JP5815309B2 - Alkali-soluble polymer, photosensitive resin composition containing the same, and use thereof - Google Patents

Description

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

  As a material for the surface protective film and interlayer insulating film of a semiconductor device, an alkaline aqueous solution-soluble polyhydroxyamide, for example, polybenzoxazole (hereinafter also referred to as “PBO”) precursor, which becomes a heat-resistant resin after curing, is photosensitive. For example, Patent Document 1 discloses a method in which a PBO precursor composition is prepared by mixing with a photoacid generator such as a reactive diazoquinone compound, and this PBO precursor composition is used as a positive photosensitive resin composition.

In the process of manufacturing a semiconductor device, the precursor composition is applied to a substrate such as a silicon wafer, patterned with actinic rays, developed, and subjected to a thermal polybenzoxazole treatment, etc. Thus, a surface protective film or an interlayer insulating film can be easily formed.
In recent years, low-cost production has been strongly demanded for dynamic random access memory and NAND flash memory, which are a kind of semiconductor memory. Even in the step of forming the surface protective film of the semiconductor memory, it is strongly required to form the surface protective film at a low cost.

  The above-described photosensitive resin composition is generally provided in a solution state (varnish) using γ-butyllactone (hereinafter referred to as GBL) as a solvent. When using the photosensitive resin composition, a predetermined amount of the photosensitive resin composition is discharged onto a silicon wafer using a pump or the like, and a film is formed by a spin coating method. When GBL is used as a solvent, if the discharge mass is large, the varnish is shaken off from the silicon wafer during spin coating, and the amount of varnish to be discarded increases. If the discharge mass is reduced, the varnish can be uniformly applied on the entire surface of the silicon wafer. There was a problem of not being.

  Attempts to reduce the amount of use and disposal of photosensitive resin compositions have been proposed by application methods, such as reducing the amount of photosensitive resin composition used by spray coating, but a new alternative to existing spin coaters. It was necessary to introduce a proper coating apparatus.

JP 63-096162 A JP 2001-139806 A JP 2007-086215 A JP 2006-031084 A JP 2003-215789 A JP-A-8-120174

  Patent Document 2 discloses a photosensitive resin composition using cyclohexanone as a solvent and Patent Document 3 using propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) as a solvent. When the coating film was applied by spin coating, the varnish was dried during spin coating, the spin coating film was whitened, and there was a problem in film thickness uniformity after coating.

  Patent Document 4 discloses in the solvent examples that 2-octanone is used as the solvent of the solvent-soluble polyimide. However, as shown in the comparative examples described later, wetting spread at the time of spin coating due to the resin is disclosed. Deterioration was seen.

  In Example 4 of Patent Document 5, there is a disclosure of a photosensitive resin composition using a novolak resin containing 2-heptanone as a solvent component. However, as shown in a comparative example described later, wetting at the time of spin coating due to the resin A worsening of the spread was observed.

  In Example 2 of Patent Document 6, there is a disclosure of a photosensitive resin composition using a polyamic acid containing 2-heptanone as a solvent component. However, as shown in a comparative example described later, wetting at the time of spin coating due to a resin A worsening of the spread was observed.

  The present invention is a photosensitive resin composition that can be uniformly applied to the entire surface of a silicon wafer by a spin coating method even with a smaller discharge mass, and has excellent in-plane uniformity of the coating film, and uses the composition. It is an object of the present invention to provide a method for producing a cured relief pattern, and a semiconductor device having the cured relief pattern.

  As a result of intensive studies in view of the above-described problems of the prior art, the present inventor uses a specific structure alkali-soluble resin and a compound having a specific structure as a solvent, and lowers the density of the photosensitive resin composition. We have found that wetting and spreading at the time of creating a coating film by the spin coating method is improved. It was also found that the in-plane uniformity of the coating is improved by selecting a combination of a solvent having an appropriate vapor pressure and an appropriate resin. As a result, it has been found that a photosensitive resin composition that solves the above problems can be obtained, and has led to the present invention.

