JP4761989B2 - Polyamic acid ester composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition having heat resistance useful for the manufacture of electrical / electronic materials such as semiconductor devices and multilayer wiring boards, and a method for producing a cured relief pattern having heat resistance using the photosensitive resin composition And a semiconductor device having the cured relief pattern. More specifically, the present invention relates to a photosensitive polyamic acid ester composition capable of shortening the processing time in the development process during the production of a relief pattern and having high resolution and storage stability.

Polyimide resin is attracting attention as a material for microelectronics due to its high thermal and chemical stability, low dielectric constant, and excellent planarization ability, and is used as a semiconductor surface protective film, interlayer insulating film, or Widely used as a material for multi-chip modules.
In the case of manufacturing a semiconductor device using a polyimide resin, conventionally, a non-photosensitive polyimide precursor is applied on a substrate to form a coating film, and after heating to convert to a polyimide resin, a lithography technique is used. Thus, a method for forming a desired pattern has been used. Specifically, on the polyimide resin film, a photoresist relief pattern is formed using a photoresist and a photomask having a pattern, and then the polyimide resin film is patterned by etching. A relief pattern forming method has been used. However, in this method, first, a relief pattern of a photoresist to be a mask is formed on the polyimide resin film, and then the polyimide resin film is etched, and finally the unnecessary photoresist is removed. The process was complicated because it had to be done. In addition, since it is an indirect relief pattern forming method, the resolution is low, and it is necessary to use a toxic substance such as hydrazine as a solvent for etching.

  In recent years, in order to overcome the above problems, a method for introducing a photopolymerizable photosensitive group into a polyimide precursor and directly forming a relief pattern on a coating film of the polyimide precursor has been developed and put into practical use. . For example, a polyimide precursor formed by bonding a compound having a photopolymerizable double bond to a polyamic acid derivative through an ester bond, an amide bond, an ionic bond or the like (hereinafter also referred to as “photosensitive polyimide precursor”). ), And a photosensitive resin composition containing a photopolymerization initiator or the like is applied on the substrate to form a coating film, and the coating film is exposed by exposing the coating film through a photomask having a pattern. The polyimide precursor is insolubilized and then subjected to a development treatment to form a relief pattern made of a polyimide precursor, and then heated to remove the photosensitive base component to form a cured relief pattern made of a polyimide resin. A conversion method has been proposed (Non-Patent Document 1). This technology is generally called photosensitive polyimide technology. Since the photosensitive polyimide technology overcomes the problems associated with the conventional process using a non-photosensitive polyimide precursor, in recent years, a relief pattern made of a polyimide resin is frequently formed by the photosensitive polyimide technology.

By the way, in recent years, as the integration of semiconductors has increased, the device area and the wafer size have also been increased. Therefore, shortening of the above-described relief pattern forming process has become an issue, with higher photosensitivity and shorter development time. There is a need for photosensitive polyimide precursor resin compositions. On the other hand, for example, Patent Document 1 discloses a method that enables the development time to be shortened by optimizing the composition of the organic solvent developer.
However, in these techniques, there is a problem in that it is disadvantageous in terms of semiconductor manufacturing costs because it is necessary to change the developing solution line chemical solution and to specialize the developing device.

Akio Yamaoka, Toshihiko Omote, Taiseisha Co., Ltd., “Polyfile”, Vol. 27, No. 2, pages 14-18 (1990) Japanese Patent Laid-Open No. 11-233949

  The present invention relates to a photosensitive polyamic acid ester composition capable of shortening the processing time in the development process during the production of a relief pattern and having high resolution and storage stability, and a method for forming a cured relief pattern using the composition. Is.

  As a result of studying the above-mentioned problems of the prior art, the present inventor has identified a specific organic solvent as an organic solvent such as N-methyl-2-pyrrolidone or γ-butyrolactone, which is usually used as a solvent for a polyamic acid ester composition. It has been found that the above-mentioned problems can be solved by combining the above, and the present invention has been made.

