JP2009230098A - Photosensitive resin composition, pattern forming method, and semiconductor device and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that gives a cured relief pattern with high resolution on copper or a copper alloy, as a useful coating film for manufacturing electric and electronic materials, and to provide a pattern forming method, a semiconductor device and a method for manufacturing the device using the above composition. <P>SOLUTION: The photosensitive resin composition contains: (A) 100 parts by mass of a polyimide precursor having a specified structure or a polybenzoxazole precursor having a specified structure; (B) 1 to 40 parts by mass of a photosensitive agent; and (C) 0.1 to 20 parts by mass of a phenolic compound having a specified structure. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition useful for the production of electrical / electronic materials such as semiconductor devices and multilayer wiring boards, a pattern forming method using the same, a semiconductor device, and a method for producing the same.

  As materials for the surface protective film and the interlayer insulating film of semiconductor elements, polyimide resins and polybenzoxazole resins having both excellent heat resistance, electrical characteristics, and mechanical characteristics capable of withstanding heat of 200 ° C. or higher are known. The polyimide resin and the polybenzoxazole resin are generally provided in the form of a photosensitive polyimide precursor composition or a photosensitive polybenzoxazole precursor composition. By applying these to a support such as a silicon wafer and patterning with actinic light, development, and thermal cyclization treatment, a microfabricated heat-resistant resin composition film can be easily formed on the support. In comparison with conventional non-photosensitive polyimide, the process can be greatly shortened. The photosensitive polyimide precursor composition and the photosensitive polybenzoxazole precursor composition are classified into two types, a positive type material and a negative type material, depending on the pattern formation method. The former positive type is a method of obtaining a pattern by making an exposed portion soluble in a developer, and the latter negative type is a method of obtaining a pattern by making an exposed portion insoluble in a developer. . In the present specification, the term “photosensitive resin composition” means a photosensitive polyimide precursor composition or a photosensitive polybenzoxazole precursor composition unless otherwise specified.

  As a negative material, a system composed of a polyimide precursor and dichromate (see Patent Document 1) was first proposed. This material has practical photosensitivity and high film forming ability. On the other hand, it has disadvantages such as lack of storage stability of the photosensitive resin composition and residual chromium ions in the polyimide, and it has not been put into practical use. In order to avoid such a problem, for example, a method of mixing a compound having a photosensitive group with a polyimide precursor (see Patent Document 2), a functional group in the polyimide precursor and a functional group of a compound having a photosensitive group. There have been proposed methods of reacting to give photosensitive groups (see Patent Documents 3 and 4) and the like, and materials made of these techniques are currently employed in the production of many semiconductor devices. Since the negative photosensitive polyimide needs to use a large amount of an organic solvent such as N-methyl-2-pyrrolidone as a developing solution in the developing process, a dilute alkali is used for the purpose of reducing the cost of the developing solution. Various photosensitive resin compositions that can be developed and patterned with an aqueous solution have been proposed. For example, in Patent Document 5, glycidyl methacrylate is allowed to act on a carboxyl group of a polyamic acid, a photosensitive group is introduced via an ester bond, and a hydroxyl group derived from an epoxy ring generated at this time is blocked with an intramolecular cyclic acid anhydride. A negative photosensitive material of the shape has been proposed.

  On the other hand, as a positive type material, a polybenzoxazole precursor composition obtained by mixing an alkaline aqueous solution-soluble hydroxypolyamide, such as a polybenzoxazole precursor, with a photoactive component such as a photosensitive diazoquinone compound is used as a positive type photosensitive resin composition. Is disclosed (see Patent Document 6). 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.

  By the way, with the progress of miniaturization of semiconductor devices and the fact that the operating frequency has reached GHz, the wiring resistance of semiconductor devices can no longer be ignored. As a result, the gold or aluminum wiring used so far has been changed to a copper or copper alloy wiring having a lower resistance. However, the conventional photosensitive resin technology has a problem in that discoloration / corrosion of copper or copper alloy occurs because the polyimide precursor and copper or copper alloy easily react.

  A photosensitive resin composition containing a phenol compound is known. For example, Patent Document 7 describes that by using a phenol compound, the transparency of the polyimide precursor resin does not decrease even by heat treatment.

  Patent Document 8 describes that by using a phenol compound in the same manner, the polybenzoxazole precursor resin is less discolored even by heat treatment.

Japanese Patent Publication No.49-17374 JP-A-54-109828 JP-A-56-24343 JP-A-60-1000014 JP-B-2-37934 Japanese Examined Patent Publication No. 63-96162 Japanese Patent Laid-Open No. 11-148008 Japanese Patent No. 3919147

  The present invention is a photosensitive resin composition that can give a high-resolution polyimide or polybenzoxazole pattern without causing discoloration or corrosion even on copper or a copper alloy, and a polyimide or polybenzoxazole using the photosensitive resin composition It is an object of the present invention to provide a pattern forming method for forming the pattern, a semiconductor device, and a manufacturing method thereof.

｛式中、Ｘは、炭素数６〜３２の４価の有機基であり、Ｙは炭素数４〜３０の２価の有機基であり、そしてＲ及びＲ’は、それぞれ独立にオレフィン性二重結合を有する１価の基又はヒドロキシル基を示す。｝で表される繰り返し単位を有するポリイミド前駆体、又は下記一般式（２）：

｛式中、Ｘ₁は少なくとも２個の炭素原子を有する４価の有機基であり、Ｘ₂、Ｙ₁、及びＹ₂は、それぞれ独立に少なくとも２個の炭素原子を有する２価の有機基であり、ｍは１〜１０００の整数であり、ｎは０〜５００の整数であり、そしてｍ／（ｍ＋ｎ）＞０．５である。なお、Ｘ₁及びＹ₁を含むｍ個の繰り返し単位、並びにＸ₂及びＹ₂を含むｎ個の繰り返し単位の配列順序は問わない。｝で表される構造を有するポリベンゾオキサゾール前駆体１００質量部、
（Ｂ）感光剤１〜４０質量部、及び
（Ｃ）下記一般式（３）：

｛式中、Ｒ₁は下記一般式（４）：

で表される有機基であり、
式（４）中、Ｒ₂及びＲ₃は、それぞれ独立に水素原子又は炭素数１〜６の１価の有機基であり、そしてＲ₄は下記一般式（５）：

で表される基又はフェニル基であり、式（５）中、Ｒ₅、Ｒ₆及びＲ₇は、それぞれ独立に水素原子又は炭素数１〜６の１価の有機基である。但し、Ｒ₅、Ｒ₆及びＲ₇のうち少なくとも２つは炭素数１〜６の１価の有機基である。｝で表される化合物からなる群から選ばれる少なくとも１種のフェノール化合物０．１〜２０質量部
を含む感光性樹脂組成物。 [1] (A) The following general formula (1):

{Wherein X is a tetravalent organic group having 6 to 32 carbon atoms, Y is a divalent organic group having 4 to 30 carbon atoms, and R and R ′ are each independently an olefinic divalent group. A monovalent group or a hydroxyl group having a heavy bond is shown. } A polyimide precursor having a repeating unit represented by the following general formula (2):

{Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, and X ₂ , Y ₁ and Y ₂ are each independently a divalent organic group having at least 2 carbon atoms. Where m is an integer from 1 to 1000, n is an integer from 0 to 500, and m / (m + n)> 0.5. The arrangement order of m repeating units including X ₁ and Y ₁ and n repeating units including X ₂ and Y ₂ is not limited. } 100 parts by mass of a polybenzoxazole precursor having a structure represented by:
(B) 1 to 40 parts by mass of photosensitizer, and (C) the following general formula (3):

{In the formula, R ₁ represents the following general formula (4):

An organic group represented by
In formula (4), R ₂ and R ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, and R ₄ is represented by the following general formula (5):

In formula (5), R ₅ , R ₆ and R ₇ are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. However, at least two of R ₅ , R ₆ and R ₇ are monovalent organic groups having 1 to 6 carbon atoms. } The photosensitive resin composition containing 0.1-20 mass parts of at least 1 sort (s) of phenolic compounds chosen from the group which consists of a compound represented by these.

で表される化合物である、上記［１］に記載の感光性樹脂組成物。 [2] The phenol compound of the above (C) is represented by the following formula (6):

The photosensitive resin composition according to the above [1], which is a compound represented by the formula:

[3] A method of forming a polyimide or polybenzoxazole pattern on a substrate,
(A) A coating film forming step in which the photosensitive resin composition according to the above [1] or [2] is applied on a substrate and dried to form a coating film,
(B) After exposing the coating film with actinic rays through a photomask or reticle having a pattern or directly, the unexposed part is removed with a solvent to obtain a polyimide precursor pattern, or the exposed part is an alkaline aqueous solution. A precursor pattern forming step of removing to obtain a pattern of a polybenzoxazole precursor;
(C) A pattern forming method including a curing step of forming a polyimide or polybenzoxazole pattern by heat curing the polyimide precursor or the polybenzoxazole precursor pattern.

  [4] A semiconductor device having a base material which is a semiconductor element, and a polyimide or polybenzoxazole pattern formed on the base material by the pattern forming method according to [3].

  [5] A method for manufacturing a semiconductor device, comprising using a semiconductor element as a substrate and including the pattern forming method according to [3] as a part of the process.

