time required for the dropwise addition was 4 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. Further, by reaction tracking by HPLC, the products of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane and 5-norbornene-2,3-dicarboxylic anhydride are all imides. It was confirmed.
Next, this was cooled to 0 ° C. with an ice bath, and separately, 13.7 g (0.068 mol) of isophthalic acid chloride and 46.5 g (0.158 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride in 180.5 g of DMDG. ) Was dissolved from the dropping funnel. The time required for the dropping was 150 minutes, and the maximum reaction solution temperature was 12 ° C. 3 hours after the completion of dropping, the above reaction solution was dropped into 20 l of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, washed with water and dehydrated appropriately, followed by vacuum drying to obtain hydroxypolyamide P-3. It was. The weight average molecular weight of the thus synthesized hydroxy polyamide by GPC was 32,000 in terms of polystyrene.

[Reference Example 4]
In a 3 l separable flask, 25.59 g (0.708 mol) 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 35.6 g (0.45 mol) pyridine, 908.55 g DMAc Was dissolved by mixing and stirring at room temperature (25 ° C.). A solution prepared by dissolving 15.13 g (0.09 mol) of methylcyclohexane-1,2-dicarboxylic anhydride in 75.65 g of γ-butyrolactone was added dropwise from a dropping funnel. The time required for the dropwise addition was 10 minutes, and the maximum reaction solution temperature was 28 ° C.
After completion of dropping, the mixture was allowed to stand for 3 hours at room temperature, and 99% of all amine end groups of the polymer chain were sealed with carboxymethylcyclohexylamide groups. The reaction rate at this time can be easily calculated by monitoring the remaining amount of methylcyclohexane-1,2-dicarboxylic anhydride added by high performance liquid chromatography (HPLC). Thereafter, the reaction solution was cooled to 0 ° C. with an ice bath, and 13.47 g (0.066 mol) of isophthalic acid chloride and 176.21 g of 4,4′-diphenyl ether dicarboxylic acid dichloride were separately added to 948.4 g of γ-butyrolactone. What dissolved (0.597 mol) was dripped from the dropping funnel. The time required for the dropping was 150 minutes, and the maximum reaction solution temperature was 12 ° C. Three hours after the completion of the dropwise addition, the above reaction solution was dropped into 20 l of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, washed with water and dehydrated appropriately, followed by vacuum drying to obtain hydroxypolyamide P-4. Obtained. The weight average molecular weight of the thus synthesized hydroxypolyamide by GPC was 22595 in terms of polystyrene.

[Reference Example 5]
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 an additional 30 minutes, and then 5.6 g of a 36 wt% hydrochloric acid aqueous solution was added at once. . 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 material obtained was vacuum-dried at 40 ° C. for 24 hours to obtain photosensitive diazoquinone compound Q-1.

[Reference Example 6]
102.4 g (0.92 mol) of resorcinol and 92.0 g (0.92 mol) of hexanol 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 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 the desired photosensitive diazoquinone compound Q-2.

[Examples 2, 3, 5, 7, 8, Reference Examples 1, 4, 6 and Comparative Examples 1-4]
<Preparation of positive photosensitive resin composition>
100 parts by mass of the hydroxy polyamide (P-1 to 4) obtained in Reference Examples 1 to 4 above, 20 parts by mass of the photosensitive diazoquinone compound of Q-1 or Q-2 obtained in Reference Examples 5 and 6 above. , 10 parts by mass of an ester compound having a structure of the following formulas E-1 to E-8 (all manufactured by Tokyo Chemical Industry Co., Ltd.), 10 parts by mass of a dehydrating agent for D-1 (polyphosphoric acid manufactured by Wako Pure Chemical Industries, Ltd.), A- 1 (manufactured by Shin Nakamura chemical Co., Ltd.: NK ester 4G) was dissolved acrylate compound of the GBL170 parts by combinations described in Table 1, was filtered through a 0.2μm filter, example 2, 3, 5 , 7, 8, Reference Examples 1 , 4 , 6 and Comparative Examples 1 to 4 were prepared as positive photosensitive resin compositions.

<Evaluation of positive photosensitive resin composition>
(1) Evaluation of Oxazolation Rate The positive photosensitive resin composition was 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. And a coating film was formed. In a vertical curing furnace (manufactured by Koyo Lindberg), curing (heat curing treatment) was performed in a nitrogen atmosphere at 250 ° C. or 350 ° C. for 1 hour. The IR spectrum of the obtained cured film was measured by a microscopic ATR method, and after adjusting the size of each spectrum using the peak at 1490 cm ⁻¹ as a reference, the peak at 1050 cm ⁻¹ , which is the characteristic absorption of the oxazole ring, was measured. Using the size, the oxazolation rate at 250 ° C. when the oxazolation rate at 350 ° C. was taken as 100% was calculated according to the following formula and shown in Table 2.
Oxazole rate (%) = (250 ℃ heat treatment the peak height of the sample 1050cm ^-1) ÷ (350 ℃ heat treatment the peak height of 1050 cm ^-1 of sample) × 100