（上記一般式（１）中、Ｘは少なくとも１つの炭素数６〜３２の４価の有機基を示し、Ｙは炭素数４〜３０の２価の芳香族基、炭素数４〜３０の２価の脂肪族基およびケイ素数２〜５０の２価のケイ素含有基からなる群から選ばれる少なくとも１つの基を示し、Ｒはオレフィン性二重結合を有する１価の基である。）
本発明の二は、（１）本発明の一の感光性樹脂組成物を層またはフィルムの形で基板上に塗布して感光性樹脂膜を形成し、（２）マスクを介して化学線で感光性樹脂膜を露光するか、光線、電子線またはイオン線を直接感光性樹脂膜に照射し、（３）感光性樹脂膜を現像し、（４）得られたレリーフパターンを加熱処理することを特徴とする硬化レリーフパターンの製造方法である。
本発明の三は、本発明の二の製造方法により得られる硬化レリーフパターン層を有してなる半導体装置である。 That is, according to one aspect of the present invention, (a) 100 parts by mass of a polyamic acid ester having a repeating unit represented by the following general formula (1), (b) 1 to 20 parts by mass of a photopolymerization initiator, and (c) organic A composition comprising 30 to 600 parts by mass of a solvent, wherein (c) the content of N-ethyl-2-pyrrolidone and / or 1,3-dimethyl-2-imidazolidinone in the organic solvent is (c) It is a photosensitive resin composition characterized by being 50% by mass or more based on the total amount of the organic solvent.

(In the general formula (1), X represents at least one tetravalent organic group having 6 to 32 carbon atoms, Y represents a divalent aromatic group having 4 to 30 carbon atoms, and 2 having 4 to 30 carbon atoms. And at least one group selected from the group consisting of a divalent aliphatic group and a divalent silicon-containing group having 2 to 50 silicon atoms, and R is a monovalent group having an olefinic double bond.)
In the second aspect of the present invention, (1) a photosensitive resin composition according to the present invention is applied on a substrate in the form of a layer or a film to form a photosensitive resin film, and (2) actinic radiation is passed through a mask. Exposing the photosensitive resin film or directly irradiating the photosensitive resin film with a light beam, an electron beam or an ion beam, (3) developing the photosensitive resin film, and (4) heating the obtained relief pattern. Is a method for producing a cured relief pattern.
A third aspect of the present invention is a semiconductor device having a cured relief pattern layer obtained by the second production method of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the processing time in the image development process at the time of relief pattern manufacture can be shortened, and the photosensitive polyamic-acid ester composition which has high resolution and storage stability can be provided. It is also possible to provide a method for producing a cured relief pattern using the composition and a semiconductor device having the cured relief pattern layer.

The present invention will be specifically described below.
<Photosensitive resin composition>
The component which comprises the photosensitive resin composition of this invention is demonstrated below.
(A) Polyamic acid ester In the photosensitive resin composition of the present invention, the repeating unit represented by the general formula (1) contained in the (a) polyamic acid ester has a heat resistance on the cured polyimide resin film. In addition, it has a function of combining chemical resistance.
The tetracarboxylic dianhydride that can be suitably used as the main raw material of the polyamic acid ester is a tetracarboxylic dianhydride (hereinafter simply referred to as “aromatic”) in which the X group is a tetravalent aromatic group having 6 to 32 carbon atoms. Group tetracarboxylic dianhydride ").

  Preferred examples include pyromellitic dianhydride, 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4 ′. -Biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxy) Phenyl) sulfide dianhydride, bis (4- (4-aminophenoxy) phenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane Dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3- Heki Fluoropropane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,3,4,7-naphthalenetetracarboxylic dianhydride And 1,4,5,8-naphthalenetetracarboxylic dianhydride. These aromatic tetracarboxylic dianhydrides can be used alone or in combination of two or more.

When the photosensitive resin composition of the present invention is formed into a relief pattern by irradiation with i-line, an aromatic tetracarboxylic dianhydride having good i-line permeability such as 4,4′-oxydiphthalic dianhydride is used. It is preferable to use it. In addition, when the cured polyimide resin film is used for an application requiring higher heat resistance, an aromatic tetracarboxylic dianhydride having a rigid structure such as pyromellitic dianhydride is preferable.
In addition to the aromatic tetracarboxylic dianhydride used as the main raw material, the tetracarboxylic dianhydride (hereinafter referred to simply as “aliphatic tetrahydride”) in which the X group is a tetravalent aliphatic group having 4 to 32 carbon atoms. Carboxylic dianhydride ") can also be used as an auxiliary material.

  Preferred examples include, for example, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, cyclo Pentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, cyclohex-1-ene-2,3,5,6-tetracarboxylic Acid dianhydride, 3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3- (1,2) , 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane- 1- (1,2), 3,4 Tetracarboxylic dianhydride, 1-propylcyclohexane-1- (1,2), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3- ( 2,3) -tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetra Carboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5 , 6-tetracarboxylic dianhydride, and 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride. These aliphatic tetracarboxylic dianhydrides can be used alone or in combination of two or more.