  According to the present invention, for example, a photosensitive resin composition capable of giving a high resolution pattern of polyimide or polybenzoxazole without causing discoloration or corrosion even on copper or a copper alloy, and a polyimide using the photosensitive resin composition Alternatively, a pattern forming method for forming a polybenzoxazole pattern, a semiconductor device, and a method for manufacturing the same can be provided.

  Hereinafter, embodiments of the present invention will be described in detail.

  The photosensitive resin composition of the present invention comprises (A) a polyimide precursor having a repeating unit represented by the following general formula (1) or a polybenzoxazole precursor having a structure represented by the following general formula (2). 100 parts by mass (hereinafter also referred to as (A) polyimide precursor or polybenzoxazole precursor), (B) 1 to 40 parts by mass of photosensitizer, and (C) represented by the general formula (3) described later. 0.1-20 mass parts of at least 1 sort (s) of phenolic compounds (henceforth (C) phenolic compound) chosen from the group which consists of a compound are included.

(A) Polyimide precursor or polybenzoxazole precursor The component (A) of the present invention is a polyimide precursor or a polybenzoxazole precursor. When the component (A) is a polyimide precursor, a negative photosensitive resin composition is obtained, and when the component (A) is a polybenzoxazole precursor, a positive photosensitive resin composition is obtained.

｛式中、Ｘは、炭素数６〜３２の４価の有機基であり、Ｙは炭素数４〜３０の２価の有機基であり、そしてＲ及びＲ’は、それぞれ独立にオレフィン性二重結合を有する１価の基又はヒドロキシル基を示す。｝
で表される繰り返し単位を有する。この繰り返し単位は、テトラカルボン酸又はその誘導体とジアミンとを縮合させて得られるポリアミド酸エステルの繰り返し単位である。 The polyimide precursor used as the component (A) (hereinafter sometimes simply referred to as “polyimide precursor”) is represented by the following general formula (1):

{Wherein X is a tetravalent organic group having 6 to 32 carbon atoms, Y is a divalent organic group having 4 to 30 carbon atoms, and R and R ′ are each independently an olefinic divalent group. A monovalent group or a hydroxyl group having a heavy bond is shown. }
It has the repeating unit represented by these. This repeating unit is a repeating unit of a polyamic acid ester obtained by condensing tetracarboxylic acid or a derivative thereof and diamine.

が挙げられ、これらは単独でも２種以上が組合されても構わない。これらのＸ基は耐熱性と感光特性を両立するという点で好ましい。 The X group in the general formula (1) is derived from the above tetracarboxylic acid or a derivative thereof. The number of carbon atoms in the X group is 6 or more for the purpose of obtaining heat resistance and 32 or less for the purpose of obtaining photosensitive characteristics.
Examples of preferred X groups include the following formula (7):

These may be used alone or in combination of two or more. These X groups are preferable in terms of achieving both heat resistance and photosensitive characteristics.

が挙げられ、これらは単独でも２種以上が組合されても構わない。これらのＹ基は、耐熱性と感光特性を両立するという点で好ましい。 The Y group in the general formula (1) is derived from the diamine. The number of carbon atoms in the Y group is 4 or more for the purpose of obtaining heat resistance and 30 or less for the purpose of obtaining photosensitive characteristics. As an example of a preferable Y group, the following formula (8):

These may be used alone or in combination of two or more. These Y groups are preferable in terms of achieving both heat resistance and photosensitive characteristics.

  Examples of methods for imparting photosensitivity when using a polyimide precursor in the photosensitive resin composition include an ester bond type and an ion bond type. The former is a method of introducing a photopolymerizable group, that is, a compound having an olefinic double bond, into the side chain of the polyimide precursor by an ester bond, and the latter is an amino compound of an acrylic compound having a carboxyl group and an amino group of the polyimide precursor. In this method, a photopolymerizable group is imparted by bonding a group via an ionic bond.

Typically, the ester bond type polyimide precursor is obtained by esterifying a tetracarboxylic dianhydride and an alcohol having an olefinic double bond to obtain a tetracarboxylic acid diester, which is reacted with a diamine. Obtained. In this case, R and R ′ in the general formula (1) are each preferably a monovalent group having an olefinic double bond.
The tetracarboxylic dianhydride is preferably a tetracarboxylic acid having the structure of the above formula (7), and the diamine is preferably a diamine having the structure of the above formula (8).
Specific examples of the alcohol having an olefinic double bond include 2-methacryloyloxyethyl alcohol, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-2-propyl alcohol, 2-methacrylamidoethyl alcohol, and 2-acrylamidoethyl alcohol. , Methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxy-3-methoxypropyl Acrylate, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy- -Butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2 -Hydroxy-3-cyclohexylalkoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloxyethyl-2-hydroxypropyl phthalate, 2-acryloxyethyl- Examples include 2-hydroxypropyl phthalate, glycerin diacrylate, and glycerin dimethacrylate. These alcohols can be used alone or in admixture of two or more.

  Further, as described in JP-A-6-80776, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and allyl alcohol are partially mixed with the alcohol having the olefinic double bond. Can also be used.

  Theoretically, the amount of alcohols used for esterification of tetracarboxylic dianhydride is 1.0 equivalent with respect to 1.0 equivalent of tetracarboxylic dianhydride. When tetracarboxylic acid diester is synthesized using alcohol so as to be 1.01 to 1.10 equivalents relative to 1.0 equivalent of dianhydride, the storage stability of the finally obtained photosensitive resin composition is improved. Since it improves, it is preferable.

  The molar ratio of the tetracarboxylic acid diester used for the synthesis of the polyimide precursor to the diamine is preferably around 1.0, but depending on the molecular weight of the polyamic acid ester which is the target polyimide precursor, 0.7 to It can be in the range of 1.3.

On the other hand, the polyimide precursor used in the ionic bond type is typically obtained by reacting tetracarboxylic dianhydride with diamine. In this case, at least one of R and R ′ in the general formula (1) is a hydroxyl group.
The tetracarboxylic dianhydride is preferably a tetracarboxylic acid having the structure of the above formula (7), and the diamine is preferably a diamine having the structure of the above formula (8). An ionic bond type is obtained by adding an acrylic compound described later to the obtained polyamide precursor to form a composition.

  As a specific method for synthesizing the polyimide precursor, a conventionally known method can be employed. About this, the method shown by the international publication 00/43439 pamphlet can be used, for example.

  The molecular weight of the polyimide precursor is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, as measured by polystyrene-reduced weight average molecular weight by gel permeation chromatography. . When the weight average molecular weight is 8,000 or more, the mechanical properties are improved, and when it is 150,000 or less, the dispersibility in the developer is improved, and the resolution performance of the relief pattern is improved. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from standard organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

｛式中、Ｘ₁は少なくとも２個の炭素原子を有する４価の有機基であり、Ｘ₂、Ｙ₁、及びＹ₂は、それぞれ独立に少なくとも２個の炭素原子を有する２価の有機基であり、ｍは１〜１０００の整数であり、ｎは０〜５００の整数であり、そしてｍ／（ｍ＋ｎ）＞０．５である。なお、Ｘ₁及びＹ₁を含むｍ個の繰り返し単位、並びにＸ₂及びＹ₂を含むｎ個の繰り返し単位の配列順序は問わない。｝
で表される繰り返し単位を有する。ポリベンゾオキサゾール前駆体は、上記一般式（２）中のｍ個のジヒドロキシジアミド単位（以下、単にジヒドロキシジアミド単位という場合がある。）を有するポリマーであり、上記一般式（２）中のｎ個のジアミド単位（以下、単にジアミド単位という場合がある。）を有してもよい。 The polybenzoxazole precursor used as the component (A) (hereinafter sometimes simply referred to as “polybenzoxazole precursor”) is represented by the following general formula (2):

{Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, and X ₂ , Y ₁ and Y ₂ are each independently a divalent organic group having at least 2 carbon atoms. Where m is an integer from 1 to 1000, n is an integer from 0 to 500, and m / (m + n)> 0.5. The arrangement order of m repeating units including X ₁ and Y ₁ and n repeating units including X ₂ and Y ₂ is not limited. }
It has the repeating unit represented by these. The polybenzoxazole precursor is a polymer having m dihydroxydiamide units in the general formula (2) (hereinafter sometimes simply referred to as dihydroxydiamide units), and n in the general formula (2). Diamide units (hereinafter sometimes simply referred to as diamide units).

The number of carbon atoms of X ₁ is 2 or more for the purpose of obtaining photosensitive characteristics, the number of carbon atoms of X ₂ is 2 or more for the purpose of obtaining photosensitive characteristics, and the number of carbon atoms of Y ₁ is 2 for the purpose of obtaining photosensitive characteristics. The number of carbon atoms of Y ₂ is 2 or more for the purpose of obtaining photosensitive characteristics.

The dihydroxydiamide unit can be synthesized from a bisaminophenol having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ and a dicarboxylic acid having a structure of Y ₁ (COOH) ₂ . Here, the two groups of amino group and hydroxy group of the bisaminophenol are in ortho positions with each other, and the dihydroxydiamide is closed by heating at about 250 to 400 ° C. to form a heat resistant resin. Changes to polybenzoxazole. m is 1 or more for the purpose of obtaining photosensitive characteristics and 1000 or less for the purpose of obtaining photosensitive characteristics. 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.

