JP5486201B2 - Photosensitive resin composition - Google Patents

Description

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

  Conventionally, polyimide resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been used for surface protective films and interlayer insulating films of semiconductor devices. This polyimide resin is currently generally used as a photosensitive polyimide precursor composition, and is applied to a substrate, patterned with actinic rays, developed, thermal imidization treatment, etc., so that a surface protective film and an interlayer are formed on a semiconductor device. An insulating film or the like can be easily formed, and the process can be significantly shortened as compared with the conventional non-photosensitive polyimide precursor composition.

However, the photosensitive polyimide precursor composition needs to use a large amount of an organic solvent such as N-methyl-2-pyrrolidone as a developing solution in the developing process. Countermeasures for organic solvents have been demanded. In response to this, recently, various heat-resistant photosensitive resin materials that can be developed with an alkaline aqueous solution have been proposed in the same manner as photoresists.
Among them, a PBO precursor composition obtained by mixing an alkaline aqueous solution-soluble hydroxypolyamide, such as polybenzoxazole (hereinafter also referred to as “PBO”) precursor, with a photoactive component such as a diazoquinone compound is used as a positive photosensitive resin composition. A method to be used has been attracting attention in recent years (for example, see Patent Document 1 below).

  The development mechanism of this positive photosensitive resin is that the unexposed portion of the diazoquinone compound is insoluble in the alkaline aqueous solution, but the exposure causes the diazoquinone compound to undergo a chemical change to become an indenecarboxylic acid compound, which becomes an alkaline aqueous solution. It utilizes the fact that it becomes soluble. By using the difference in dissolution rate with respect to the developer between the exposed portion and the unexposed portion, a relief pattern of only the unexposed portion can be created.

The PBO precursor composition described above can form a positive relief pattern by exposure and development with an alkaline aqueous solution. Further, when heated (hereinafter also referred to as “cure”), an oxazole ring is generated, and the cured PBO film has the same thermosetting film characteristics as a polyimide film. Has attracted attention as an alternative material.
In recent years, polyimide has also been used as a passivation layer in the subsequent process of semiconductors, and it has become necessary to have resistance to flux during reflow in the process of forming solder bumps and resistance to a stripping solution during resist stripping.

However, the above-mentioned PBO film has poor flux resistance and solvent resistance during reflow, and cracks may occur in the film or the film may dissolve after the reflow and resist stripping steps.
Further, in the bump forming step, when a wiring layer is formed on the passivation layer from the electrode in the opening of the passivation layer, a metal seed layer may be formed by sputtering. When the metal layer is formed by sputtering as described above, it is desirable that the side wall angle of the opening of the passivation film is gentle and the side wall shape has no corners in order to form a uniform film thickness of the metal layer.

Usually, when the chemical resistance is improved, a three-dimensional cross-link of the polymer is formed, so that the corners of the side wall shape are easily formed. Therefore, when PBO is used as an alternative material for polyimide, a composition having a good balance between the above-mentioned chemical resistance and side wall shape is required.
As a method for improving the chemical resistance of the PBO film, there is a method using a thermal crosslinking agent, and it is known that a combination of an acid generator that promotes a ring-opening reaction between an oxetane compound and oxetane is effective. (For example, see Patent Documents 2, 3, and 4 below). However, depending on the type of the acid generator, there is a risk of remaining in the film after curing and corroding the metal layer. In addition, in the case where the oxetane compound does not have an acid generator for promoting the ring-opening reaction, the crosslinking reaction does not proceed sufficiently, and excellent chemical resistance cannot be obtained.
Moreover, although a methylol containing compound may be used as a thermal crosslinking agent for improving the chemical resistance of the PBO film, when the methylol containing compound is used, the side wall shape tends to have a corner.

JP 2002-328472 A JP 2008-107512 A JP 2008-139328 A JP 2008-145579 A

  The problems to be solved by the present invention include a novel photosensitive resin composition used in a semiconductor post-process reflow or resist stripping process, sufficient resistance to flux and solvent using the composition, and sidewalls It is an object to provide a method for producing a cured relief pattern having no corners in shape, and a semiconductor device having the cured relief pattern.

As a result of intensive studies in order to solve the above problems, the present inventors combined a compound containing an oxetanyl group and a thermal crosslinking agent in a specific ratio with a hydroxypolyamide having a specific structure and a diazoquinone compound, The inventors have found a photosensitive resin composition that has sufficient resistance to a flux and a solvent and can obtain a cured relief pattern having no corners in the side wall shape, and has led to the present invention.
That is, the present invention is as follows.

[1] (A) The following general formula (1):
{Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, and Y ₁ is a divalent organic group having at least 2 carbon atoms. } Containing 100 parts by mass of a hydroxy polyamide having a structure represented by: (B) 1 to 100 parts by mass of a diazoquinone compound, (C) a compound containing an oxetanyl group, and (D) a thermal crosslinking agent, The total content of the compound containing an oxetanyl group and the (D) thermal crosslinking agent is 20 to 50 parts by mass, and the mass of the (D) thermal crosslinking agent relative to the compound containing the (C) oxetanyl group A photosensitive resin composition having a ratio of 0.06 to 0.67.

[2] The thermal crosslinking agent (D) is represented by the following general formula (2):
{In the formula, R ₁ is a monovalent organic group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms; R ₂ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms; It is a monovalent organic group selected from the group consisting of a hydroxyl group, an ester group having 2 to 10 carbon atoms, and a urethane group having 2 to 10 carbon atoms, n is an integer of 1 to 3, and p is 1 to 1 5 is an integer of 5, q is an integer of 0 to 4, (p + q) = 5, k is an integer of 1 to 4, and when k = 1, X is C _n H _2n OR ₁ or R ₂ , and when k = 2 to 4, X represents a single bond or a divalent to tetravalent organic group, p and q in the case where p and q are plural, and C _n H _2n OR ₁ , And when R ₂ is present in plural, (C _n H _2n OR ₁ ) n, R ₁ , and R ₂ may be the same as or different from each other. } And the following general formula (3):
{In the formula, R ₁ is a monovalent organic group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 3. } The photosensitive resin composition as described in [1] above, which is at least one alkoxyalkyl group-containing compound selected from the group consisting of compounds represented by:

[3] The (D) thermal crosslinking agent has the following general formula (2):
{In the formula, R ₁ is a monovalent organic group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms; R ₂ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms; It is a monovalent organic group selected from the group consisting of a hydroxyl group, an ester group having 2 to 10 carbon atoms, and a urethane group having 2 to 10 carbon atoms, n is an integer of 1 to 3, and p is 1 to 1 5 is an integer of 5, q is an integer of 0 to 4, (p + q) = 5, k is an integer of 1 to 4, and when k = 1, X is C _n H _2n OR ₁ or R ₂ , and when k = 2 to 4, X represents a single bond or a divalent to tetravalent organic group, p and q in the case where p and q are plural, and C _n H _2n OR ₁ , And when R ₂ is present in plural, (C _n H _2n OR ₁ ) n, R ₁ , and R ₂ may be the same as or different from each other. } The photosensitive resin composition as described in [1] above, which is at least one alkoxyalkyl group-containing compound represented by:

  [4] The above (D) thermal crosslinking agent is at least one compound selected from the group consisting of methoxymethylbiphenyl, dimethoxymethylbenzene, bis (methoxymethyl) biphenyl, dimethoxymethyldiphenyl ether, and dimethoxymethyldiphenylmethane. 1]. The photosensitive resin composition as described in 1].