In the polyamic acid ester, the ratio of the X group derived from the aliphatic tetracarboxylic dianhydride to the X group derived from all the tetracarboxylic dianhydrides should be within a range where desired heat resistance and chemical resistance can be obtained. There is no particular limitation.
In the polyamic acid ester, the R group in the repeating unit is derived from alcohols used for the esterification reaction of the tetracarboxylic dianhydride. In order to impart photosensitivity, the alcohol preferably uses an alcohol having an olefinic double bond as a main component.
Specifically, 2-methacryloyloxyethyl alcohol, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-2-propyl alcohol, 2-methacrylamide ethyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl Examples include vinyl ketone, 2-hydroxyethyl methacrylate, glycerol monomethacrylate, and glycerol monoacrylate. These alcohols having an olefinic double bond can be used alone or in combination of two or more.

Examples of the alcohol having an olefinic double bond include polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, polyethylene glycol polypropylene glycol monomethacrylate, polyethylene glycol polypropylene glycol monoacrylate, and poly (ethylene glycol-tetramethylene glycol) mono. Long chain polyalkylene glycol acrylates such as acrylates can also be used.
Furthermore, alcohols having two or more olefinic double bonds in the molecule can also be suitably used. Specifically, glycerol dimethacrylate, glycerol diacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and the like can be given.

Further, as described in JP-A-6-80776, an olefinic double bond such as methyl alcohol, ethyl alcohol, n-propyl alcohol, or isopropyl alcohol is added to the alcohol having the olefinic double bond. You may mix and use some alcohols which do not have.
In the polyamic acid ester, the R group derived from alcohols having no olefinic double bond is preferably in the range of 0 to 30 mol% with respect to the R groups derived from all alcohols. More preferably within the range of 10 mol%, most preferably 0 mol%. When the sum of R groups derived from alcohols having no olefinic double bond is 30 mol% or less, the lithography performance is excellent.
Stoichiometrically, the amount of alcohol used for esterification of tetracarboxylic dianhydride is 1.00 equivalent (monovalent) per 1.00 equivalent (0.50 mol) of tetracarboxylic dianhydride. However, when synthesizing a polyamic acid ester, 1.01 to 1.10 equivalents of alcohol per 1.00 equivalent of tetracarboxylic dianhydride is used to synthesize tetracarboxylic acid. It is preferable to synthesize a diester because the storage stability of the finally obtained photosensitive resin composition is improved.

Next, the Y group of the polyamic acid ester will be described. The Y group is a divalent aromatic group having 4 to 30 carbon atoms and is derived from aromatic diamines used as raw materials. By introducing an aromatic group into the diamine together with the tetracarboxylic dianhydride described above, the heat resistance of the cured polyimide resin film can be increased.
Specific examples of aromatic diamines include paraphenylene diamine, metaphenylene diamine, 4,4'-diaminodiphenyl ether, 4,4'-methylenebis (2-methylaniline), 4,4'-diaminodiphenyl sulfide, 4,4′-diaminobenzophenone, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfoxide, 3,3′- Dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4 '-Diaminobiphenyl, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) ) Benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) benzene, 9 , 10-bis (4-aminophenyl) anthracene, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane, 1,1,1,3,3 3-hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-amino 4-methylphenyl) propane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, or a part of the hydrogen atoms directly bonded to the aromatic ring of these aromatic diamines is a methyl group, an ethyl group, and Examples thereof include those substituted with a group selected from the group consisting of halogen groups. Any of the above aromatic diamines can be used alone or in admixture of two or more.

When the photosensitive resin composition of the present invention is formed into a relief pattern by i-line irradiation, bis (4- (4-aminophenoxy) phenyl) sulfone, 4,4′-diaminodiphenyl ether, 4,4′-methylenebis It is preferable to use aromatic diamines having good i-line permeability such as (2-methylaniline).
Examples of the divalent aliphatic group having 4 to 30 carbon atoms of the Y group include aliphatic diamines having an acyclic structure (hereinafter simply referred to as “aliphatic diamines”) or alicyclic structures. The diamines (hereinafter simply referred to as “alicyclic diamines”) can be preferably used.
Specific examples of the aliphatic diamines include ethylene glycol diamines such as bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, and bis (2-aminomethoxy) ethyl. ] Ether, bis [2- (2-aminoethoxy) ethyl] ether, bis [2- (3-aminoprotoxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2 -Aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether , Diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) Ether, methylenediamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diamino Examples include octane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane. These aliphatic diamines may be used alone or in combination of two or more.