The polybenzoxazole precursor may be condensed with n diamide units as necessary. The diamide unit can be synthesized from a diamine having a X ₂ (NH ₂ ) ₂ structure and a dicarboxylic acid having a Y ₂ (COOH) ₂ structure. n is in the range of 0 to 500. When n is 500 or less, good photosensitive characteristics can be obtained. n is more preferably in the range of 0-10. If the ratio of the diamide unit to the dihydroxydiamide unit is too high, the solubility in an alkaline aqueous solution used as a developer is lowered. Therefore, the value of m / (m + n) in the general formula (2) is more than 0.5. It is more preferably 0.7 or more, and most preferably 0.8 or more.

で示されるものが、感光特性の点で好ましい。 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 can be used alone or in combination of two or more. As the X ₁ group in the bisaminophenol, the following formula (9):

Is preferable in terms of photosensitive characteristics.

As the diamine having a structure of X ₂ (NH _{2) 2,} an aromatic diamine, a silicon diamine, and the like. Among these, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl ether, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'- Diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2′-bis (4-aminophenyl) ) Propane, 2,2'-bis (4-aminophenyl) hexa Fluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2,4-bis (4-aminophenyl) -1-pentene, 4-methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-4-aminobenzyl) benzene, Imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6) -amino-1- (4-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4,4′-diaminoazobenzene, 4,4′-diaminodi Phenylurea, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 4,4'-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, 4,4′-diaminobiphenyl, 4,4 '-Diaminobenzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-dia Minobiphenyl, o-toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-amino) Phenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-di- (3-aminophenoxy) diphenylsulfone, 4,4 At least one selected from the group consisting of a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, and a phenyl group, such as' -diaminobenzanilide and the aromatic nucleus of these aromatic diamines And compounds substituted by groups or atoms.

  Further, as the diamine, silicon diamine can be selected in order to enhance the adhesion to the substrate, and examples thereof include bis (4-aminophenyl) dimethylsilane and bis (4-aminophenyl) tetramethylsiloxane. Bis (4-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane Examples thereof include siloxane and bis (γ-aminopropyl) tetraphenyldisiloxane.

（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価の基を表す。）
から選ばれる芳香族基であるものが挙げられる。これらは感光特性の点で好ましい。 Further, it preferred dicarboxylic acid having Y ₁ (COOH) ₂ or Y ₂ (COOH) ₂ structure, Y _1, Y ₂ is represented by the following general formula (10):

Wherein A is a divalent group selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —. Represents a group.)
What is an aromatic group chosen from these is mentioned. These are preferable in terms of photosensitive characteristics.

で示されるものが挙げられる。 The polybenzoxazole precursor may have a terminal group sealed with a specific organic group. Examples of such a sealing group include groups having an unsaturated bond as described in JP-A-5-197153, and when sealed with these, the photosensitive resin composition of the present invention is used. It is expected that the mechanical properties (particularly elongation) and the cured relief pattern shape of the coated film after heat curing will be good. As a suitable example of such a sealing group, the following formula (11):

The thing shown by is mentioned.

  The polystyrene-reduced weight average molecular weight of the polybenzoxazole precursor by gel permeation chromatography is preferably 3,000 to 70,000, and more preferably 6,000 to 50,000. The weight average molecular weight is preferably 3,000 or more from the viewpoint of the physical properties of the cured relief pattern. Moreover, from a viewpoint of resolution, 70,000 or less is preferable. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from standard organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

(B) Photosensitizer (B) Photosensitizer, which is a component of the photosensitive resin composition of the present invention, uses a negative polyimide precursor or a positive polybenzoxazole precursor as component (A). It depends on what you do.

  First, the case where a polyimide precursor is used as the component (A) will be described. In this case, a photoinitiator is used as the photosensitizer (B), for example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenylketone, dibenzylketone, benzophenone derivatives such as fluorenone, Acetophenone derivatives such as 2′-diethoxyacetophenone and 2-hydroxy-2-methylpropiophenone, thioxanthone derivatives such as 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone, Benzyl derivatives such as benzyl, benzyldimethyl ketal and benzyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin methyl ether, 2,6-di (4′-diazidobenzal) -4 Azides such as methylcyclohexanone and 2,6′-di (4′-diazidobenzal) cyclohexanone, 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenylpropanedione-2- (O-methoxycarbonyl) oxime, 1-phenylpropanedione-2- (O-ethoxycarbonyl) oxime, 1-phenylpropanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2- ( O-ethoxycarbonyl) oxime, oximes such as 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, N-arylglycines such as N-phenylglycine, and peroxidations such as benzoyl peroxide , Aromatic biimidazoles, titanocenes Etc. are used. Among these, the said oximes are preferable at the point that thick film i-line curability and photosensitivity are favorable.

  Furthermore, as described above, in the case of the ionic bond type, an acrylic compound having an amino group is used to impart a photopolymerizable group to the side chain via an ionic bond. For example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate Dialkylaminoalkyl acrylate or methacrylate such as diethylaminobutyl methacrylate is preferable, and among them, from the viewpoint of photosensitive properties, the alkyl group on the amino group is a dialkylaminoalkyl acrylate having 1 to 10 carbon atoms and an alkyl chain having 1 to 10 carbon atoms. Preferred methacrylate Used in.

  The addition amount of these photoinitiators is 1-40 mass parts with respect to 100 mass parts of polyimide precursors, and 2-20 mass parts is preferable. The photoinitiator is excellent in photosensitivity by adding 1 part by mass or more to 100 parts by mass of the (A) polyimide precursor, and thick film curability is excellent by adding 40 parts by mass or less.

  Next, the case where a polybenzoxazole precursor is used as the component (A) will be described. In this case, a photoacid generator is used as the photosensitive agent (B). Specifically, a naphthoquinone diazide compound, an onium salt, a halogen-containing compound, and the like can be used. From the viewpoint of solvent solubility and storage stability. Therefore, a compound having a naphthoquinonediazide structure (hereinafter also referred to as “naphthoquinonediazide compound”) is preferable.

  Examples of the onium salt include iodonium salts, sulfonium salts, fosiphonium salts, phosphonium salts, ammonium salts, and diazonium salts. The onium selected from the group consisting of diaryl iodonium salts, triaryl sulfonium salts, and trialkyl sulfonium salts. Salts are preferred.

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and the like, and trichloromethyltriazine is preferable.

  Examples of the naphthoquinone diazide compound include compounds having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure, such as US Pat. No. 2,772,972, US Pat. No. 2,797,213. No., US Pat. No. 3,669,658, and the like. The naphthoquinonediazide structure is typically a 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and a 1,2-naphthoquinonediazide of the polyhydroxy compound. It is at least one compound selected from the group consisting of -5-sulfonic acid esters (hereinafter also referred to as “NQD compound”).

  The NQD compound can be obtained by subjecting the naphthoquinone diazide sulfonic acid compound to sulfonyl chloride with chlorosulfonic acid or thionyl chloride and subjecting the obtained naphthoquinone diazide sulfonyl chloride to a polyhydroxy compound according to a conventional method. . For example, a predetermined amount of a polyhydroxy compound and 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride is mixed with a base such as triethylamine in a solvent such as dioxane, acetone, or tetrahydrofuran. It can be obtained by carrying out esterification in the presence of a sex catalyst and washing the resulting product with water and drying.

  The example of the NQD compound of the preferable hydroxy compound in this invention is given to the following.

｛式中、ｎ₁〜ｎ₄は、それぞれ独立に１又は２を示す。また、Ｒ₈〜Ｒ₁₇は、それぞれ独立に水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アリル基、及びアシル基からなる群から選択される少なくとも１つの１価の基を示す。また、Ｙ₃〜Ｙ₅は、それぞれ独立に、単結合、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−ＣＯ₂−、シクロペンチリデン、シクロヘキシリデン、フェニレン、及び下記一般式（１３）〜（１５）：

（式中、Ｒ₁₈及びＲ₁₉は、それぞれ独立に水素原子、アルキル基、アルケニル基、アリル基、及び置換アリル基からなる群から選択される少なくとも１つの１価の基を示す。）

（Ｒ₂₀〜Ｒ₂₃は、それぞれ独立に水素原子又はアルキル基を示す。ｍ₁は１〜５の整数を示す。）

（Ｒ₂₄〜Ｒ₂₇は、それぞれ独立に水素原子又はアルキル基を示す。）
で示される有機基からなる群から選択される少なくとも１つの２価の基を示す。｝
で表されるポリヒドロキシ化合物のＮＱＤ化合物が挙げられる。 As a preferable NQD compound, the following general formula (12):

{Wherein, n ₁ ~n ₄ each independently represent 1 or 2. R _{8 to} R ₁₇ each independently represent at least one monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, and an acyl group. Y _{3 to} Y ₅ are each independently a single bond, —O—, —S—, —SO—, —SO ₂ —, —CO—, —CO ₂ —, cyclopentylidene, cyclohexylidene, Phenylene and the following general formulas (13) to (15):

(Wherein R ₁₈ and R ₁₉ each independently represents at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an allyl group, and a substituted allyl group.)