  [5] The photosensitive resin composition according to any one of [1] to [4], wherein the content of the compound containing the (C) oxetanyl group is 15 to 35 parts by mass.

  [6] A step of forming a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [5] on a substrate, an exposure step of exposing the photosensitive resin layer, a step of developing, A method for producing a cured relief pattern, comprising a step of heating the obtained relief pattern.

  [7] A semiconductor device having a cured relief pattern layer obtained by the production method according to [6].

  According to the present invention, a hydroxy polyamide and a diazoquinone compound having a specific structure are combined with a compound containing an oxetanyl group and a thermal cross-linking agent in a specific ratio to have sufficient resistance to a flux and a solvent, and have a sidewall shape. A cured relief pattern with no corners can be obtained, a photosensitive resin composition used in a semiconductor reflow process and a resist stripping process, and has sufficient resistance to flux and solvent using the composition. In addition, a method for manufacturing a cured relief pattern having no corners in the side wall shape and a semiconductor device having the cured relief pattern are provided.

Relief pattern side wall shape (the side wall has no corners and is evaluated as good) Side wall shape of relief pattern (the side wall has corners and is evaluated as defective)

Each component which comprises the photosensitive resin composition of this invention is demonstrated concretely below.
<Photosensitive resin composition>
(A) Hydroxypolyamide Hydroxypolyamide, which is the base polymer of the photosensitive resin composition of the present invention, has the following general formula (1):
{Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, and Y ₁ is a divalent organic group having at least 2 carbon atoms. } Is included. Moreover, in order to control alkali solubility, you may substitute a part of repeating unit structure shown by the said General formula (1).
Specifically, the following general formula (4):
{Wherein X ₁ is a tetravalent organic group having a carbon atom, and X ₂ , Y ₁ and Y ₂ are each independently a divalent organic group having 2 or more carbon atoms. , L is an integer from 2 to 1,000, m is an integer from 1 to 500, l / (l + m)> 0.5, and ₁ dihydroxydiamide containing X ₁ and Y ₁ The arrangement order of the units and m diamide units including X ₂ and Y ₂ is not limited. }, A polymer having a diamine structure having a X ₁ (NH ₂ ) ₂ structure as a part of bisaminophenol having a X ₁ (NH ₂ ) ₂ (OH) ₂ structure represented by
X ₁ is preferably a tetravalent organic group having 2 or more and 30 or less carbon atoms. X ₂ , Y ₁ and Y ₂ are preferably each independently a divalent organic group having 2 or more and 30 or less carbon atoms.

The dihydroxydiamide unit of the hydroxypolyamide has a structure obtained by polycondensation of a dicarboxylic acid having a Y ₁ (COOH) ₂ structure and a bisaminophenol having a X ₁ (NH ₂ ) ₂ (OH) ₂ structure. Here, the two amino groups and the hydroxy group of the bisaminophenol are each in the ortho position, and the dihydroxydiamide unit is closed by heating the hydroxypolyamide at about 280 to 400 ° C. Thus, the benzoxazole unit, which is a heat resistant resin, is changed. m is preferably in the range of 2 to 1,000, more preferably in the range of 2 to 200, still more preferably in the range of 3 to 50, and most preferably in the range of 3 to 20.

If necessary, the hydroxypolyamide may be condensed with n diamide units of the general formula (4). The diamide unit has a structure in which a diamine having a structure of X ₂ (NH ₂ ) ₂ and a dicarboxylic having a structure of Y ₂ (COOH) ₂ are polycondensed. n is preferably in the range of 0 to 500, and more preferably in the range of 0 to 10. The higher the ratio of hydroxypolyamide units in the hydroxypolyamide, the higher the solubility in an alkaline aqueous solution used as a developer, and the shorter the time required for development, the value of l / (l + m) is 0.5 or more. Preferably, it is 0.7 or more, more preferably 0.8 or more.

Examples of the bisaminophenol having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, and 4,4 ′. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino- 4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis -(4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis -(4-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-diamino-4,6-dihydroxybenzene and the like. These bisaminophenols may be used alone or in combination.

Of these bisaminophenols, particularly preferred are those where X ₁ is:
In the case of an aromatic group selected from the group consisting of

Preferred examples of the diamine having the X ₂ (NH ₂ ) ₂ structure include aromatic diamines and silicon diamines.
Among these, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl ether, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′- Diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2′-bis (4-aminophenyl) ) Propane, 2,2'-bis (4-aminophenyl) hexa 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, and 4, 4′-diaminobenzanilide, and at least one selected from the group consisting of a hydrogen atom of an aromatic nucleus of these aromatic diamines consisting of a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, and a phenyl group And a compound substituted by a group or an atom.

Further, silicon diamine can be selected in order to enhance the adhesion to the substrate. Examples of this include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, and bis (4 -Aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis ( γ-aminopropyl) tetraphenyldisiloxane and the like.
Examples of the dicarboxylic acid having the structure of Y ₁ (COOH) ₂ or Y ₂ (COOH) ₂ include those in which Y ₁ and Y ₂ are an aliphatic group or an aromatic group having a linear, branched, or cyclic structure. Can be mentioned. Among these, when Y ₁ or Y ₂ is an aromatic group, for example, the following:
{In the formula, A is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, and a single bond. R represents a group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, and a halogen atom, and k represents an integer of 0 to 4. } Groups are preferred.