  Specific examples of the alicyclic diamines include, for example, isophorone diamine, 4,4′-diaminodicyclohexylmethane, 1,8-diamino-p-menthane, 1,4-cyclohexanebis (methylamine), 1,3- Cyclohexanebis (methylamine), 2,5-diaminomethyl-bicyclo [2,2,2] octane, 2,5-diaminomethyl-7,7-dimethylbicyclo [2,2,1] heptane, 2,5- Diaminomethyl-7,7-difluorobicyclo [2,2,1] heptane, 2,5-diaminomethyl-7,7,8,8-tetrafluorobicyclo [2,2,2] octane, 2,5-diamino Methyl-7,7-bis (hexafluoromethyl) bicyclo [2,2,1] heptane, 2,5-diaminomethyl-7-oxabicyclo [2,2,1] hepta 2,5-diaminomethyl-7-thiabicyclo [2,2,1] heptane, 2,5-diaminomethyl-7-oxobicyclo [2,2,1] heptane, 2,5-diaminomethyl-7-azabicyclo [2,2,1] heptane, 2,6-diaminomethyl-bicyclo [2,2,2] octane, 2,6-diaminomethyl-7,7-dimethylbicyclo [2,2,1] heptane, 2, 6-diaminomethyl-7,7-difluorobicyclo [2,2,1] heptane, 2,6-diaminomethyl-7,7,8,8-tetrafluorobicyclo [2,2,2] octane, 2,6 -Diaminomethyl-7,7-bis (hexafluoromethyl) bicyclo [2,2,1] heptane, 2,6-diaminomethyl-7-oxybicyclo [2,2,1] heptane, 2,6-diaminomethyl 7-thiobicyclo [2,2,1] heptane, 2,6-diaminomethyl-7-oxobicyclo [2,2,1] heptane, 2,6-diaminomethyl-7-iminobicyclo [2,2,1] Heptane, 2,5-diamino-bicyclo [2,2,1] heptane, 2,5-diamino-bicyclo [2,2,2] octane, 2,5-diamino-7,7-dimethylbicyclo [2,2 , 1] heptane, 2,5-diamino-7,7-difluorobicyclo [2,2,1] heptane, 2,5-diamino-7,7,8,8-tetrafluorobicyclo [2,2,2] Octane, 2,5-diamino-7,7-bis (hexafluoromethyl) bicyclo [2,2,1] heptane, 2,5-diamino-7-oxabicyclo [2,2,1] heptane, 2,5 -Diamino-7-thiabicyclo [2,2,1] heptane, 2,5-diamino-7-oxobicyclo [2,2,1] heptane, 2,5-diamino-7-azabicyclo [2,2,1] heptane, 2,6- Diamino-bicyclo [2,2,1] heptane, 2,6-diamino-bicyclo [2,2,2] octane, 2,6-diamino-7,7-dimethylbicyclo [2,2,1] heptane, 2 , 6-Diamino-7,7-difluorobicyclo [2,2,1] heptane, 2,6-diamino-7,7,8,8-tetrafluorobicyclo [2,2,2] octane, 2,6- Diamino-7,7-bis (hexafluoromethyl) bicyclo [2,2,1] heptane, 2,6-diamino-7-oxybicyclo [2,2,1] heptane, 2,6-diamino-7-thiobicyclo [2,2,1] heptane, 2,6 Diamino-7-oxobicyclo [2,2,1] heptane, 2,6-diamino-7-iminobicyclo [2,2,1] heptane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1, 4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,4-di (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) ) Methane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, bicyclo [2,2,1] heptanebismethylamine, and the following formula ( Examples thereof include compounds represented by 2) and (3). These alicyclic diamines may be used alone or in combination of two or more.

（式中、Ｒ_１およびＲ_４は二価の炭化水素基を示し、それぞれ同一でも異なっていてもよく、Ｒ_２およびＲ_３は一価の炭化水素基を示し、それぞれ同一でも異なっていてもよく、ｐは１以上５０以下の整数を表す。） Examples of the diamine having a divalent silicon-containing group having 2 to 50 silicon atoms of the Y group (hereinafter simply referred to as “silicon-containing diamine”) include, for example, diamino (poly (polyethylene)) represented by the following formula (4): ) Siloxane can be preferably used.

(Wherein R ₁ and R ₄ represent a divalent hydrocarbon group, which may be the same or different, and R ₂ and R ₃ represent a monovalent hydrocarbon group, which may be the same or different, respectively. Well, p represents an integer of 1 to 50.)

Preferable structures of R ₁ and R ₂ include a methylene group, an ethylene group, a propylene group, a butylene group, and a phenylene group. Preferred examples of R ₂ and R ₃ include methyl group, ethyl group, propyl group, butyl group, and phenyl group.
The number average molecular weight of the polyamic acid ester is preferably 3000 to 100,000, more preferably 3000 to 50000. When the molecular weight is 3000 or more, heat resistance and strength are improved, and when it is 100,000 or less, solubility in a solvent is improved.
The polyamic acid ester can be synthesized by any known acid chloride method, DCC method, or isoimide method.