(R _{20 to} R ₂₃ each independently represents a hydrogen atom or an alkyl group. M ₁ represents an integer of ₁ to 5.)

(R _{24 to} R ₂₇ each independently represent a hydrogen atom or an alkyl group.)
And at least one divalent group selected from the group consisting of organic groups represented by }
The NQD compound of the polyhydroxy compound represented by these is mentioned.

  Specific examples of the compound include NQD compounds of polyhydroxy compounds described in (Chemical Formula 18) to (Chemical Formula 32) of JP-A No. 2001-109149.

のポリヒドロキシ化合物のＮＱＤ化合物が、感度が高く、感光性樹脂組成物中での析出性が低いことから好ましい。 In particular, the following formula (16):

NQD compounds of polyhydroxy compounds are preferred because of their high sensitivity and low precipitation in the photosensitive resin composition.

（Ｘ₃は下記式（１８）：

で表される有機基から選ばれる少なくとも１つの４価の基を示す。Ｒ₂₈〜Ｒ₃₁はそれぞれ独立に１価の有機基を示し、ｌは０又は１を示し、ｍ₂〜ｍ₅はそれぞれ独立に０〜３の整数を示し、ｎ₅〜ｎ₈はそれぞれ独立に０〜２の整数を示す。）
で表されるポリヒドロキシ化合物のＮＱＤ化合物が挙げられる。 Other preferred NGD compounds include the following general formula (17):

(X ₃ is the following formula (18):

And at least one tetravalent group selected from organic groups represented by the formula: R _{28 to} R ₃₁ each independently represents a monovalent organic group, l represents 0 or 1, m _{2 to} m ₅ each independently represents an integer of 0 to 3, and n _{5 to} n ₈ each independently Represents an integer of 0-2. )
The NQD compound of the polyhydroxy compound represented by these is mentioned.

Specific examples of the compound include those described in (Chemical Formula 23) to (Chemical Formula 28) of JP-A No. 2001-092138. Among them, the following NQD compounds of polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the photosensitive resin composition.

（ｍ₆は３〜８の整数を示し、ｍ₆×ｊ個のＬ₃はそれぞれ独立に１個以上の炭素原子を有する１価の有機基を示し、ｊは１〜５の整数を示し、ｍ₆個のＬ₁、及びｍ₆個のＬ₂はそれぞれ独立に水素原子及び１価の有機基からなる群から選択される１価の基を示す。）
で表されるポリヒドロキシ化合物のＮＱＤ化物が挙げられる。 As another preferable NGD compound, the following general formula (19):

(M ₆ represents an integer of 3 to 8, m ₆ × j number of L ₃ is a monovalent organic group having 1 or more carbon atoms each independently, j is an integer of 1 to 5, m ₆ L ₁ and m ₆ L ₂ each independently represent a monovalent group selected from the group consisting of a hydrogen atom and a monovalent organic group.
NQD compounds of polyhydroxy compounds represented by the formula:

  Specific preferred examples include those described in (Chemical Formula 24) and (Chemical Formula 25) of JP-A-2004-347902.

（式中、ｐは０から９の整数である。）
で表されるポリヒドロキシ化合物のＮＱＤ化物が、感度が高く、感光性樹脂組成物中での析出性が低いことから好ましい。 Among them, the following general formula:

(Wherein p is an integer from 0 to 9)
NQD compounds of the polyhydroxy compound represented by the formula are preferred because of their high sensitivity and low precipitation in the photosensitive resin composition.

（Ａ₂は脂肪族の３級又は４級炭素を含む２価の有機基を示し、Ｍは下記の化学式：

で表される基から選ばれる少なくとも１つの２価の基を示す。）
で表されるポリヒドロキシ化合物のＮＱＤ化物が挙げられる。 Other preferred NQD compounds include
The following general formula (20):

(A ₂ represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and M represents the following chemical formula:

And at least one divalent group selected from the group represented by: )
NQD compounds of polyhydroxy compounds represented by the formula:

  Specific examples of the compound include those described in (Chemical Formula 22) to (Chemical Formula 28) of JP-A No. 2003-131368.

（Ｌ₃は−ＣＨ₂−、−Ｏ−からなる群から選択される基を示し、Ｌ₄は水素原子、又はメチル基を示す。）

（Ｌ₅は−ＣＨ₂−、−Ｏ−からなる群から選択される基を示し、Ｌ₆は水素原子、又はメチル基を示す。） Among them, the following NQD compounds of polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the photosensitive resin composition.

(L ₃ represents a group selected from the group consisting of —CH ₂ — and —O—, and L ₄ represents a hydrogen atom or a methyl group.)

(L ₅ represents a group selected from the group consisting of —CH ₂ — and —O—, and L ₆ represents a hydrogen atom or a methyl group.)

（式中、Ｒ₃₁〜Ｒ₃₃は下記の一般式で表される１価の有機基を示し、それぞれ同じであっても異なっていてもよい。また、ｍ₇〜ｍ₉はそれぞれ独立に０〜２の整数である。）
で表されるポリヒドロキシ化合物のＮＱＤ化合物が挙げられる。

（Ｒ₃₄は、それぞれ独立に、アルキル基、及びシクロアルキル基から選ばれる少なくとも１つの１価の有機基を示す。また、ｍ₁₀はそれぞれ独立に０〜２の整数である。）
具体的な化合物としては、特開２００４−１０９８４９号公報の（化１７）〜（化２２）に記載されるポリヒドロキシ化合物のＮＱＤ化合物が挙げられる。
その中でも、下記のポリヒドロキシ化合物のＮＱＤ化物が、感度が高く、感光性樹脂組成物中での析出性が低いことから好ましい。

Examples of other preferable NQD compounds include the following general formula (21):

(In the formula, R _{31 to} R ₃₃ represent monovalent organic groups represented by the following general formula, and may be the same or different. M _{7 to} m ₉ are each independently 0. It is an integer of ~ 2.)
The NQD compound of the polyhydroxy compound represented by these is mentioned.

(R ₃₄ independently represents at least one monovalent organic group selected from an alkyl group and a cycloalkyl group. M ₁₀ is each independently an integer of 0 to 2.)
Specific examples of the compound include NQD compounds of polyhydroxy compounds described in (Chemical Formula 17) to (Chemical Formula 22) of JP-A No. 2004-109849.
Among these, NQD compounds of the following polyhydroxy compounds are preferable because of their high sensitivity and low precipitation in the photosensitive resin composition.

（Ｒ₃₅は水素原子、アルキル基、アルコキシ基、及びシクロアルキル基から選ばれた少なくとも１つの１価の有機基を示す。）
で表されるポリヒドロキシ化合物のＮＱＤ化合物が挙げられる。 Examples of other preferable NQD compounds include the following general formula (22):

(R ₃₅ represents at least one monovalent organic group selected from a hydrogen atom, an alkyl group, an alkoxy group, and a cycloalkyl group.)
The NQD compound of the polyhydroxy compound represented by these is mentioned.

  Specific examples of the compound include those described in (Chemical Formula 18) to (Chemical Formula 22) of JP-A No. 2001-356475.

他の好ましいＮＱＤ化合物の例としては、下記一般式（２３）：

｛Ｒ₃₆は下記の一般式：

（式中、Ｒ₄₀は、１価のアルキル基又はシクロアルキル基を示す。また、ｍ₁₄は０〜２の整数を示す。）
で表される１価の有機基を示す。また、ｍ₁₁〜ｍ₁₃はそれぞれ独立に０〜２の整数を示す。また、Ｒ₃₇〜Ｒ₃₉はそれぞれ独立に水素原子、アルキル基又はシクロアルキル基を示す。）
で表されるポリヒドロキシ化合物のＮＱＤ化合物が挙げられる。 Among these, NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the photosensitive resin composition.

Examples of other preferable NQD compounds include the following general formula (23):

{ _R36 is the following general formula:

(In the formula, R ₄₀ represents a monovalent alkyl group or cycloalkyl group. M ₁₄ represents an integer of 0 to 2.)
The monovalent organic group represented by these is shown. M _{11 to} m ₁₃ each independently represents an integer of 0 to 2. R _{37 to} R ₃₉ each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group. )
The NQD compound of the polyhydroxy compound represented by these is mentioned.

  Specific examples of the compound include NQD compounds of polyhydroxy compounds described in (Chemical 15) and (Chemical 16) of JP-A-2005-008626.

Among them, the following NQD compounds of polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the photosensitive resin composition.

As other NQD compounds, for example, the following NQD compounds of polyhydroxy compounds are preferable.

  As the naphthoquinone diazide sulfonyl group in the NQD compound as described above, both a 5-naphthoquinone diazide sulfonyl group and a 4-naphthoquinone diazide sulfonyl group are preferably used. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. Further, the 5-naphthoquinonediazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. Further, a naphthoquinone diazide sulfonyl ester compound in which 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, or 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester compound. Can also be used in combination.

  The compounding quantity of these photo-acid generators is 1-40 mass parts with respect to 100 mass parts of polybenzoxazole precursors, and 5-30 mass parts is preferable. If the blending amount of the photoacid generator is 1 part by mass or more, the patterning property by the photosensitive resin composition is good, and if it is 40 parts by mass or less, the tensile elongation of the film after curing of the photosensitive resin composition is high. Good and little development residue (scum) in the exposed area.