It is also preferable to use a derivative of 5-aminoisophthalic acid for a part or all of the dicarboxylic acid having the Y ₁ (COOH) ₂ or Y ₂ (COOH) ₂ structure.
Specific compounds to be reacted with 5-aminoisophthalic acid to obtain the derivative include 5-norbornene-2,3-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3, 6-tetrahydrophthalic anhydride, 3-ethynyl-1,2-phthalic anhydride, 4-ethynyl-1,2-phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 1 -Cyclohexene-1,2-dicarboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, allyl succinic anhydride , Isocyanate ethyl methacrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate 3-cyclohexene-1-carboxylic acid chloride, 2-furancarboxylic acid chloride, crotonic acid chloride, cinnamic acid chloride, methacrylic acid chloride, acrylic acid chloride, propiolic acid chloride, tetrolic acid chloride, thiophene-2-acetyl chloride, p-styrene sulfonyl chloride, glycidyl methacrylate, allyl glycidyl ether, chloroformate methyl ester, chloroformate ethyl ester, chloroformate n-propyl ester, chloroformate isopropyl ester, chloroformate isobutyl ester, chloroformate 2- Ethoxy ester, chloroformate-sec-butyl ester, chloroformate benzyl ester, chloroformate 2-ethylhexyl ester, chloroformate allyl ester, chloroformate phenyl ester, chloride Formic acid 2,2,2-trichloroethyl ester, chloroformic acid-2-butoxyethyl ester, chloroformic acid-p-nitrobenzyl ester, chloroformic acid-p-methoxybenzyl ester, isobornyl benzyl chloroformate , Chloroformic acid-p-biphenylisopropylbenzyl ester, 2-t-butyloxycarbonyl-oxyimino-2-phenylacetonitrile, St-butyloxycarbonyl-4,6-dimethyl-thiopyrimidine, di-t-butyl- Dicarbonate, N-ethoxycarbonylphthalimide, ethyldithiocarbonyl chloride, formic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, methanesulfonic acid chloride, acetyl chloride, trityl chloride, trimethylchlorosilane, hexamethyldisi Zan, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (dimethylamino) trimethylsilane, trimethylsilyldiphenylurea, bis (trimethylsilyl) urea, isocyanic acid Examples include phenyl, n-butyl isocyanate, n-octadecyl isocyanate, o-tolyl isocyanate, 1,2-phthalic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, glutaric anhydride, and the like.

Furthermore, as a dicarboxylic acid having a Y ₁ (COOH) ₂ or Y ₂ (COOH) ₂ structure, a compound obtained by ring-opening a tetracarboxylic dianhydride with a monoalcohol, a monoamine or the like can also be used. Examples of the monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, benzyl alcohol and the like, and examples of the monoamine include butylamine and aniline. Examples of the tetracarboxylic dianhydrides include the following:
_{Wherein, B is, -CH 2 -, - O - , - S -, - SO 2 -, - CO -, - NHCO-, and -C _{(CF 3) 2} - ₂ is selected from the group consisting of Is a valent group. }.

Further, by reacting trimellitic acid chloride to the bisaminophenol generates tetracarboxylic dianhydride, by ring-opening in the same way _Y 1 _{(COOH) 2} or _{Y 2 (COOH)} 2 It can also be used as a dicarboxylic acid having a structure. The tetracarboxylic dianhydride obtained here is as follows:
{Wherein X ₃ represents X ₁ (OH) ₂ (NH—) ₂ , and X ₁ is the same as defined in the above general formula (I). }.

  Alternatively, the tetracarboxylic dianhydride and the bisaminophenol can be reacted, and the resulting carboxylic acid residue can be esterified or amidated with a monoalcohol or monoamine.

When Y ₁ or Y ₂ is an aliphatic group, substituents such as an alkyl chain, a cyclobutyl ring, a cyclopentyl ring, a cyclohexyl ring, and a bicyclo ring are exemplified. Examples of the dicarboxylic acid having a Y ₁ (COOH) ₂ or Y ₂ (COOH) ₂ structure having an aliphatic group include malonic acid, methyl malonic acid, dimethyl malonic acid, succinic acid, glutaric acid, adipic acid, and itaconic acid. , Maleic acid, diglycolic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, octahydro-1H-4,7-methanoindenedicarboxylic acid and the like can be mentioned, but as dicarboxylic acid having an aliphatic group , Octahydro-1H-4,7-methanoindene dicarboxylic acid When using the, for compatible and high transparency, a high solubility in solvents, preferred.

As a method for polycondensation of a dicarboxylic acid having a Y ₁ (COOH) ₂ structure and a bisaminophenol having a X ₁ (NH ₂ ) ₂ (OH) ₂ structure to produce a dihydroxydiamide unit, a dicarboxylic acid is used. And thionyl chloride to form diacid chloride and then react with bisaminophenol, and dicarboxylic acid and bisaminophenol are polycondensed with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be allowed to act simultaneously.

The above-mentioned (A) hydroxypolyamide is also preferably used with its end group sealed with an organic group (hereinafter referred to as “sealing group”).
In the polycondensation of hydroxypolyamide, when the dicarboxylic acid component is used in an excessive number of moles compared to the sum of the bisaminophenol component and the diamine component, a compound having an amino group or a hydroxyl group is used as the sealing group. Is preferred. Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, hydroxyethyl acrylate and the like.
Conversely, when the sum of the bisaminophenol component and the diamine component is used in an excessive number of moles compared to the dicarboxylic acid component, the sealing group has an acid anhydride, carboxylic acid, acid chloride, isocyanate group, etc. It is preferable to use a compound. Examples of the compound include benzoyl chloride, norbornene dicarboxylic anhydride, norbornene carboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, methylcyclohexane dicarboxylic anhydride Products, cyclohexenedicarboxylic anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, tosylic chloride and the like.

  (A) The weight average molecular weight in terms of polystyrene by gel permeation chromatography (hereinafter also referred to as “GPC”) of hydroxypolyamide is preferably 3,000 to 50,000, and preferably 6,000 to 30,000. It is more preferable. The weight average molecular weight is preferably 3,000 or more from the viewpoint of physical properties of the cured relief pattern, and is preferably 50,000 or less from the viewpoint of resolution. As developing solvents for GPC, tetrahydrofuran (hereinafter also referred to as “THF”) and N-methyl-2-pyrrolidone (hereinafter also referred to as “NMP”) are recommended. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended to select standard monodisperse polystyrene from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko.

(B) Diazoquinone Compound The diazoquinone compound used in the photosensitive resin composition is a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure. US Pat. No. 2,772,972, No. 2,797,213, No. 3,669,658 and the like. Examples of preferred ones include, for example:
{Wherein Q is a hydrogen atom or the following:
The naphthoquinonediazide sulfonate group shown in FIG. 5 and all Q's are not simultaneously hydrogen atoms. }.

  (B) As for the compounding quantity of a diazoquinone compound, 1-100 mass parts is preferable with respect to 100 mass parts of (A) hydroxy polyamide, and 10-30 mass parts is more preferable. When the blending amount of the (B) diazoquinone compound is 1 part by mass or more, the patterning property of the resin is good. Scum) is low.

(C) Oxetanyl group-containing compound The oxetanyl group-containing compound is a compound represented by the following general formula:
It is a compound containing the compound represented by these.