(B) Photopolymerization initiator Although the photosensitive resin composition of the present invention has photosensitivity derived from the double bond of the polyamic acid ester, the photosensitivity is further improved by adding a photopolymerization initiator. It is preferable.
Specific examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2,2′-diethoxyacetophenone, 2 Acetophenone derivatives such as hydroxy-2-methylpropiophenone, thioxanthone derivatives such as 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethyl ketal, benzyl-β- Benzyl derivatives such as methoxyethyl acetal, benzoin derivatives such as benzoin methyl ether, 2,6-di (4′-diazidobenzal) -4-methylcyclohexanone, 2,6′-di ( Azides such as' -diazidobenzal) cyclohexanone, 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenylpropanedione-2- (O-methoxycarbonyl) oxime, 1-phenylpropane Dione-2- (O-ethoxycarbonyl) oxime, 1-phenylpropanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3 -Oximes such as ethoxypropanetrione-2- (O-benzoyl) oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl peroxide, aromatic bisimidazoles, titanocenes, etc. Used, but oximes are preferred in terms of light sensitivity There. The addition amount of these photopolymerization initiators is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the (a) polyamic acid ester.

(C) Organic solvent In the present invention, the above-mentioned polyamic acid ester and photopolymerization initiator are dissolved in an organic solvent and used as a varnish-like composition. The organic solvent contains N-ethyl-2-pyrrolidone or 1,3-dimethyl-2-imidazolidinone or a mixture of both as an essential component, and the content thereof is 50% by mass or more based on the total amount of the organic solvent. However, the content is more preferably 80% by mass or more, and most preferably 100%. When the content is 50% by mass or more, there is an effect of shortening the development time, which is preferable.
The remaining components of the organic solvent are not particularly limited as long as they dissolve the above-described polyamic acid ester and photopolymerization initiator. Preferred examples of the good solvent for the polyamic acid ester include N, N-dimethylformamide, N-methylpyrrolidone (hereinafter also referred to as NMP), N, N-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, Examples include α-acetyl-γ-butyrolactone, tetramethylurea, N-cyclohexyl-2-pyrrolidone, and the like. These can be used alone or in combination of two or more.
These solvents can be used in the range of 100 to 600 parts by weight, preferably 120 to 400 parts by weight, based on 100 parts by weight of the polyamic acid ester, depending on the coating film thickness and viscosity.
Furthermore, in order to improve the storage stability of the polyamic acid ester composition of the present invention, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, ethanol and the like are used in an organic solvent used as a solvent. It is preferable to contain various alcohols.

The alcoholic solvent that can be used is not particularly limited as long as it has an alcoholic hydroxyl group in the molecule. Specific examples thereof include methyl alcohol, ethyl alcohol, n-propyl 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-2-ethyl ether, propylene glycol-1 -(N-propyl) ether, propylene glycol-2- (n-propyl) ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether Monoalcohols, ethylene glycol, di alcohols such as propylene glycol, and the like. Among these, ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1- (n-propyl) ether are more preferable.
The content of the alcoholic solvent in the total organic solvent is preferably 5 to 50% by weight, more preferably 10 to 30% by weight. When the content of the alcoholic solvent is 5 to 50% by weight, the storage stability of the polyamic acid ester composition is good. For example, when the polyamic acid ester composition left at room temperature for 2 weeks is used as a coating film, No precipitate is observed.

(D) Other components In order to further improve the photosensitivity, a compound having a reactive carbon-carbon double bond that does not correspond to the component (a) can be added to the photosensitive resin composition of the present invention. . Such compounds include 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate (2-20 moles of ethylene monomer units), pentaerythritol diacrylate, dipenta Examples include erythritol hexaacrylate, tetramethylol methane tetraacrylate, methylene bisacrylamide, N-methylol acrylamide, and compounds obtained by substituting acrylate or acrylamide with methacrylate or methacrylamide, respectively. The compound having such a reactive carbon-carbon double bond is preferably added in an amount of 1 to 100 parts by weight, particularly 1 to 70 parts by weight, based on 100 parts by weight of the (a) polyamic acid ester.

  To further improve the photosensitivity, a sensitizer can be added to the photosensitive resin composition of the present invention. 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-dimethylaminocinnamylidene Indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) isonaphth Thiazole, 1,3-bis (4′-di Tilaminobenzal) 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 and the like.