（式中、Ｒ₁は下記一般式（４）：

で表される有機基であり、式（４）中、Ｒ₂及びＲ₃はそれぞれ独立に水素原子又は炭素数１〜６の１価の有機基であり、そしてＲ₄は下記一般式（５）：

で表される基又はフェニル基であり、式（５）中、Ｒ₅、Ｒ₆及びＲ₇はそれぞれ独立に水素原子又は炭素数１〜６の１価の有機基である。但し、Ｒ₅、Ｒ₆及びＲ₇のうち少なくとも２つは炭素数１〜６の１価の有機基である。｝
で表される化合物からなる群から選ばれる少なくとも１種のフェノール化合物である。 (C) Phenol compound The (C) phenol compound which is a component of the photosensitive resin composition of the present invention is represented by the following general formula (3):

(In the formula, R ₁ represents the following general formula (4):

In the formula (4), R ₂ and R ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, and R ₄ is represented by the following general formula (5) ):

In formula (5), R ₅ , R ₆ and R ₇ are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. However, at least two of R ₅ , R ₆ and R ₇ are monovalent organic groups having 1 to 6 carbon atoms. }
At least one phenol compound selected from the group consisting of compounds represented by:

(C) Phenol compound (C) A phenol compound has the effect | action which prevents discoloration of copper or a copper alloy, when forming the photosensitive resin composition of this invention on copper or a copper alloy, for example. In the present invention, by using a specific phenol compound, that is, the phenol compound represented by the above general formula (3), no discoloration or corrosion occurs on the copper or copper alloy, and high resolution polyimide or poly The advantage that a benzoxazole pattern can be obtained is obtained.

  (C) As a phenol compound, for example, 1,3,5-tris (3-hydroxy-2,6-dimethyl-4-isopropylbenzyl) -1,3,5-triazine-2,4,6- (1H , 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H , 3H, 5H) -trione, 1,3,5-tris (4-s-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H , 3H, 5H) -trione, 1,3,5-tris [4- (1-ethylpropyl) -3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6 -(1H, 3H, 5H) -trione, 1,3,5-tris [4-to Liethylmethyl-3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (3-hydroxy- 2,6-Dimethyl-4-phenylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl- 3-hydroxy-2,5,6-trimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t- Butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris ( 4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzi L) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2) , 5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-5,6-diethyl) -3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3) -Hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3-hydroxy -2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, H) -trione, 1,3,5-tris (4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione and the like. Among these, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H ) -Trione is particularly preferred.

  (C) The addition amount of a phenol compound is 0.1-20 mass parts with respect to 100 mass parts of (A) polyimide precursor or polybenzoxazole precursor, and 0.5-10 mass parts is preferable. (C) If the addition amount with respect to 100 mass parts of (A) polyimide precursor or polybenzoxazole precursor of a phenol compound is 0.1 mass part or more, the photosensitive resin composition of this invention on copper or a copper alloy, for example When an object is formed, discoloration / corrosion of copper or a copper alloy is prevented, and the photosensitivity is excellent if it is 20 parts by mass or less.

(D) Other components The photosensitive resin composition of this invention may contain components other than the said (A)-(C) component. The preferred other components differ depending on whether a polyimide precursor or a polybenzoxazole precursor is used as the component (A).

  When a polyimide precursor is used as the component (A), each component of the photosensitive resin composition is dissolved in a solvent to form a varnish and used as a solution of the negative photosensitive resin composition. Mention may be made of solvents. As the solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility in the component (A) polyimide precursor and (B) photosensitive agent. Specifically, N, N-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone , Tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone and the like, and these can be used alone or in combination of two or more.

  The said solvent can be used in 30-1500 mass parts with respect to 100 mass parts of polyimide precursors according to the desired coating film thickness and viscosity of the photosensitive resin composition.

  Furthermore, in order to improve the storage stability of the photosensitive resin composition, a solvent containing alcohols is preferable.

  Alcohols that can be used are typically alcohols having an alcoholic hydroxyl group in the molecule and no olefinic double bond. Specific examples include methyl alcohol, ethyl alcohol, and n-propyl. Lactic acid esters such as alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, Propylene glycol monoalkyl ethers such as propylene glycol-2-ethyl ether, propylene glycol-1- (n-propyl) ether, propylene glycol-2- (n-propyl) ether, ethylene glycol methyl Ether, ethylene glycol ethyl ether, mono-alcohols such as ethylene glycol -n- propyl ether, 2-hydroxyisobutyric acid esters, ethylene glycol, di alcohols such as propylene glycol, and the like. Among these, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, and ethyl alcohol are preferable. Particularly, ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, propylene Glycol-1- (n-propyl) ether is more preferred.

  The content of the alcohol having no olefinic double bond in all the solvents is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When the content of alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition is improved. Moreover, when it is 50 mass% or less, the solubility of a polyimide precursor becomes favorable.

  Further, a sensitizer can be optionally added to improve the photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzal). ) Cyclohexanone, 2,6-bis (4′-diethylaminobenzal) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) chalcone, 4,4′-bis (diethylamino) chalcone, p-dimethylaminocinna Milidenindanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) Isonaphthothiazole, 1,3-bis (4 ′ Dimethylaminobenzal) acetone, 1,3-bis (4′-diethylaminobenzal) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxy Carbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N′-ethylethanolamine N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) ) Naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, benzotriazole, 5-methylbenzotriazole, 5-phenyltetrazole and the like. These can be used alone or in combination of, for example, 2 to 5 kinds.

  The sensitizer for improving the photosensitivity is preferably used in an amount of 0.1 to 25 parts by mass with respect to 100 parts by mass of the polyimide precursor.

  In order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond can be optionally added. Such a monomer is preferably a (meth) acryl compound that undergoes a radical polymerization reaction with a photopolymerization initiator, and is not particularly limited to the following, but includes ethylene glycol such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. Polyethylene glycol mono or diacrylate and methacrylate, propylene glycol or polypropylene glycol mono or diacrylate and methacrylate, glycerol mono, di or triacrylate and methacrylate, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol di Acrylate and dimethacrylate, 1,6-hexanediol diacrylate and dimethacrylate, neopentyl glycol Acrylate and dimethacrylate, mono or diacrylate and methacrylate of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, trimethylolpropane triacrylate and methacrylate, di or tri of glycerol Mention may be made of compounds such as acrylates and methacrylates, di, tri, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

  It is preferable that 1-50 mass parts is used for the monomer which has said photopolymerizable unsaturated bond for improving the resolution of a relief pattern with respect to 100 mass parts of (A) component polyimide precursor.

  In addition, an adhesion aid can be optionally added to improve the adhesion between the film formed using the photosensitive resin composition of the present invention and the substrate. Adhesion aids include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3- Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3′-bis (N- [3-triethoxysilyl] propylamide) -4,4′-dicarboxylic acid, benzene-1, 4-bis (N- [3-trie Toxisilyl] propylamide) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propyl succinic anhydride, silane coupling agents such as N-phenylaminopropyltrimethoxysilane, and aluminum tris (ethyl acetoacetate), Examples thereof include aluminum adhesion assistants such as aluminum tris (acetylacetonate) and ethyl acetoacetate aluminum diisopropylate.

  In these, it is more preferable to use a silane coupling agent from the point of adhesive force. The addition amount of the adhesion assistant is preferably in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of the component (A) polyimide precursor.

  In addition, a thermal polymerization inhibitor can be optionally added to improve the viscosity of the photosensitive resin composition solution during storage and the stability of photosensitivity. Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6 -Di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N- Sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.

  As a quantity of the thermal-polymerization inhibitor added to the photosensitive resin composition, the range of 0.005-12 mass parts is preferable with respect to 100 mass parts of polyimide precursors.

  Further, as a crosslinking agent, when the relief pattern is heat-cured, a polyimide precursor can be crosslinked, or a crosslinking agent that can form a crosslinked network by itself is added to further enhance heat resistance and chemical resistance. be able to. As the cross-linking agent, amino resins or derivatives thereof are preferably used, and among them, urea resins, glycol urea resins, hydroxyethylene urea resins, melamine resins, benzoguanamine resins, and derivatives thereof are preferably used. Particularly preferred is an alkoxymethylated melamine compound, and hexamethoxymethylmelamine is mentioned as an example.

  In consideration of various performances other than heat resistance and chemical resistance, the addition amount of the crosslinking agent is preferably 2 to 40 parts by weight, more preferably 100 parts by weight of the polyimide precursor of the component (A). 5 to 30 parts by mass. When the addition amount is 2 parts by mass or more, good heat resistance and chemical resistance are exhibited, and when it is 40 parts by mass or less, the storage stability is excellent.

  On the other hand, when a polybenzoxazole precursor is used as the component (A) in the photosensitive resin composition of the present invention, if necessary, dyes and surfactants that are conventionally used as additives for photosensitive resin compositions It is possible to add a bonding aid, a crosslinking agent, etc. for improving the adhesiveness with the agent and the substrate.