Preferred examples of the oxetanyl group-containing compound represented by the above general formula include 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis [1-ethyl (3-oxetanyl)]. Methyl ether, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4′-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol bis (3-ethyl- 3-oxetanylmethyl) ether, diethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenoate, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, Pentaerythritol tetrakis (3-ethyl-3-oxe Nylmethyl) ether, 3-ethyl-3-hydroxymethyloxetane (OXT-101), 2-ethylhexyl oxetane (OXT-212), xylylenebisoxetane (OXT-121), 3-ethyl-3-{[( 3-ethyloxetane-3-yl) methoxy] methyl} oxetane (OXT-221), the following:
Examples include Etanacol EHO, OXBP, OXMA, OXIPA, HBOX, etc., from Ube Industries.
The oxetanyl group-containing compound of the present invention is not particularly limited as long as it is a compound having an oxetanyl group.
Among these, OXBP, OXIPA, OXT-121, and OXT-221 are preferable from the viewpoint of solubility in a developer.

(D) Thermal cross-linking agent A thermal cross-linking agent is a compound that causes a cross-linking reaction with hydroxypolyamide by heat, and the temperature at which the cross-linking reaction occurs is preferably 150 to 350 ° C. Specifically, the following general formula (2):
{In the formula, R ₁ is a monovalent organic group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms; R ₂ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms; It is a monovalent organic group selected from the group consisting of a hydroxyl group, an ester group having 2 to 10 carbon atoms, and a urethane group having 2 to 10 carbon atoms, n is an integer of 1 to 3, and p is 1 to 1 5 is an integer of 5, q is an integer of 0 to 4, (p + q) = 5, k is an integer of 1 to 4, and when k = 1, X is C _n H _2n OR ₁ or R ₂ , and when k = 2 to 4, X represents a single bond or a divalent to tetravalent organic group, p and q in the case where p and q are plural, and C _n H _2n OR ₁ , And when R ₂ is present in plural, (C _n H _2n OR ₁ ) n, R ₁ , and R ₂ may be the same as or different from each other. } And the following general formula (3):
{In the formula, R ₁ is a monovalent organic group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 3. } A compound having an alkoxyalkyl group or a hydroxyalkyl group selected from the group consisting of compounds represented by:

Preferred examples of the thermal crosslinking agent represented by the general formula (2) include hydroxymethylbenzene, methoxymethylbenzene, ethoxymethylbenzene, hydroxyethylbenzene, methoxyethylbenzene, and ethoxymethyl as those having one alkoxyalkyl group. Benzene, 2-hydroxymethyltoluene, 2-methoxymethyltoluene, 3-hydroxymethyltoluene, 3-methoxymethyltoluene, 4-hydroxymethyltoluene, 4-methoxymethyltoluene, 2-hydroxymethylbiphenyl, 2-methoxymethylbiphenyl, 3-hydroxymethylbiphenyl, 3-methoxymethylbiphenyl, 4-hydroxymethylbiphenyl, 4-methoxymethylbiphenyl, and the like; examples having two include 1,2-dihydroxy Tylbenzene, 1,2-dimethoxymethylbenzene, 1,3-dihydroxymethylbenzene, 1,3-dimethoxymethylbenzene, 1,4-dihydroxymethylbenzene, 1,4-dimethoxymethylbenzene, 1,2-diethoxymethylbenzene 1,3-diethoxymethylbenzene, 1,4-diethoxymethylbenzene, 2,4′-bis (hydroxymethyl) biphenyl, 2,4′-bis (methoxymethyl) biphenyl, 3,4′-bis ( Hydroxymethyl) biphenyl, 3,4'-bis (methoxymethyl) biphenyl, 4,4'-bis (hydroxymethyl) biphenyl, 4,4'-bis (methoxymethyl) biphenyl, 2,4'-dihydroxymethyldiphenyl ether, 2,4′-dimethoxymethyldiphenyl ether, 3,4′-dihydroxy Til diphenyl ether, 3,4'-dimethoxymethyl diphenyl ether, 4,4'-dihydroxymethyl diphenyl ether, 4,4'-dimethoxymethyl diphenyl ether, 2,4'-dihydroxymethyl diphenyl methane, 2,4'-dimethoxymethyl diphenyl methane, 3, 4'-dihydroxymethyldiphenylmethane, 3,4'-dimethoxymethyldiphenylmethane, 4,4'-dihydroxymethyldiphenylmethane, 4,4'-dimethoxymethyldiphenylmethane, 2,4'-dihydroxymethyldiphenylsulfone, 2,4'-dimethoxy Methyldiphenylsulfone, 3,4'-dihydroxymethyldiphenylsulfone, 3,4'-dimethoxymethyldiphenylsulfone, 4,4'-dihydroxymethyldiphenylsulfone, 4,4'-dimeth Xymethyldiphenylsulfone, 2,4'-dimethoxymethyldiphenylpropane, 2,4'-dihydroxymethyldiphenylpropane, 3,4'-dihydroxymethyldiphenylpropane, 3,4'-dimethoxymethyldiphenylpropane, 4,4'- Dihydroxymethyldiphenylpropane, 4,4'-dimethoxymethyldiphenylpropane, 2,4'-dihydroxymethyldiphenylhexafluoropropane, 2,4'-dimethoxymethyldiphenylhexafluoropropane, 3,4'-dihydroxymethyldiphenylhexafluoropropane 3,4'-dimethoxymethyldiphenylhexafluoropropane, 4,4'-dihydroxymethyldiphenylhexafluoropropane, 4,4'-dimethoxymethyldiphenylhexafluoropropane, etc. It is; and examples of those having three or more of the following:
{Wherein L may be the same or different from each other, hydroxymethyl group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, hydroxyethyl group, methoxyethyl group, ethoxyethyl group, hydroxypropyl group , A methoxypropyl group or a methoxyisopropyl group. } The compound represented by this is mentioned.

Furthermore, from the viewpoint of heat resistance of the crosslinked structure by curing, the following general formula (5):
{In the formula, R ₁ is a monovalent organic group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, n is an integer of 1 to 3, and p is An integer of 1 to 5, k is 1 or 2, and when k = 1, X is a hydrogen atom or C _n H _2n OR ₁ , and when k = 2, X is a single bond or The following general formula (6):
In the case where there are a plurality of p, n and R ₁ in (C _n H _2n OR ₁ ) may be the same as or different from each other. } At least one thermal crosslinking agent having a structure represented by