From the viewpoint of sensitivity, it is preferable to use a combination of a sensitizer having a mercapto group and a sensitizer having a dialkylaminophenyl group. These can be used alone or in combination of 2 to 5 kinds. The sensitizer for improving the photosensitivity is preferably used in an amount of 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass with respect to 100 parts by mass of the (a) polyamic acid ester.
In addition, an adhesion aid can be added to the photosensitive resin composition of the present invention in order to improve the adhesion to 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] phthalimidic acid, benzophenone-3,3′-bis (N- [3-triethoxysilyl] propylamide) -4,4′-dicarboxylic acid, and benzene-1 , 4-bis (N- [3-tri Toxisilyl] propylamide) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propyl succinic anhydride, silane coupling agents such as N-phenylaminopropyltrimethoxysilane, and aluminum tris (ethyl acetoacetate), Aluminum adhesion assistants such as aluminum tris (acetylacetonate) and ethyl acetoacetate aluminum diisopropylate are listed. 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 50 parts by mass, particularly 0.5 to 20 parts by mass with respect to (a) 100 parts by mass of the polyamic acid ester.

  In addition, a thermal polymerization inhibitor can be added to the photosensitive resin composition of the present invention in order to improve the viscosity of the 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 a thermal-polymerization inhibitor, the range of 0.005-30 mass parts with respect to 100 mass parts of (a) polyamic-acid ester is preferable especially 0.005-10 mass parts.

In the polyamic acid ester composition of the present invention, an organic titanium compound can be used as a component for improving heat resistance and chemical resistance. The usable organic titanium compound is not particularly limited as long as the organic chemical substance is bonded to the titanium atom through a covalent bond or an ionic bond.
Specific examples of organotitanium compounds that can be used are first titanocenes. As the titanocene, pentamethylcyclopentadienyl titanium trimethoxide and the like are used. In this case, if titanocenes that function as a photoinitiator such as bis (2,6-difluoro-3- (1-hydropyrrol-1-yl) phenyl) titanocene are used, there are other cases that may be used in the present invention. An organic titanium compound that does not function as a photoinitiator may be more preferable because a good pattern may be difficult to obtain due to interference with the initiator.
Another specific example of the organic titanium compound that can be used in the present invention is a titanium chelate. In the present invention, among titanium chelates, those having two or more alkoxy groups are more preferred because of the stability of the composition and good pattern, and specific preferred examples include titanium bis (triethanol Amine) diisopropoxide, titanium di (n-butoxide) (bis-2,4-pentanedionate), titanium diisopropoxide (bis-2,4-pentanedionate), titanium diisopropoxide bis ( Tetramethylheptanedionate), titanium diisopropoxide bis (ethylacetoacetate) and the like.

In the present invention, titanium tetra (n-butoxide), titanium tetraethoxide, titanium tetra (2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetra Methoxypropoxide, titanium tetramethylphenoxide, titanium tetra (n-nonoxide), titanium tetra (n-propoxide), titanium tetrastearyloxide, titanium tetrakis (bis-2,2- (allyloxymethyl) butoxide), etc. Tetraalkoxides, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide, etc. Iodides, Titanium oxide bis (pentanedionate), Titanium oxide bis (tetramethylheptanedionate), Titanium oxides such as phthalocyanine titanium oxide, Tetraacetylacetonates such as titanium tetraacetylacetonate, Isopropyltridodecylbenzenesulfonyl Titanate coupling agents such as titanate can also be used.
The amount of these organic titanium compounds added is preferably 0.3 to 10 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the polyamic acid ester used as the component (A). is there. When the addition amount is 0.3 to 10 parts by weight, the heat resistance and chemical resistance are excellent and the storage stability is excellent.
The photosensitive resin composition of the present invention can be obtained by mixing the above-described components in any order. Moreover, components other than the polyamic acid ester may be dissolved in a solvent in advance, and then the polyamic acid ester may be dissolved.

<Method for forming cured relief pattern>
As one aspect of the method of forming the cured relief pattern which consists of a polyimide resin from the photosensitive resin composition of this invention, the following processes are preferable.
(I) The process of forming a coating film on this base material by apply | coating said photosensitive resin composition to a base material, and drying.
(Ii) A step of irradiating the coating film with ultraviolet rays through a photomask having a pattern or directly.
(Iii) A step of removing an unexposed portion of the coating film by developing with a developer, thereby forming a relief pattern on the substrate.
(Iv) A step of imidizing the polyamic acid ester in the pattern by heating the relief pattern, thereby forming a cured relief pattern made of a polyimide resin on the substrate.