That is, the present invention is as follows.
[1] An alkali-soluble resin (a) containing a structure having a repeating unit represented by the following general formula (1), a photoacid generator (b), and a ketone compound having a vapor pressure of 50 to 500 Pa at 25 ° C. there solvent (c), at least including the photosensitive resin composition, and photosensitive resin composition density of the photosensitive resin composition is ^{0.95g / cm 3 ~1.10g / cm 3} .

(In the formula, X ₁ and Y ₁ each independently represent a divalent to tetravalent organic group having at least 2 carbon atoms, and R ₁ and R ₂ each independently represent from _{1 to} 10 carbon atoms. And n ₁ + n ₂ + n ₃ + n ₄ > 0, and m ₁ is an integer from 1 to 1000.)

[2] (Mass of total alkali-soluble resin) / [(Mass of total alkali-soluble resin) + (Mass of all solvent)] = 0.2 to 0.5 The photosensitive resin composition according to [1] .
[3] In the above [1] or [2], the solvent includes the solvent (c) and γ-butyllactone, and the proportion of γ-butyllactone in the total solvent is in the range of 10 to 65% by weight. The photosensitive resin composition as described.
[4] The photosensitive resin composition according to any one of [1] to [3], further including a crosslinking agent (d).
[5] The photosensitive resin composition according to any one of [1] to [4], further comprising a carboxylic acid compound or a phenolic compound as a dissolution accelerator (e).
[6] The photosensitivity according to any one of [1] to [5], wherein the solvent (c) is at least one solvent selected from the group consisting of 2-nonanone, 2-octanone, and 2-heptanone. Resin composition.
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the photoacid generator (b) is a quinonediazide compound.

[8] A step of forming the photosensitive resin composition according to any one of [1] to [7] on a substrate in the form of a layer or a film,
Exposing the photosensitive resin composition;
A method for producing a cured relief pattern, comprising: developing a photosensitive resin composition after the exposure to form a relief pattern; and heating the relief pattern to form a cured relief pattern.
[9] A semiconductor device comprising a cured relief pattern obtained by the method for producing a cured relief pattern according to [8].

  According to the present invention, a photosensitive resin composition that is excellent in wetting and spreading at the time of creating a coating film by a spin coating method with a smaller discharge mass and excellent in-plane uniformity of the coating film, the photosensitive resin composition The manufacturing method of the used cured relief pattern and the semiconductor device having the cured relief pattern can be provided.

<Photosensitive resin composition>
Each component which comprises the photosensitive resin composition of this invention is demonstrated concretely below.
[Alkali-soluble resin (a) including a structure having a repeating unit represented by the following general formula (1)]

(In the formula, X ₁ and Y ₁ each independently represent a divalent to tetravalent organic group having at least 2 carbon atoms, and R ₁ and R ₂ each independently represent from _{1 to} 10 carbon atoms. And n ₁ + n ₂ + n ₃ + n ₄ > 0, and m ₁ is an integer from 1 to 1000.)

The photosensitive resin composition in the present invention is represented by the above general formula (1) from the viewpoint that the discharge mass at the time of coating film creation by spin coating can be reduced and the in-plane uniformity of the coating film is improved. The alkali-soluble resin (a) containing a structure having a repeating unit, that is, a polybenzoxazole precursor structure is partially included in the entire alkali-soluble resin.
A resin having a polybenzoxazole precursor structure (hereinafter also referred to as “PBO precursor” or “polyhydroxyamide”) will be described in detail.

The repeating unit constituting the dihydroxydiamide is a dicarboxylic acid having a structure of Y ₁ (OH) _n2 (COOR ₂ ) _n4 (COOH) ₂ , and an X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁ ) _n3 structure. A diamine having a structure such as bisaminophenol is polycondensed. The two amino and hydroxy groups of the bisaminophenol are each in the ortho position. When the polyhydroxyamide is heated to about 280 to 400 ° C., the ring is closed, and the polyhydroxyamide is changed to polybenzoxazole which is a heat resistant resin. m ₁ is preferably in the range of ₁ to 1000, more preferably in the range of 3 to 50, and most preferably in the range of 3 to 30.