Specific examples include methoxymethylbenzene, ethoxymethylbenzene, methoxyethylbenzene, ethoxymethylbenzene, 2-methoxymethyltoluene, 3-methoxymethyltoluene, 4-methoxymethyltoluene, 2-methoxymethylbiphenyl, 3-methoxymethylbiphenyl, 4-methoxymethylbiphenyl, 1,2-dimethoxymethylbenzene, 1,3-dimethoxymethylbenzene, 1,4-dimethoxymethylbenzene, 1,2-diethoxymethylbenzene, 1,3-diethoxymethylbenzene, 1, 4-diethoxymethylbenzene, 2,4′-bis (methoxymethyl) biphenyl, 3,4′-bis (methoxymethyl) biphenyl, 4,4′-bis (methoxymethyl) biphenyl, 2,4′-dimethoxymethyl Diphenyl ether, 3, 4'-dimethoxymethyl diphenyl ether, 4,4'-dimethoxymethyl diphenyl ether, 2,4'-dimethoxymethyl diphenyl methane, 3,4'-dimethoxymethyl diphenyl methane, 4,4'-dimethoxymethyl diphenyl methane, 2,4'-dimethoxymethyl Diphenylsulfone, 3,4'-dimethoxymethyldiphenylsulfone, 4,4'-dimethoxymethyldiphenylsulfone, 2,4'-dimethoxymethyldiphenylpropane, 3,4'-dimethoxymethyldiphenylpropane, 4,4'-dimethoxymethyl Diphenylpropane, 2,4′-dimethoxymethyldiphenylhexafluoropropane, 3,4′-dimethoxymethyldiphenylhexafluoropropane, 4,4′-dimethoxymethyldiphenylhexafluoropropane, the following:
{In the formula, L may be the same or different from each other, and is a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group or a methoxyisopropyl group. } Etc. are mentioned.
Furthermore, (D) as a thermal crosslinking agent, from the viewpoint of the effect of suppressing the shrinkage of the film thickness due to curing, methoxymethylbiphenyl, dimethoxymethylbenzene, bis (methoxymethyl) biphenyl, bis (methoxymethylphenyl) ether, bis (methoxymethyl) Particularly preferred is at least one compound selected from the group consisting of phenyl) methane.

Preferable examples of the thermal crosslinking agent represented by the general formula (3) include the following:
The compound represented by these is mentioned.
(D) Thermal crosslinking agents may be used alone or in combination of two or more.

The optimum blending amount for obtaining an appropriate side wall shape while maintaining chemical resistance to the stripping solution is (C) a compound containing an oxetanyl group and (D) thermal crosslinking with respect to 100 parts by mass of hydroxypolyamide. The total content with the agent is preferably 20 to 50 parts by mass, and the mass ratio of (D) the thermal crosslinking agent to the compound containing (C) the oxetanyl group is preferably 0.06 to 0.67.
When the total content of (C) the oxetanyl compound and (D) the thermal crosslinking agent is less than 20 parts by mass, there is a problem that sufficient chemical resistance cannot be obtained or corners are generated in the side wall shape. On the other hand, if the total content of (C) the oxetanyl compound and (D) the thermal crosslinking agent exceeds 50 parts by mass, there is a problem that corners are generated in the side wall shape or the opening of the relief pattern is filled.

(C) When the weight ratio of the (D) thermal crosslinking agent to the compound containing an oxetanyl group exceeds 0.67, a corner is formed on the side wall of the opening of the relief pattern, and stress is applied when forming the metal wiring layer. When the weight ratio of the (D) thermal crosslinking agent to the compound containing the (C) oxetanyl group is less than 0.06, the fluidity at the time of curing is There is a problem that the relief pattern is too raised and the opening of the relief pattern is filled.
Moreover, within the said range, with respect to 100 mass parts of (A) hydroxy polyamide, the compound containing (C) oxetanyl group is 20-30 mass parts, and (D) thermal crosslinking agent is 1-10 mass parts. More preferably it is.

A thermal radical generator may be added to the photosensitive resin composition. The radical generator used here is preferably one that generates radicals under heat treatment conditions, and preferred examples include organic peroxides such as dicumyl peroxide and organic non-peroxides such as dimethyldiphenylbutane. .
When adding a thermal radical generating agent, 0-20 mass parts is preferable with respect to 100 mass parts of (A) hydroxy polyamide, and 0.1-10 mass parts is more preferable. If the addition amount is within 20 parts by mass, the storage stability is good.

In the photosensitive resin composition, if necessary, a phenol compound, a dye, a surfactant, an adhesion aid for increasing the adhesion to the substrate, a stability, which are conventionally used as additives of the photosensitive resin composition, It is also possible to add an agent or the like.
More specifically, the above additives include ballast agents, paracumylphenol, bisaminophenol, resorcinol and the like. In addition, a ballast agent means the phenol compound currently used as a raw material for the above-mentioned diazoquinone compound which is a phenol compound in which a part of the phenolic hydrogen atom is converted to naphthoquinonediazide sulfonic acid ester. Examples of the dye include methyl violet, crystal violet, and malachite green.
When adding a phenol compound, it is preferable that it is 0-50 mass parts with respect to 100 mass parts of (A) hydroxy polyamide, and it is more preferable that it is 1-30 mass parts. If the addition amount is within 50 parts by mass, the tensile elongation of the film after thermosetting is good.

  In addition, as the surfactant, for example, non-ionic surfactants made of polyglycols such as polypropylene glycol and polyoxyethylene lauryl ether or derivatives thereof, such as Fluorard (registered trademark, trade name, manufactured by Sumitomo 3M), Fluorosurfactants such as Megafuck (registered trademark, trade name, manufactured by Dainippon Ink and Chemicals), Lumiflon (registered trademark, trade name, manufactured by Asahi Glass), such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) And organosiloxane surfactants such as DBE (trade name, manufactured by Chisso Corporation) and Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

  When adding a surfactant, the addition amount is preferably 0 to 10 parts by mass and more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of (A) hydroxypolyamide. If the addition amount is within 10 parts by mass, the tensile elongation of the film after thermosetting is good. By adding the surfactant, it is possible to make it more difficult for the coating film to be repelled at the wafer edge during coating.

Examples of the adhesion assistant include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, epoxy polymer, various silane coupling agents, and the like.
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, 3-aminopropyl dialkoxyalkyl Examples include silane, its acid anhydride or dianhydride reaction product, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane amino group converted to urethane group or urea group, etc. It is possible. In this case, the alkyl group is methyl, ethyl, butyl, etc., the acid anhydride is maleic anhydride, phthalic anhydride, etc., and the acid dianhydride is pyromellitic acid 2 An anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride and the like, and a urethane group such as t-butoxycarbonylamino group is a urea group Examples thereof include a phenylaminocarbonylamino group.

When the adhesion assistant is added, the addition amount is preferably 0 to 30 parts by mass and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of (A) hydroxypolyamide. If the addition amount is within 30 parts by mass, the tensile elongation of the film after thermosetting is good.
The above-mentioned photosensitive resin composition can be dissolved in a solvent to form a varnish and used as a photosensitive resin composition solution.
Examples of such a solvent include N-methyl-2-pyrrolidone, γ-butyrolactone (hereinafter also referred to as “GBL”), isophorone, N, N-dimethylacetamide (hereinafter also referred to as “DMAc”), dimethylimidazo. Linone, tetramethylurea, dimethyl sulfoxide, diethylene glycol dimethyl ether (hereinafter also referred to as “DMDG”), diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol 3-monomethyl ether, methyl pyruvate, ethyl pyruvate, include methyl 3-methoxy propionate or the like, they can be used alone or in combination. Among these solvents, non-amide solvents are preferable because they have little influence on photoresists. Specifically, as non-amide solvents, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol mono Examples thereof include ethyl ether and propylene glycol monomethyl ether acetate.
The amount of the solvent added is preferably 50 to 1,000 parts by mass with respect to 100 parts by mass of (A) hydroxypolyamide. It is preferable that the addition amount of the solvent is set to a viscosity suitable for the coating apparatus and the coating thickness within the above range from the viewpoint of facilitating the production of the cured relief pattern.