Examples of the substrate that can be used in the method for forming a cured relief pattern of the present invention include a silicon wafer, a metal, glass, a semiconductor, a metal oxide insulating film, and silicon nitride. A silicon wafer is preferably used. The thickness of the substrate is preferably 200 μm to 800 μm, but is not limited thereto.
As a method for applying the photosensitive resin composition of the present invention on a substrate, methods conventionally used for applying a photosensitive resin composition, for example, spin coater, bar coater, blade coater, curtain coater, or A method of applying with a screen printer or the like, or a method of applying with a spray coater 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 to dry the coating film under conditions that do not cause imidation of the polyamic acid ester in the composition. Specifically, when air drying or heat drying is performed, it is preferably performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour.
The coating film thus obtained is subjected to pattern exposure with an ultraviolet light source or the like using an exposure apparatus such as a contact aligner, mirror projection, or stepper, and then developed.

As the developer used for development, a good solvent for the polyamic acid ester or a combination of the good solvent and the poor solvent is preferable. Preferred good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. It is done. As the poor solvent, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable. When a good solvent and a poor solvent are mixed and used, the ratio of the poor solvent to the good solvent is adjusted by the solubility of the polyamic acid ester. Moreover, several types of solvents can be used in combination.
As a method used for development, an arbitrary method can be selected and used from conventionally known photoresist development methods such as a rotary spray method, a paddle method, and an immersion method involving ultrasonic treatment.

By heating the relief pattern of the polyamic acid ester obtained as described above, and volatilizing the photopolymerized group having an olefinic double bond, it is converted into a cured relief pattern made of polyimide resin. To do. 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 a method for heat conversion. Heating can be performed at 280 ° C. to 450 ° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas for heat conversion, and an inert gas such as nitrogen or argon may be used.
In still another aspect of the present invention, a semiconductor device having a polyimide pattern formed by the above-described method is provided. The semiconductor device can be obtained by combining the above-described polyimide pattern forming method with a known method for manufacturing a semiconductor device.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but these do not limit the scope of the present invention.
In Examples, Comparative Examples, and Reference Examples, the physical properties of the photosensitive compositions were measured and evaluated according to the following methods.
(1) Number average molecular weight The number average molecular weight (Mn) of each polyamic acid ester was measured by the gel permeation chromatography method (standard polystyrene conversion).
(2) Resolution of photosensitive resin composition and accuracy of polyimide pattern The photosensitive composition was spin-coated on a 5-inch silicon wafer and dried to form a 10 μm thick coating film. This coating film was irradiated with energy of 250 mJ / cm ² using an i-line stepper NSR2005i8A (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. At this time, the minimum development time required for complete dissolution and removal of the unexposed portion was examined.

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 Thermo Systems, Japan). As a result, 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 exposure through a reticle with a test pattern in the same manner as described above, and the area of the obtained pattern opening corresponds to the corresponding pattern mask opening. If the area is ½ or more of the area, 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 defined 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. In addition, pattern accuracy was evaluated based on the following criteria.
“Good”: The pattern cross section is not slid, no swelling or bridging occurs, and the aspect ratio is 1 or more. Furthermore, the pattern shape does not change during heat curing.
"Bad" ... Any one of the above conditions is not satisfied.

(Synthesis of polyamic acid ester A)
Place 159.9 g of 4,4′-oxydiphthalic dianhydride (ODPA) in a 2 liter separable flask, add 136.8 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 210.4 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 96.4 g in 350 ml of γ-butyrolactone 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 obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polyamic acid ester A). When the molecular weight of the polyamic acid ester A was measured by gel permeation chromatography (standard polystyrene conversion), the number average molecular weight (Mn) was 14,000.

(Synthesis of polyamic acid ester B)
165.9 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) was placed in a 2 liter separable flask, 136.8 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone. The mixture was stirred at room temperature, and 81.5 g of pyridine was added with stirring 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 210.4 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by bis [4- (4-aminophenoxy) A suspension of 208.0 g of phenyl] sulfone in 350 ml of γ-butyrolactone 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 dried in vacuo to obtain a powdery polymer (polyamic acid ester B). When the molecular weight of the polyamic acid ester B was measured by gel permeation chromatography (standard polystyrene conversion), the number average molecular weight (Mn) was 17,000.

<Example 1>
Using the obtained polyamic acid ester A, a photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. 100 g of polyamic acid ester A, 4 g of diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime (photoinitiator), 4 g of tetraethylene glycol dimethacrylate, 1 g of 1-phenyl-5-mercaptotetrazole, 4 g of N-phenyldiethanolamine, N -After dissolving in 200 g of 1,3-dimethyl-2-imidazolidinone (DMI) together with 3 g of [3- (triethoxysilyl) propyl] phthalamic acid and 0.05 g of 2-nitroso-1-naphthol, 1 μm Teflon The photosensitive resin composition (A-1) was adjusted by filtering with a filter.
The resolution of the polyimide coating film obtained from the photosensitive resin composition was 8 μm when the film thickness after coating and drying was 10 μm, the aspect ratio was 1 or more, and the pattern accuracy was good. The minimum development time at this time was as good as 17 seconds.