  The additives will be described more specifically. Examples of the dye include methyl violet, crystal violet, and malachite green. 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 and Chemicals) or Lumiflon (trade name, manufactured by Asahi Glass), such as KP341 (trade name, manufactured by Shin-Etsu Chemical), DBE (trade name, manufactured by Chisso) ) And granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like. 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 dianhydride reactant, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane amino group converted to urethane group or urea group It can be mentioned. In this case, as the alkyl group, methyl group, ethyl group, butyl group, etc., as the acid anhydride, maleic anhydride, phthalic anhydride, etc., as the acid dianhydride, pyromellitic 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.

  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 nickel (II) Salt, trifluoroacetylacetone aluminum (III) salt, trifluoroacetylacetone titanium (IV) salt, trifluoroacetylacetone chromium (III) salt, trif Metal chelating agents such as oroacetylacetone 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.

  When a polybenzoxazole precursor is used as the component (A), the above-described components of the photosensitive resin composition are dissolved in a solvent to form a varnish and used as a solution of 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 admixture of two or more. Of these solvents, non-amide solvents are preferred from the viewpoint of little influence on photoresists, and specific more preferred examples include γ-butyrolactone, cyclopentanone, cyclohexanone, isophorone and the like.

<Pattern Forming Method, Semiconductor Device, and Manufacturing Method Thereof>
The present invention also provides a pattern forming method for forming a cured relief pattern using the above-described photosensitive resin composition of the present invention, a semiconductor device using the pattern forming method, and a method for manufacturing the same.

The pattern forming method of the present invention comprises:
(A) A coating film forming step of applying the above-described photosensitive resin composition of the present invention on a substrate and drying to form a coating film,
(B) After exposing the coating film with actinic rays through a photomask or reticle having a pattern or directly, the unexposed part is removed with a solvent to obtain a polyimide precursor pattern, or the exposed part is an alkaline aqueous solution. A precursor pattern forming step of removing to obtain a pattern of a polybenzoxazole precursor;
(C) It includes a curing step of forming a polyimide or polybenzoxazole pattern by heat curing the polyimide precursor or polybenzoxazole precursor pattern.

  First, the pattern formation method in the case of using a polyimide precursor as the component (A) will be described. In this case, in the precursor pattern forming step (b), the coating film is exposed to actinic rays, preferably ultraviolet rays, through a photomask or reticle having a pattern, or directly, and then developed with a developer. This removes the unexposed portion of the coating film with a solvent, thereby forming a polyimide precursor pattern on the substrate. In the curing step (c), the polyimide precursor pattern is heated and cured to imidize the polyimide precursor in the pattern, thereby forming a cured relief pattern made of polyimide resin on the substrate.

  The developer used for development is preferably a good solvent for the photosensitive resin composition or a combination of the good solvent and the poor solvent. As the good solvent, N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, and the like are preferable. Toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate and water are preferred. When mixing and using a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. Moreover, several types of solvents can be used in combination.

  As a developing method, an arbitrary method can be selected and used from conventionally known photoresist developing methods such as a rotary spray method, a paddle method, and an immersion method involving ultrasonic treatment.

  Next, the case where a polybenzoxazole precursor is used as the component (A) will be described. In this case, in the precursor pattern forming step (b), the coating film is exposed to actinic rays, preferably ultraviolet rays, through a photomask or reticle having a pattern, or directly, and then developed with a developer. Thus, the exposed portion of the coating film is removed with an alkaline aqueous solution, thereby forming a polybenzoxazole precursor pattern on the substrate. In the curing step (c), the polybenzoxazole precursor pattern is heat-cured to oxidize the polybenzoxazole precursor in the pattern, whereby a cured relief pattern comprising a polybenzoxazole resin on the substrate. Form.

  The developer used for development dissolves and removes the alkaline aqueous solution-soluble polymer and needs to be an alkaline aqueous solution in which an alkali compound is dissolved. The alkali compound dissolved in the developer may be either an inorganic alkali compound or an organic alkali compound.

  Examples of the inorganic alkali compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate. , Lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, and ammonia.

  Examples of the organic alkali compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, diethylamine. -N-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, triethanolamine, etc. are mentioned.

  Furthermore, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a storage stabilizer, and a resin dissolution inhibitor can be added to the alkaline aqueous solution. .

  As a method for coating the photosensitive resin composition used in the present invention on a substrate, methods conventionally used for coating a photosensitive resin composition, for example, spin coater, bar coater, blade coater, curtain coater A method of applying with a screen printer or the like, a method of applying with a spray coater, or the like can be used.

As a method for drying the coating film, methods such as air drying, heat drying with an oven or hot plate, and vacuum drying are used. Moreover, it is desirable that the coating film be dried under conditions such that imidation of the polyamic acid ester in the photosensitive resin composition does not occur. Specifically, when performing air drying or heat drying, it can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour.
The coating film thus obtained is exposed through a photomask or reticle having a pattern, or directly by an ultraviolet light source or the like, using an exposure apparatus such as a contact aligner, mirror projection, or stepper.

  Thereafter, post-exposure baking (PEB) or a pre-development baking by any combination of temperature and time may be performed as necessary for the purpose of improving photosensitivity. The range of the baking conditions is preferably 40 to 120 ° C. and the time of 10 to 240 seconds, but is not limited to this range as long as the various characteristics of the photosensitive resin composition of the present invention are not impaired.

  As a developing method, an arbitrary method can be selected and used from conventionally known photoresist developing methods such as a rotary spray method, a paddle method, and an immersion method involving ultrasonic treatment. Further, after development, for the purpose of adjusting the shape of the relief pattern, post-development baking at any combination of temperature and time may be performed as necessary.

  The pattern of the polyimide precursor or polybenzoxazole precursor is converted into a cured relief pattern composed of polyimide or polybenzoxazole by heating to dilute the photosensitive component and imidizing or oxazolating each. Various methods such as a method using a hot plate, a method using an oven, and a method using a temperature rising oven capable of setting a temperature program can be selected as the method for heat curing. Heating can be performed at 200 ° C. to 400 ° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas for heat curing, and an inert gas such as nitrogen or argon may be used.

  The present invention also provides a semiconductor device having a base material that is a semiconductor element and a pattern of polyimide or polybenzoxazole formed on the base material by the pattern forming method described above.

  Moreover, this invention provides the manufacturing method of the semiconductor device which uses a semiconductor element as a base material and includes the pattern formation method mentioned above as a part of process. In the semiconductor device of the present invention, the cured relief pattern formed by the above pattern forming method is used to protect a surface protection film, an interlayer insulating film, a rewiring insulating film, a flip chip device protective film, or a semiconductor device having a bump structure. As a film | membrane, it can manufacture by combining with the manufacturing method of a well-known semiconductor device.

  The photosensitive resin composition of the present invention is useful not only for application to semiconductor devices as described above but also for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad plates, solder resist films, or liquid crystal alignment films. It is.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

  In Examples, Comparative Examples and Reference Examples, the physical properties of the photosensitive resin composition were measured and evaluated according to the following methods.

(1) Weight average molecular weight The weight average molecular weight (Mw) of each polyimide precursor or polybenzoxazole precursor was measured by the gel permeation chromatography method (standard polystyrene conversion). The column used for the measurement is a trade name Shodex 805M / 806M series manufactured by Showa Denko KK, and the standard monodisperse polystyrene is Shodex STANDARD SM-105 manufactured by Showa Denko KK, and the developing solvent is N-methyl-2-pyrrolidone. The detector used was a trade name Shodex RI-930 manufactured by Showa Denko.

(2) Evaluation of patterning characteristics of polyimide pattern A photosensitive resin composition was spin-coated on a 6-inch silicon wafer or a copper substrate and dried to form a 10 μm thick coating film. This coating film was irradiated with energy of 300 mJ / cm ² using an i-line stepper NSR1755i7B (Nikon Corporation, Japan) using a reticle with a test pattern. Subsequently, the coating film formed on the wafer is spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone, rinsed with propylene glycol methyl ether acetate, and polyamide An acid ester pattern was obtained.

  The wafer on which the pattern is formed is heat-treated in a nitrogen atmosphere at 200 ° C. for 1 hour and then at 350 ° C. for 2 hours using a temperature-programmed cure furnace (VF-2000 type, manufactured by Koyo Lindberg, Japan). Thus, a polyimide pattern having a thickness of 5 μm was obtained on the silicon wafer. About each obtained pattern, the width | variety of the pattern shape and the pattern part was observed under the optical microscope, and the resolution was calculated | required. Regarding the resolution, a pattern having a plurality of openings with different areas is formed by the above method by exposing through a reticle with a test pattern, and the area of the obtained pattern opening is equal to the corresponding pattern mask opening area. If it is 1/2 or more, it is considered that it has been resolved, and the length of the opening side of the mask corresponding to the resolved opening having the smallest area is taken as the resolution. The resolution is good if it is 10 μm or less, that is, if the aspect ratio (film thickness after coating / drying) is 1 or more.

(3) Patterning characteristic evaluation of polybenzoxazole (A) A positive photosensitive resin composition using a polybenzoxazole precursor as a component is applied to a 5-inch silicon wafer by a spin coater (Dspin 636) manufactured by Dainippon Screen Mfg. Co., Ltd. Spin coating was performed and prebaking was performed at 130 ° C. for 180 seconds on a hot plate to form a coating film having a thickness of 10.7 μm. The film thickness was measured with a film thickness measuring device (Lambda Ace) manufactured by Dainippon Screen Mfg. This coating film was exposed with an i-line stepper NSR1755i7B (manufactured by Nikon Corporation, Japan) having an exposure wavelength of i-line (365 nm) through a reticle with a test pattern 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.