<Curing relief pattern and method for manufacturing semiconductor device>
Next, a method for producing a cured relief pattern by applying the photosensitive resin composition of the present invention to a substrate will be specifically described below.
(1) Step of forming a photosensitive resin layer made of a photosensitive resin composition on a substrate (first step)
The photosensitive resin composition solution is applied to a substrate such as a silicon wafer, a ceramic substrate, or an aluminum substrate by spin coating using a spin coater or a coater such as a die coater or a roll coater. Or it is also possible to apply | coat to a predetermined place using an inkjet nozzle or a dispenser. This is dried at 50 to 140 ° C. using an oven or a hot plate to remove the solvent (“pre-bake”).

(2) Step of exposing the photosensitive resin layer (second step)
Subsequently, the photosensitive resin layer is exposed to actinic rays through a mask. That is, exposure with actinic radiation is performed using a contact aligner or a stepper. Alternatively, exposure is performed by directly irradiating a light beam, an electron beam or an ion beam. As actinic rays, g-line, h-line, i-line, and KrF laser can be used.

(3) Step of developing (third step)
As a third step, the exposed portion or irradiated portion is eluted or removed with a developer. Subsequently, a desired relief pattern is obtained preferably by rinsing with a rinsing liquid. As a developing method, methods such as spray, paddle, dip, and ultrasonic can be used. As the rinsing liquid, distilled water, deionized water, or the like can be used.

The developer used for developing the photosensitive resin layer made of the photosensitive resin composition dissolves and removes the alkali-soluble polymer and needs to be an alkaline aqueous solution in which an alkali compound is dissolved. The alkali compound dissolved in the alkaline aqueous solution may be either an inorganic alkali compound or an organic alkali compound.
Examples of the inorganic alkali compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate. Lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia and the like.

Examples of the organic alkali compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, diethylamine. -N-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, triethanolamine and the like.
Furthermore, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a storage stabilizer, a resin dissolution inhibitor, or the like can be added to the alkaline aqueous solution.

(4) Step of heating the obtained relief pattern (fourth step)
Finally, the obtained relief pattern is heat-treated to form a heat-resistant cured relief pattern made of a resin having a polybenzoxazole structure. As the heating device, an oven furnace, a hot plate, a vertical furnace, a belt conveyor furnace, a pressure oven, or the like can be used. As a heating method, heating by hot air, infrared rays, electromagnetic induction, or the like is recommended. The temperature is preferably 200 to 450 ° C, more preferably 250 to 400 ° C.
The heating time is preferably 15 minutes to 8 hours, and more preferably 1 hour to 4 hours.
The atmosphere is preferably in an inert gas such as nitrogen or argon. A semiconductor device combines a cured relief pattern with a known method for manufacturing a semiconductor device as a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, or a protective film for a device having a bump structure. Can be manufactured.
The photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad plates, solder resist films, and liquid crystal alignment films.

The present invention will be described based on reference examples and examples. The photosensitive resin compositions in the examples were evaluated according to the following methods.
<Evaluation of photosensitive resin composition>
(1) Side wall shape of relief pattern The photosensitive resin composition is spin-coated on a 5-inch silicon wafer with a spin coater (Dspin SW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.), and 125 ° C. with a hot plate. , Pre-baked for 180 seconds to form a coating film. This coating film was exposed through a reticle with a test pattern by using a Nikon stepper (NSR2005i8A) having an exposure wavelength of i-line (365 nm) while changing the exposure stepwise. This was developed using an alkali developer (AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution) manufactured by AZ Electric Materials, so that the residual film ratio of the unexposed area was 85%. Paddle development was performed under conditions of 23 ° C. by adjusting the time, and rinsing with pure water was performed to form a positive relief pattern. This coating film is heat-treated (cured) at 320 ° C. for 1 hour in a nitrogen atmosphere using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.) to form a cured film on the silicon wafer. I got it. The film thickness was measured with an optical film thickness measuring device (Lambda Ace VM-1200, manufactured by Dainippon Screen Mfg. Co., Ltd.) with a refractive index of 1.65. At this time, the applied film thickness of the coating film was set by calculating backward from the cure shrinkage so that the final film thickness of the relief pattern obtained by performing the curing at 320 ° C. for 1 hour was 7.0 μm.

In the relief pattern obtained as described above, an opening having a width of 50 μm of an exposure pattern of 300 mJ / cm ² was cleaved, and the cross-sectional shape thereof was observed with a Scanning Electron Microscope (S-2400, Hitachi Measurement Service).
In the above observation, as shown in FIG. 1, those having no corners on the side walls were evaluated as “good”, and on the other hand, those having corners on the side walls as shown in FIG. Moreover, the thing with which the opening part of 20 micrometers in width was filled with the flow of the coating film by a cure was evaluated as "bad".

(2) Chemical resistance The thickness of the relief pattern obtained as described above was measured, immersed in an N-methylpyrrolidone (NMP) solvent at 70 ° C. for 5 minutes, washed with pure water, and dried. The film thickness was measured, and the remaining film ratio before and after chemical treatment was confirmed. Moreover, the pattern observation was performed using the optical microscope, and it was confirmed whether there was generation | occurrence | production of the residue by a crack or coating-film elution.
As described above, in the remaining film rate, a variation of less than 10% was evaluated as “good”, and a variation of 10% or more was evaluated as “bad”.
In addition, in the pattern observation, cracks do not occur in the corners of the opening of 10 μm, and no residue is generated in the openings. Those that did not were evaluated as “good”, and those in which the corners of the 50 μm opening cracked or residues formed in the opening were evaluated as “bad”.

<Synthesis of hydroxy polyamide>
[Reference Example 1]
In a 2 L separable flask, 197.8 g (0.54 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 75.9 g (0.96 mol) of pyridine and 692 g of DMAc were added at room temperature. (25 ° C.) The mixture was stirred and dissolved. A solution obtained by dissolving 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic anhydride in 88 g of DMDG was added dropwise thereto from a dropping funnel. The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 28 ° C.
After completion of the dropwise addition, the mixture was heated to 50 ° C. with a hot water bath and stirred for 18 hours, and then the IR spectrum of the reaction solution was measured to confirm that characteristic absorption of imide groups at 1385 cm ⁻¹ and 1772 cm ⁻¹ appeared.