Examples of diamines having a X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁ ) _n3 structure, such as bisaminophenol compounds, include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4 ′. -Dihydroxybiphenyl, 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) hexa Fluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxy) Cyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4′-diamino-3,3′-dihydroxybenzophenone, 3,3′-diamino-4,4′-dihydroxy Benzophenone, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino Examples include -2,4-dihydroxybenzene and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenol compounds may be used alone or in combination.
Among these diamines having the X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁ ) _n3 structure, particularly preferred is the case where X ₁ is an organic group selected from the following.

In addition, as a diamine having the X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁ ) _n3 structure, two diamine bonds having an amide bond and a phenolic hydroxyl group in the ortho position relative to each other in the molecule (hereinafter referred to as “intramolecular It is also possible to use a diamine having a PBO precursor structure. Examples thereof include diamines represented by the following general formula, which are obtained by reacting bisaminophenol with two molecules of nitrobenzoic acid for reduction.

(In the formula, X ₃ is a tetravalent organic group having at least 2 carbon atoms, and is at least one organic group selected from the group consisting of preferable organic groups represented by X ₁ described above. Is preferred.)

As another method for obtaining a diamine having a PBO precursor structure in the molecule, the dicarboxylic acid dichloride having the structure of Y ₃ (COCl) ₂ is reacted with two molecules of nitroaminophenol for reduction. There are also ways to obtain the indicated diamines.

(In the formula, Y ₃ is a divalent organic group having at least 2 carbon atoms, and is at least one organic group selected from the group consisting of preferable organic groups represented by Y ₁ described later. Is preferred.)

In addition, as a bisaminophenol having a X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁ ) _n3 structure, it has two polyimide precursor structures in the molecule (hereinafter referred to as “PI precursor structure in the molecule”). Can also be used. As a method for obtaining such a bisaminophenol compound, for example, dicarboxylic acid obtained by ring-opening tetracarboxylic dianhydride with monoalcohol or monoamine, and aniline having a hydroxy group and a nitro group at the ortho positions of each other are used. There is also a method of obtaining bisaminophenol represented by the following general formula by condensing two molecules and then reducing the nitro group.

(In the formula, Y ₄ is a tetravalent organic group having at least 4 carbon atoms, and R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms.)

In addition to the structure derived from the diamine having the raw material X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁ ) _n3 structure, a diamine partially having no hydroxy group may be used. Examples of such diamines 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-a Nophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2 , 4-bis (4-aminophenyl) -1-pentene, 4-methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-4-amino) Benzyl) benzene, imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6)- Amino-1- (4-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4,4′-diaminoazobenzene 4,4′-diaminodiphenylurea, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4′-bis (4-aminophenoxy) diphenylsulfone, 4,4′- Bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, 4,4 ′ -Diaminobiphenyl, 4,4'-diaminobenzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobipheny 3,3′-dimethyl-4,4′-diaminobiphenyl, o-toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4- Aminophenoxyphenyl) sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4′- Di- (3-aminophenoxy) diphenylsulfone, 4,4′-diaminobenzanilide and the like, and the hydrogen atom of the aromatic nucleus of these aromatic diamines are a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, Substituted by at least one group or atom selected from the group consisting of a cyano group and a phenyl group Compounds, and the like.

Moreover, in order to improve adhesiveness with a base material, silicon diamine can be selected as a part of diamine having X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁ ) _n3 structure. Bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (4-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4- Examples thereof include bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, and bis (γ-aminopropyl) tetraphenyldisiloxane.
As the dicarboxylic acid having a structure of Y ₁ (OH) _n2 (COOR ₂ ) _n4 (COOH) ₂ , Y ₁ is a group containing an aromatic group, an alicyclic group, or an aliphatic group selected from the following: Dicarboxylic acid is mentioned.

Wherein A ₁ is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, and a single bond. A divalent group selected; m ₅ is an integer of 1 to 30; L ₁ is a group selected from the group consisting of an alkyl group, an unsaturated group, and a halogen atom; 4, k is an integer from 0 to 1, and l is an integer from 0 to 2.)