  Further, the obtained relief pattern was subjected to curing (heat curing treatment) at 350 ° C. for 1 hour in a vertical curing furnace (manufactured by Koyo Lindberg Co., Ltd.) to obtain a polybenzoxazole film which is a heat-resistant coating film. did.

(4) Accuracy evaluation of each pattern of polyimide and polybenzoxazole Based on the following criteria, the accuracy of each pattern of polyimide or polybenzoxazole formed in the above (2) and (3) was evaluated.
“Good”: The cross section of the pattern does not slide, undercut, swelling, or bridging does not occur, and the aspect ratio is 1 or more, and the pattern shape does not change during heat curing. thing. Furthermore, in the case of a copper substrate, there is no discoloration or corrosion of copper.
“Bad”: Those that do not satisfy at least one of the above conditions.

<Reference Example 1> (Synthesis of polyimide precursor A)
Place 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in a 2 liter separable flask, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone and stir at room temperature. While stirring, 81.5 g of pyridine was added to obtain a reaction mixture. After completion of the exothermic reaction, the mixture was allowed to cool to room temperature and left for 16 hours.
Next, under ice cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4′-diaminodiphenyl ether (DADPE). A suspension of 93.0 g in γ-butyrolactone 350 ml was added over 60 minutes with stirring. After further stirring for 2 hours at room temperature, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

  The obtained reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 liter of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate a polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polyimide precursor A). When the molecular weight of the polyimide precursor A was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20000.

Reference Example 2 (Synthesis of polyimide precursor B)
As described in Reference Example 1 above, except that 147.1 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4′-oxydiphthalic dianhydride. Reaction was performed in the same manner as in the method to obtain a polyimide precursor B. When the molecular weight of the polyimide precursor B was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

<Reference Example 3> (Synthesis of polyimide precursor C)
Instead of 155.1 g of 4,4′-oxydiphthalic dianhydride, 77.6 g of 4,4′-oxydiphthalic dianhydride and 73.6 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride A polyimide precursor C was obtained by reacting in the same manner as described in Reference Example 1 except that was used. When the molecular weight of the polyimide precursor C was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 27,000.

<Reference Example 4> (Synthesis of polyimide precursor D)
In place of 155.1 g of 4,4′-oxydiphthalic dianhydride, 147.1 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride was replaced with 93.0 g of 4,4′-diaminodiphenyl ether (DADPE). A polyimide precursor D was obtained by reacting in the same manner as described in Reference Example 1 except that 105.1 g of 4,4′-methylene-di-O-toluidine was used instead. When the molecular weight of the polyimide precursor D was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

<Reference Example 5> (Synthesis of polyimide precursor E)
In place of 155.1 g of 4,4′-oxydiphthalic dianhydride, 147.1 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride was used, and 4,4′-diaminodiphenyl ether (DADPE) 93. A polyimide precursor E was obtained by reacting in the same manner as described in Reference Example 1 except that 50.2 g of p-phenylenediamine was used instead of 0 g. When the molecular weight of the polyimide precursor E was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 38,000.

<Reference Example 6> (Synthesis of polyimide precursor F)
Instead of 155.1 g of 4,4′-oxydiphthalic dianhydride, 32.7 g of pyromellitic dianhydride and 103.0 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride were used. Reacted in the same manner as described in Reference Example 1 to obtain a polyimide precursor F. When the molecular weight of the polyimide precursor F was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

Reference Example 7 (Synthesis of polyimide precursor G)
In place of 155.1 g of 4,4′-oxydiphthalic dianhydride, 161.1 g of 3,3′4,4′-benzophenone tetracarboxylic dianhydride was used, and 4,4′-diaminodiphenyl ether (DADPE) 93. A polyimide precursor G was obtained in the same manner as described in Reference Example 1 except that 200.9 g of bis [4- (aminophenoxy) phenyl] sulfone was used instead of 0 g. When the molecular weight of the polyimide precursor G was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 32,000.

<Reference Example 8> (Synthesis of polybenzoxazole precursor H)
In a 3 L separable flask, 183.1 g (0.5 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 640.9 g of N, N-dimethylacetamide (DMAc) Then, 63.3 g (0.8 mol) of pyridine was mixed and stirred at room temperature (25 ° C.) to obtain a uniform solution. A solution prepared by dissolving 118.0 g (0.4 mol) of 4,4′-diphenyl ether dicarbonyl chloride in 354 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 dropping was 40 minutes, and the temperature of the reaction solution was 30 ° C. at the maximum.

Three hours after the completion of the dropping, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction solution, and the mixture was allowed 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 2 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). A polybenzoxazole precursor H having a weight average molecular weight of 9000 (polystyrene conversion) was obtained.
After redissolving the polymer obtained above in γ-butyrolactone (GBL), this was treated with a cation exchange resin and an anion exchange resin, and the resulting solution was poured into ion exchange water, followed by precipitation. The purified polymer was separated by filtration, washed with water, and vacuum dried to obtain a purified polymer.

<Example 1>
Using the polyimide precursor A, a photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. 100 g of polyimide precursor A which is a polyamic acid ester was added to 10 g of 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (photoinitiator), 1,3,5-tris (4-t -Butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (phenol compound) 2 g, N-phenyldiethanolamine 8 g, 0.05 g of 7-diethylamino-3-ethoxycarbonylcoumarin, 5 g of hexamethoxymethylmelamine, 8 g of tetraethylene glycol dimethacrylate, 1.5 g of N- [3- (triethoxysilyl) propyl] phthalamic acid, and 2-nitroso-1 -N-methylpyrrolidone (hereinafter referred to as NMP) 80 together with 0.05 g of naphthol And it was dissolved in a mixed solvent of ethyl lactate 20g. The viscosity of the resulting solution was adjusted to about 75 poise by further adding a small amount of the mixed solvent to obtain a photosensitive resin composition.

  The resolution of the polyimide coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the method described above is 8 μm when the film thickness after coating and drying is 10 μm, and after curing. The film thickness was 5 μm. Each of them satisfied the aspect ratio of 1 or more, and the pattern accuracy was good, and no discoloration or corrosion was observed on the copper substrate.

<Example 2>
1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione ( A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that the addition amount of the phenol compound) was changed to 0.5 g. The resolution of the polyimide coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the method described above is 8 μm when the film thickness after coating and drying is 10 μm, and after curing. The film thickness was 5 μm. Each of them satisfied the aspect ratio of 1 or more, and the pattern accuracy was good, and no discoloration or corrosion was observed on the copper substrate.

<Example 3>
1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione ( A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that the addition amount of the phenol compound was 10 g. The resolution of the polyimide coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the method described above is 8 μm when the film thickness after coating and drying is 10 μm, and after curing. The film thickness was 5 μm. Each of them satisfied the aspect ratio of 1 or more, and the pattern accuracy was good, and no discoloration or corrosion was observed on the copper substrate.

<Example 4>
A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that the polyimide precursor B was used instead of the polyimide precursor A. The resolution of the polyimide coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the method described above is 8 μm when the film thickness after coating and drying is 10 μm, and after curing. The film thickness was 5 μm. Each of them satisfied the aspect ratio of 1 or more, and the pattern accuracy was good, and no discoloration or corrosion was observed on the copper substrate.

<Example 5>
A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that the polyimide precursor C was used instead of the polyimide precursor A. The resolution of the polyimide coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the method described above is 8 μm when the film thickness after coating and drying is 10 μm, and after curing. The film thickness was 5 μm. Each of them satisfied the aspect ratio of 1 or more, and the pattern accuracy was good, and no discoloration or corrosion was observed on the copper substrate.

<Example 6>
A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that the polyimide precursor D was used instead of the polyimide precursor A. The resolution of the polyimide coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the method described above is 8 μm when the film thickness after coating and drying is 10 μm, and after curing. The film thickness was 5 μm. Each of them satisfied the aspect ratio of 1 or more, and the pattern accuracy was good, and no discoloration or corrosion was observed on the copper substrate.

<Example 7>
A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that the polyimide precursor E was used instead of the polyimide precursor A. The resolution of the polyimide coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the method described above is 8 μm when the film thickness after coating and drying is 10 μm, and after curing. The film thickness was 5 μm. Each of them satisfied the aspect ratio of 1 or more, and the pattern accuracy was good, and no discoloration or corrosion was observed on the copper substrate.

<Example 8>
A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that the polyimide precursor F was used instead of the polyimide precursor A. The resolution of the polyimide coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the method described above is 8 μm when the film thickness after coating and drying is 10 μm, and after curing. The film thickness was 5 μm. Each of them satisfied the aspect ratio of 1 or more, and the pattern accuracy was good, and no discoloration or corrosion was observed on the copper substrate.

<Example 9>
A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that the polyimide precursor G was used instead of the polyimide precursor A. The resolution of the polyimide coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the method described above is 8 μm when the film thickness after coating and drying is 10 μm, and after curing. The film thickness was 5 μm. Each of them satisfied the aspect ratio of 1 or more, and the pattern accuracy was good, and no discoloration or corrosion was observed on the copper substrate.