Next, this was cooled to 8 ° C. with a water bath, and a solution obtained by dissolving 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride in 398 g of DMDG was added dropwise thereto from a dropping funnel. The time required for the dropping was 80 minutes, and the maximum reaction solution temperature was 12 ° C. Three hours after the completion of the dropwise addition, the reaction solution was dropped into 12 liters of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water as appropriate, dehydrated and then vacuum-dried. 1) was obtained. The weight average molecular weight of the thus synthesized hydroxy polyamide by GPC was 14,000 in terms of polystyrene. The analysis conditions for GPC are as follows:
Column: Showa Denko Co., Ltd. Trade name: Shodex 805/804/803 in series Separation: Tetrahydrofuran 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko brand name Shodex RI SE-61

[Reference Example 2]
In Reference Example 1, instead of 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride, 125.35 g (0.48 mol) of octahydro-1H-4,7-methanoindene dicarboxylic acid dichloride, and Instead of 197.8 g (0.54 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) -propane 139. A polybenzoxazole resin precursor was obtained in the same manner as in Reference Example 1 except that 45 g (0.54 mol) was used (P-2). The polystyrene equivalent weight average molecular weight of this resin was 22,000 (Mw).

[Reference Example 3]
In a 1 L separable flask, 109.9 g (0.3 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 330 g of tetrahydrofuran (THF), 47.5 g (0.6 mol) of pyridine. Into this, 98.5 g (0.6 mol) of 5-norbornene-2,3-dicarboxylic anhydride was added in powder form at room temperature. After stirring for 3 days at room temperature, the reaction was confirmed by HPLC. As a result, no starting material was detected, and the product was detected as a single peak with a purity of 99%. This reaction solution was dropped as it was into 1 L of ion-exchanged water with stirring, and the precipitate was filtered off, and then 500 mL of THF was added to dissolve it with stirring. The homogeneous solution was passed through a glass column packed with a cation-exchange resin. Residual pyridine was removed. Next, this solution was dropped into 3 L of ion exchange water under high-speed stirring to precipitate a product, which was filtered off and then vacuum-dried.

The product is imidized, appear characteristic absorption of an imide group 1394Cm ^-1 and 1774 cm ^-1 in the IR spectrum, it no characteristic absorption of amide groups in the vicinity of 1540 cm ^-1 and 1650 cm ^-1, and NMR The spectrum was confirmed by the absence of amide and carboxylic acid proton peaks.
Next, 65.9 g (0.1 mol) of the product, 53.7 g (0.2 mol) of 1,2-naphthoquinonediazide-4-sulfonyl chloride and 560 g of acetone were added and dissolved by stirring at 20 ° C. A solution prepared by diluting 21.2 g (0.21 mol) of triethylamine with 106.2 g of acetone was added dropwise thereto at a constant rate over 30 minutes. At this time, the temperature of the reaction solution was controlled in the range of 20 to 30 ° C. using an ice water bath or the like.
After completion of the dropwise addition, the mixture was allowed to stir at 20 ° C. for an additional 30 minutes, and then 5.6 g of a 36 wt% hydrochloric acid aqueous solution was added at once. . The filtrate obtained at this time was dropped into 5 L of a 0.5% by weight aqueous hydrochloric acid solution over 1 hour with stirring to precipitate the desired product, which was collected by suction filtration. The obtained cake-like recovered material was dispersed again in 5 L of ion-exchanged water, stirred, washed, collected by filtration, and this water washing operation was repeated three times. Finally, the cake-like material obtained was vacuum-dried at 40 ° C. for 24 hours to obtain a diazoquinone compound (Q-1).

[Reference Example 4]
In a 1 L separable flask, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (trade name Tris-P-PA-MF, Honshu Chemical Industry Co., Ltd.) 30.6 g (0.1 mol), 1,2-naphthoquinonediazide-4-sulfonyl chloride 67.1 g (0.25 mol), and acetone 560 g were added and stirred and dissolved at 20 ° C. A solution prepared by diluting 26.2 g (0.26 mol) of triethylamine with 131.1 g of acetone was added dropwise thereto at a constant rate over 30 minutes. At this time, the temperature of the reaction solution was controlled in the range of 20 to 30 ° C. using an ice water bath or the like.
After completion of the dropwise addition, the mixture was allowed to stir at 20 ° C. for an additional 30 minutes, and then 5.6 g of a 36 wt% hydrochloric acid aqueous solution was added at once. . The filtrate obtained at this time was dropped into 5 L of a 0.5% by weight aqueous hydrochloric acid solution over 1 hour with stirring to precipitate the desired product, which was collected by suction filtration. The obtained cake-like recovered material was dispersed again in 5 L of ion-exchanged water, stirred, washed, collected by filtration, and this water washing operation was repeated three times. Finally, the cake-like product obtained was vacuum-dried at 40 ° C. for 24 hours to obtain a diazoquinone compound (Q-2).

[Example 1]
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-1) obtained in Reference Example 3 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-1) obtained in Reference Example 1 above. (Ube Industries) After dissolving 20 parts by mass and 10 parts by mass of 4,4′-bis (methoxymethyl) biphenyl (hereinafter referred to as BPDM) as a thermal cross-linked product in 170 parts by mass of γ-butyrolactone, 0.2 μm It filtered with the filter and the photosensitive resin composition A was prepared. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

[Example 2]
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-1) obtained in Reference Example 3 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-1) obtained in Reference Example 1 above. (Ube Industries) 30 parts by mass and 10 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare a photosensitive resin composition B. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

Example 3
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-1) obtained in Reference Example 3 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-1) obtained in Reference Example 1 above. (Ube Industries) 30 parts by mass and 4 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare a photosensitive resin composition C. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

Example 4
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-1) obtained in Reference Example 3 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-1) obtained in Reference Example 1 above. (Ube Industries) 25 parts by mass and 5 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare a photosensitive resin composition D. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

Example 5
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-2) obtained in Reference Example 4 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-2) obtained in Reference Example 2 above. (Ube Industries) 20 parts by mass and 10 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare a photosensitive resin composition E. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

Example 6
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-2) obtained in Reference Example 4 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-2) obtained in Reference Example 2 above. (Ube Industries) 30 parts by mass and 10 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare a photosensitive resin composition F. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

Example 7
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-2) obtained in Reference Example 4 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-2) obtained in Reference Example 2 above. (Ube Industries) 30 parts by mass and 4 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare a photosensitive resin composition G. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

Example 8
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-2) obtained in Reference Example 4 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-2) obtained in Reference Example 2 above. (Ube Industries) 25 parts by mass and 5 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare photosensitive resin composition H. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

Example 9
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-2) obtained in Reference Example 4 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-2) obtained in Reference Example 2 above. (Ube Industries) 20 parts by mass and 12 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare photosensitive resin composition I. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

Example 10
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-2) obtained in Reference Example 4 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-2) obtained in Reference Example 2 above. (Ube Industries) 35 parts by mass and 12 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare a photosensitive resin composition J. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

Example 11
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-2) obtained in Reference Example 4 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-2) obtained in Reference Example 2 above. (Ube Industries) 40 parts by mass and 4 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare a photosensitive resin composition K. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