<Example 2>
50 g of the resulting polyamic acid ester A and 50 g of the polyamic acid ester B were mixed with 4 g of diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime (photoinitiator), 4 g of tetraethylene glycol dimethacrylate, 1-phenyl-5-mercaptotetrazole. 1 g, dissolved in 180 g of N-ethyl-2-pyrrolidone (NEP) together with 4 g of N-phenyldiethanolamine, 3 g of N- [3- (triethoxysilyl) propyl] phthalamic acid, and 0.05 g of 2-nitroso-1-naphthol Then, it filtered with a 1 micrometer Teflon filter and adjusted the photosensitive resin composition (A-2).
The resolution of the polyimide coating film obtained from the photosensitive resin composition was 8 μm when the film thickness after coating and drying was 10 μm, the aspect ratio was 1 or more, and the pattern accuracy was good. The minimum development time at this time was good at 18 seconds.

<Example 3>
A photosensitive resin composition (A-3) was prepared in the same manner as in Example 2 except that N-ethyl-2-pyrrolidone (NEP) in Example 2 was changed to 1,3-dimethyl-2-imidazolidine. .
The resolution of the polyimide coating film obtained from the photosensitive resin composition was 8 μm when the film thickness after coating and drying was 10 μm, the aspect ratio was 1 or more, and the pattern accuracy was good. The minimum development time at this time was good at 16 seconds.

<Example 4>
Photosensitivity was the same as in Example 2 except that 180 g of N-ethyl-2-pyrrolidone (NEP) in Example 2 was changed to 90 g of 1,3-dimethyl-2-imidazolidine and 90 g of N-methyl-2-pyrrolidone. Resin composition (A-4) was prepared.
The resolution of the polyimide coating film obtained from the photosensitive resin composition was 8 μm when the film thickness after coating and drying was 10 μm, the aspect ratio was 1 or more, and the pattern accuracy was good. At this time, the minimum development time was 20 seconds, which was good.

<Comparative Example 1>
A photosensitive resin composition (B-1) was prepared in the same manner as in Example 1 except that 1,3-dimethylimidazolidinone (DMI) in Example 1 was changed to N-methyl-2-pyrrolidone (NMP). did.
The resolution of the polyimide coating film obtained from the photosensitive resin composition was 8 μm when the film thickness after coating and drying was 10 μm, the aspect ratio was 1 or more and the pattern accuracy was good, but the minimum development time was As long as 25 seconds, the requirement was not met.

<Comparative example 2>
A photosensitive resin composition (B-2) was prepared in the same manner as in Example 2 except that N-ethyl-2-pyrrolidone (NEP) in Example 2 was changed to N-methyl-2-pyrrolidone (NMP). .
The resolution of the polyimide coating film obtained from the photosensitive resin composition was 8 μm when the film thickness after coating and drying was 10 μm, the aspect ratio was 1 or more and the pattern accuracy was good, but the minimum development time was It was 26 seconds long and did not meet the requirements.

  The composition of the present invention and the method for producing a cured relief pattern having heat resistance using the composition can be suitably used in the field of semiconductor device production.

Claims (2)

(A) including 100 parts by mass of a polyamic acid ester having a repeating unit represented by the following general formula (1), (b) 1 to 20 parts by mass of a photopolymerization initiator, and (c) 30 to 600 parts by mass of an organic solvent. It is a composition, and (c) the content of N-ethyl-2-pyrrolidone and / or 1,3-dimethyl-2-imidazolidinone in the organic solvent is 50 mass with respect to the total amount of (c) organic solvent % Photosensitive resin composition characterized by being at least%.

(In the general formula (1), X represents at least one tetravalent organic group having 6 to 32 carbon atoms, and Y represents a divalent aromatic group, aliphatic group and silicon number having 4 to 30 carbon atoms. And at least one group selected from the group consisting of ˜50 divalent silicon-containing groups, R represents a monovalent group having an olefinic double bond.)   (1) The photosensitive resin composition according to claim 1 is applied on a substrate in the form of a layer or a film to form a photosensitive resin film, and (2) the photosensitive resin film is applied with actinic radiation through a mask. Curing characterized by exposing to light, electron beam or ion beam directly on the photosensitive resin film, (3) developing the photosensitive resin film, and (4) heat-treating the obtained relief pattern A method for producing a relief pattern.