<Example 10>
A photosensitive resin composition was prepared by using the polybenzoxazole precursor H by the following method, and the prepared composition was evaluated. 100 g of polybenzoxazole precursor H is mixed with 20 g of a photosensitive diazoquinone compound (photoacid generator) represented by the following general formula (24), 1,3,5-tris (4-t-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (phenol compound) 2 g and a γ-butyrolactone solvent, and a photosensitive resin composition It was.

  The resolution of the polybenzoxazole coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the above-described method satisfies an aspect ratio of 1 or more, and the pattern accuracy is also good. Even on the copper substrate, no discoloration / corrosion was observed, which was good.

<Comparative Example 1>
Using the polyimide precursor A, a photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. 100 g of polyimide precursor A was mixed with 10 g of 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (photoinitiator), 8 g of N-phenyldiethanolamine, 7-diethylamino-3-ethoxycarbonylcoumarin 0 .05 g, hexamethoxymethylmelamine 5 g, tetraethylene glycol dimethacrylate 8 g, N- [3- (triethoxysilyl) propyl] phthalamic acid 1.5 g, and 2-nitroso-1-naphthol 0.05 g, NMP 80 g And 20 g of ethyl lactate were dissolved in a mixed solvent. The viscosity of the resulting solution was adjusted to about 75 poise by further adding a small amount of the mixed solvent to obtain a photosensitive resin composition.

  The resolution of the polyimide coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the method described above is 8 μm when the film thickness after coating and drying is 10 μm, and after curing. The film thickness was 5 μm. In the case of a silicon wafer, the aspect ratio was 1 or more and the pattern accuracy was good. However, because a (C) phenol compound was not used, in the case of a copper substrate, there was a development residue, and copper corrosion occurred and was defective. Met.

<Comparative Example 2>
Using the polyimide precursor A, a photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. 100 g of polyimide precursor A was mixed with 10 g of 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (photoinitiator), 1,3,5-tris (4-t-butyl-3- Hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (phenolic compound) 25 g, N-phenyldiethanolamine 8 g, 7-diethylamino-3 0.05 g of ethoxycarbonylcoumarin, 5 g of hexamethoxymethylmelamine, 8 g of tetraethylene glycol dimethacrylate, 1.5 g of N- [3- (triethoxysilyl) propyl] phthalamic acid, and 2-nitroso-1-naphthol 0 .05g and N-methylpyrrolidone (hereinafter referred to as NMP) 80g and ethyl lactate 20g It was dissolved in a mixed solvent that. The viscosity of the resulting solution was adjusted to about 75 poise by further adding a small amount of the mixed solvent to obtain a photosensitive resin composition.

  The polyimide coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the above-mentioned method did not show copper discoloration / corrosion on the copper substrate. ) The amount of phenolic compound used was too high, resulting in poor resolution and pattern accuracy.

<Comparative Example 3>
Using the polyimide precursor A, a photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. 100 g of the polyamic acid ester A was mixed with 10 g of 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (photoinitiator), pentaerythrityl-tetrakis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate] (phenol compound not corresponding to the above component (C)) 2 g, N-phenyldiethanolamine 8 g, 7-diethylamino-3-ethoxycarbonylcoumarin 0.05 g, hexamethoxymethylmelamine 5 g, A mixed solvent consisting of 80 g of NMP and 20 g of ethyl lactate together with 8 g of tetraethylene glycol dimethacrylate, 1.5 g of N- [3- (triethoxysilyl) propyl] phthalamic acid and 0.05 g of 2-nitroso-1-naphthol. Dissolved. The viscosity of the resulting solution was adjusted to about 75 poise by further adding a small amount of the mixed solvent to obtain a photosensitive resin composition.

  The resolution of the polyimide coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the method described above is 8 μm when the film thickness after coating and drying is 10 μm, and after curing. The film thickness was 5 μm. In the case of a silicon wafer, the aspect ratio was 1 or more and the pattern accuracy was good, but (C) a phenolic compound that does not correspond to a phenolic compound was used. Because it happened, it was bad.

<Comparative example 4>
Using the polyimide precursor A, a photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. 100 g of polyimide precursor A was added to 10 g of 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (photoinitiator), tris- (3,5-di-t-butyl-4-hydroxy (Benzyl) -isocyanurate (phenolic compound not corresponding to the above component (C)) 2 g, N-phenyldiethanolamine 8 g, 7-diethylamino-3-ethoxycarbonylcoumarin 0.05 g, hexamethoxymethylmelamine 5 g, tetraethylene glycol di Along with 8 g of methacrylate, 1.5 g of N- [3- (triethoxysilyl) propyl] phthalamic acid, and 0.05 g of 2-nitroso-1-naphthol, it was dissolved in a mixed solvent composed of 80 g of NMP and 20 g of ethyl lactate. The viscosity of the resulting solution was adjusted to about 75 poise by further adding a small amount of the mixed solvent to obtain a photosensitive resin composition.

  The resolution of the polyimide coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the method described above is 8 μm when the film thickness after coating and drying is 10 μm, and after curing. The film thickness was 5 μm. In the case of a silicon wafer, the aspect ratio was 1 or more and the pattern accuracy was good, but (C) a phenolic compound that does not correspond to a phenolic compound was used. Because it happened, it was bad.

<Comparative Example 5>
A photosensitive resin composition was prepared and evaluated in the same manner as in Comparative Example 3 except that the polyimide precursor B was used instead of the polyimide precursor A. The resolution of the polyimide coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the above-described method is 8 μm when the film thickness after coating and drying is 10 μm, and after curing. The film thickness was 5 μm. In the case of a silicon wafer, the aspect ratio was 1 or more and the pattern accuracy was good, but (C) a phenolic compound that does not correspond to a phenolic compound was used. Because it happened, it was bad.

<Comparative Example 6>
A photosensitive resin composition was prepared by using the polybenzoxazole precursor H by the following method, and the prepared composition was evaluated. 100 g of polybenzoxazole precursor H was dissolved in a γ-butyrolactone solvent together with 20 g of a photosensitive diazoquinone compound (photoacid generator) represented by the following general formula (24) to obtain a photosensitive resin composition.

  The resolution of the polybenzoxazole coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the above-described method satisfies an aspect ratio of 1 or more in the case of a silicon wafer, and has a pattern. Although the accuracy was good, (C) a phenol compound was not used, so in the case of a copper substrate, there was a development residue, and copper corrosion occurred, which was poor.

  The photosensitive resin composition of the present invention can be suitably used in the field of photosensitive materials useful for the production of electrical / electronic materials such as semiconductor devices and multilayer wiring boards. More specifically, the composition of the present invention can be suitably used as a photosensitive resin composition on copper or a copper alloy.

Claims (5)

(A) The following general formula (1):

{Wherein X is a tetravalent organic group having 6 to 32 carbon atoms, Y is a divalent organic group having 4 to 30 carbon atoms, and R and R ′ are each independently an olefinic divalent group. A monovalent group or a hydroxyl group having a heavy bond is shown. } A polyimide precursor having a repeating unit represented by the following general formula (2):

{Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, and X ₂ , Y ₁ and Y ₂ are each independently a divalent organic group having at least 2 carbon atoms. Where m is an integer from 1 to 1000, n is an integer from 0 to 500, and m / (m + n)> 0.5. The arrangement order of m repeating units including X ₁ and Y ₁ and n repeating units including X ₂ and Y ₂ is not limited. } 100 parts by mass of a polybenzoxazole precursor having a structure represented by:
(B) 1 to 40 parts by mass of photosensitizer, and (C) the following general formula (3):

{In the formula, R ₁ represents the following general formula (4):

An organic group represented by
In formula (4), R ₂ and R ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, and R ₄ is represented by the following general formula (5):

In formula (5), R ₅ , R ₆ and R ₇ are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. However, at least two of R ₅ , R ₆ and R ₇ are monovalent organic groups having 1 to 6 carbon atoms. }
The photosensitive resin composition containing 0.1-20 mass parts of at least 1 sort (s) of phenolic compounds chosen from the group which consists of a compound represented by these. The phenol compound of (C) is represented by the following formula (6):

The photosensitive resin composition of Claim 1 which is a compound represented by these. A method of forming a polyimide or polybenzoxazole pattern on a substrate,
(A) A coating film forming step in which the photosensitive resin composition according to claim 1 or 2 is applied on a substrate and dried to form a coating film;
(B) After exposing the coating film with actinic rays through a photomask or reticle having a pattern or directly, the unexposed part is removed with a solvent to obtain a polyimide precursor pattern, or the exposed part is an alkaline aqueous solution. A precursor pattern forming step of removing to obtain a pattern of a polybenzoxazole precursor;
(C) The pattern formation method including the hardening process which forms the pattern of a polyimide or a polybenzoxazole by heat-hardening the pattern of the said polyimide precursor or the said polybenzoxazole precursor.   The semiconductor device which has a base material which is a semiconductor element, and the pattern of the polyimide or polybenzoxazole formed by the pattern formation method of Claim 3 on the said base material.   The manufacturing method of a semiconductor device which uses the semiconductor element as a base material and includes the pattern formation method of Claim 3 as a part of process.