Example 12
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-2) obtained in Reference Example 4 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-2) obtained in Reference Example 2 above. (Ube Industries) 15 parts by mass and 6 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare a photosensitive resin composition L. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

Example 13
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-2) obtained in Reference Example 4 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-2) obtained in Reference Example 2 above. (Ube Industries) 20 parts by mass and 2 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare a photosensitive resin composition M. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

Example 14
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-2) obtained in Reference Example 4 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-2) obtained in Reference Example 2 above. (Ube Industries) 30 parts by mass and 20 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare a photosensitive resin composition N. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

Example 15
OX121 as a compound containing 20 parts by mass of the diazoquinone compound (Q-2) obtained in Reference Example 4 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-2) obtained in Reference Example 2 above. (Ube Industries) 25 parts by mass and 10 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare a photosensitive resin composition O. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

Example 16
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-2) obtained in Reference Example 4 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-2) obtained in Reference Example 2 above. 20 parts by mass (Ube Industries) and 10 parts by mass of MX270 (Mitsui Cytec) as a thermal cross-linked product are dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to obtain a photosensitive resin composition. P was prepared. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

[Comparative Example 1]
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-2) obtained in Reference Example 4 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-2) obtained in Reference Example 2 above. (Ube Industries) 20 parts by mass and 16 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare photosensitive resin composition Q. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

[Comparative Example 2]
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-2) obtained in Reference Example 4 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-2) obtained in Reference Example 2 above. (Ube Industries) 45 parts by mass and 10 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare a photosensitive resin composition R. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

[Comparative Example 3]
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-2) obtained in Reference Example 4 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-2) obtained in Reference Example 2 above. (Ube Industries) After dissolving 25 mass parts in 170 mass parts of (gamma) -butyrolactone, it filtered with a 0.2 micrometer filter, and prepared the photosensitive resin composition S. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

[Comparative Example 4]
OXBP as a compound containing 20 parts by mass of the diazoquinone compound (Q-2) obtained in Reference Example 4 and an oxetanyl group with respect to 100 parts by mass of the hydroxypolyamide (P-2) obtained in Reference Example 2 above. (Ube Industries) 5 parts by mass and 6 parts by mass of BPDM as a thermal cross-linked product were dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare a photosensitive resin composition T. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the side wall shape was evaluated. In addition, chemical resistance was evaluated by the method described above.

The composition list of the photosensitive resin compositions of Examples 1 to 16 and Comparative Examples 1 to 4 is shown in the following Table 1, and the evaluation results of the relief patterns obtained using the photosensitive resin composition are shown in the following table. It is shown in 2.
From Table 2, a photosensitive resin composition having sufficient resistance to a solvent and having no corners in the side wall shape by combining a compound containing an oxetanyl group and a thermal crosslinking agent in a certain range of weight and ratio. It turns out that it is obtained.
On the other hand, the relief pattern obtained by using the photosensitive resin compositions of Comparative Examples 1 to 4 deviating from the weight and ratio in the certain range is inferior in chemical resistance or has a corner in the side wall shape of the relief pattern. Or it turns out that the malfunction that the opening part is filled has arisen.

  The photosensitive resin composition of the present invention includes a surface protective film for a semiconductor device, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, a protective film for a device having a bump structure, an interlayer insulating film for a multilayer circuit, It can be suitably used for producing a flexible copper-clad plate cover coat, solder resist film, liquid crystal alignment film, and the like.

Claims (7)

(A) The following general formula (1):
{Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, and Y ₁ is a divalent organic group having at least 2 carbon atoms. } Containing 100 parts by mass of a hydroxy polyamide having a structure represented by: (B) 1 to 100 parts by mass of a diazoquinone compound, (C) a compound containing an oxetanyl group, and (D) a thermal crosslinking agent, The total content of the compound containing an oxetanyl group and the (D) thermal crosslinking agent is 20 to 50 parts by mass, and the mass of the (D) thermal crosslinking agent relative to the compound containing the (C) oxetanyl group A photosensitive resin composition having a ratio of 0.06 to 0.67. The (D) thermal crosslinking agent has the following general formula (2):
{In the formula, R ₁ is a monovalent organic group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms; R ₂ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms; It is a monovalent organic group selected from the group consisting of a hydroxyl group, an ester group having 2 to 10 carbon atoms, and a urethane group having 2 to 10 carbon atoms, n is an integer of 1 to 3, and p is 1 to 1 5 is an integer of 5, q is an integer of 0 to 4, (p + q) = 5, k is an integer of 1 to 4, and when k = 1, X is C _n H _2n OR ₁ and when k = 2 to 4, X represents a single bond or a divalent to tetravalent organic group, p and q in the case where there are a plurality of p and q, and C _n H _2n OR ₁ and R _{N in} a case where _two or more ₂ exist (C _n H _2n OR ₁ ), R ₁ and R ₂ may be the same as or different from each other. } In represented Ru reduction if Mono及 beauty following:
The photosensitive resin composition of Claim 1 which is an at least 1 type of alkoxyalkyl group containing compound chosen from the group which consists of a compound represented by these. The (D) thermal crosslinking agent has the following general formula (2):
{In the formula, R ₁ is a monovalent organic group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms; R ₂ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms; It is a monovalent organic group selected from the group consisting of a hydroxyl group, an ester group having 2 to 10 carbon atoms, and a urethane group having 2 to 10 carbon atoms, n is an integer of 1 to 3, and p is 1 to 1 5 is an integer of 5, q is an integer of 0 to 4, (p + q) = 5, k is an integer of 1 to 4, and when k = 1, X is C _n H _2n OR ₁ and when k = 2 to 4, X represents a single bond or a divalent to tetravalent organic group, p and q in the case where there are a plurality of p and q, and C _n H _2n OR ₁ and R _{N in} a case where _two or more ₂ exist (C _n H _2n OR ₁ ), R ₁ and R ₂ may be the same as or different from each other. } The photosensitive resin composition of Claim 2 which is an at least 1 type of alkoxyalkyl group containing compound represented by these.   2. The photosensitive resin according to claim 1, wherein the thermal crosslinking agent (D) is at least one compound selected from the group consisting of dimethoxymethylbenzene, bis (methoxymethyl) biphenyl, dimethoxymethyldiphenyl ether, and dimethoxymethyldiphenylmethane. Composition.   The photosensitive resin composition as described in any one of Claims 1-4 whose content of the compound containing the said (C) oxetanyl group is 15-35 mass parts.   The process of forming the photosensitive resin layer which consists of the photosensitive resin composition as described in any one of Claims 1-5 on a board | substrate, the exposure process of exposing a photosensitive resin layer, the process of image development, the relief obtained A method for producing a cured relief pattern, comprising a step of heating the pattern.   A semiconductor device comprising a cured relief pattern layer obtained by the production method according to claim 6.