(2) Evaluation of mechanical properties The positive photosensitive resin composition was spin-coated on a 5-inch silicon wafer on which an aluminum film was previously formed by sputtering with a spin coater (Dspin 636) manufactured by Dainippon Screen Mfg. Co., Ltd. Pre-baking was performed at 130 ° C. for 180 seconds to form a coating film having a thickness of 11.0 μm. This coating film was exposed with PLA-501F manufactured by Canon using a photomask having a 10 mm strip pattern. Next, the exposed portion was dissolved and removed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 1 minute, and then rinsed with pure water for 30 seconds. In a vertical curing furnace (manufactured by Koyo Lindberg), curing was performed at 250 ° C. for 1 hour in a nitrogen atmosphere. This film was immersed in a 3% hydrofluoric acid aqueous solution, the strip-shaped film was peeled off, thoroughly washed with pure water, and dried to obtain a strip-shaped test sample. This film was pulled with Tensilon (load = 2 kgf, pulling speed = 40 mm / min), and the elongation at break was measured as mechanical property evaluation and shown in Table 2.

(3) Patterning characteristic evaluation 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 10.7 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. Using an alkali developer (AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide aqueous solution) manufactured by Clariant Japan, the development time was adjusted so that the film thickness after development was 9.1 μm at 23 ° C. Development was then performed to form a positive relief pattern. Table 3 shows the development time and sensitivity of the positive photosensitive resin composition. The sensitivity of the positive photosensitive resin composition was 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.

(4) Stability evaluation The positive photosensitive resin composition was allowed to stand at room temperature for 1 week, and the rate of change in viscosity after being allowed to stand was measured. The change rate of the viscosity is shown in Table 3.
From Table 2, it can be seen that by using the positive photosensitive resin composition of the present invention, the ring-closure reaction from the PBO precursor to PBO proceeds sufficiently even by heat curing at 250 ° C. The elongation at break was also a high value.
From Table 3, it can be seen that the positive photosensitive resin composition of the present invention does not deteriorate the development time, sensitivity and stability. On the other hand, the composition of Comparative Example 3 in which the ring-closing reaction sufficiently progressed at 250 ° C. in Table 2 significantly reduced the sensitivity and stability.

  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 (4)

100 parts by mass of a hydroxypolyamide having a repeating unit represented by the following general formula (1), at least one ester compound represented by the following general formula (3 ) or at least one compound 0 represented by the following general formula (5) A positive photosensitive resin composition comprising 1 to 30 parts by mass and 1 to 100 parts by mass of a photosensitive diazoquinone compound.

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

(In the formula, R ₅ is a monovalent monovalent alkyl having 1 to 8 carbon atoms which may be substituted with at least one of a halogen atom, a nitro group, a cyano group, an alkylcarbonyl group, an amide group, an imide group, or an ester group. R ₆ represents an organic group or a hydrogen atom, and R ₆ is an alkyl group, an alkylcarbonyloxy group, a hydroxyl group, an amide group, an amino group, or an imino group. R ₇ represents a divalent organic group having 3 to 8 carbon atoms, which may be substituted with at least one of a halogen atom, a nitro group, a cyano group, an alkoxyl group, an amino group, or an imino group. R ₈ represents an organic group, and R ₈ represents a monovalent organic group having 6 to 10 carbon atoms which may be substituted with a halogen atom or a hydroxyl group.

(In the formula, R ₁₀ represents a divalent organic group which may be substituted with at least one of a halogen atom, a nitro group, a cyano group, an alkoxyl group, an amino group, or an imino group.)
Provided that R ¹ R ² C═N—O—SO ₂ —R (wherein R is an aryl group, alkyl group, perfluoroalkyl group, R ¹ is a cyano group, R ² is a methoxyphenyl group, A compound represented by the following formula C18, a compound represented by the following formula C3, 1,3-butane sultone, methanesulfonic acid methyl ester, methanesulfonic acid ethyl ester, methanesulfonic acid The phenyl ester and methanesulfonic acid 2-isopropylethyl ester are excluded.

Relative to 100 parts by weight of hydroxy polyamides, positive photosensitive resin composition of claim 1 which further comprises an acrylate-based compound to 100 parts by weight. (1) The positive photosensitive resin composition according to claim 1 or 2 is formed on a substrate in the form of a layer or a film, and (2) exposure with actinic radiation through a mask, A method for producing a cured relief pattern, comprising directly irradiating an electron beam or an ion beam, (3) eluting and removing an exposed portion or an irradiated portion, and (4) heat-treating the obtained relief pattern. A semiconductor device comprising a cured relief pattern layer obtained by the method for producing a cured relief pattern according to claim 3 .