In addition, a derivative of 5-aminoisophthalic acid can be used for a part or all of the dicarboxylic acid having the Y ₁ (OH) _n2 (COOR ₂ ) _n4 (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, chloroformate 2,2,2-trichloroethyl ester, chloroformate-2-butoxyethyl ester, chloroformate-p-nitrobenzyl ester, chloroformate-p-methoxybenzyl ester, chloroformate isobornylbenzyl ester, chloro Formic acid-p-biphenylisopropylbenzyl ester, 2-t-butyloxycarbonyl-oxyimino-2-phenylacetonitrile, St-butyloxycarbonyl-4,6-dimethyl-thiopyrimidine, di-tert-butyl-dicarbonate N-ethoxycarbonylphthalimide, ethyldithiocarbonyl chloride, formic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, methanesulfonic acid chloride, acetyl chloride, trityl chloride, trimethylchlorosilane, hexamethyldisilazaza N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (dimethylamino) trimethylsilane, trimethylsilyldiphenylurea, bis (trimethylsilyl) urea, phenyl isocyanate N-butyl isocyanate, n-octadecyl isocyanate, o-tolyl isocyanate, 1,2-phthalic anhydride, and cis-1,2-cyclohexanedicarboxylic anhydride, and glutaric anhydride.

Furthermore, as a dicarboxylic acid having a Y ₁ (OH) _n2 (COOR ₂ ) _n4 (COOH) ₂ structure, a dicarboxylic acid obtained by ring-opening a tetracarboxylic dianhydride with a monoalcohol or a monoamine can also be used. . Here, examples of monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, benzyl alcohol and the like. Examples of monoamines include butylamine and aniline. As an example of said tetracarboxylic dianhydride, the compound shown by following Chemical formula is mentioned.

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

Alternatively, tetracarboxylic dianhydride can be reacted with bisaminophenol or diamine, and the resulting carboxylic acid residue can be esterified or amidated with a monoalcohol or monoamine.
Also, trimellitic acid chloride is reacted with bisaminophenol to produce tetracarboxylic dianhydride, and ring-opened in the same manner as the above tetracarboxylic dianhydride and used as dicarboxylic acid You can also. Examples of the tetracarboxylic dianhydride obtained here include chemical formulas shown below.

(In the formula, X ₄ represents a divalent organic group represented by X ₁ (OH) ₂ (NH—) ₂ ).

  As a method of polycondensation of the dicarboxylic acid and bisaminophenol compound (diamine) for synthesizing polyhydroxyamide, dicarboxylic acid and thionyl chloride are used to form diacid chloride, and then bisaminophenol (diamine) is used. And a method of polycondensation of dicarboxylic acid and bisaminophenol (diamine) with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be allowed to act simultaneously.

  In the polyhydroxyamide having the repeating unit represented by the above general formula (1), it is also preferable to use the terminal group by sealing the end group with an organic group (hereinafter referred to as “sealing group”). In the polycondensation of hydroxypolyamide, when the dicarboxylic acid component is used in an excess number of moles compared to the sum of the bisaminophenol component and the diamine component, an amino group or a compound having a hydroxyl group is used as the sealing group. Is preferred. Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, and hydroxyethyl acrylate.

  Conversely, when the sum of the bisaminophenol component and the diamine component is used in an excessive number of moles compared to the dicarboxylic acid component, the sealing group has an acid anhydride, carboxylic acid, acid chloride, isocyanate group, etc. It is preferable to use a compound. Examples of the compound include benzoyl chloride, norbornene dicarboxylic anhydride, norbornene carboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, methylcyclohexane dicarboxylic anhydride Products, cyclohexenedicarboxylic anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, and tosyl chloride.

In addition to the above-described alkali-soluble resin (a) having a polybenzoxazole precursor structure in the molecule, other alkali-soluble resins such as phenol resin and phenol resin derivatives are mixed into the photosensitive resin composition. May be. Specific examples include novolak resins, resole resins, and polyhydroxystyrene resins.
As the novolac resin, those widely used in the technical field of resists can be used. This novolac resin can be obtained, for example, by reacting phenols with aldehydes or ketones in the presence of an acidic catalyst.

  Among these, a novolak resin obtained by concomitant use of metacresol and paracresol and a condensation reaction of these with formaldehyde, formalin or paraformaldehyde is particularly preferable from the viewpoint of sensitivity controllability. The charging mass ratio of metacresol to paracresol is usually 20:80 to 80:20, preferably 50:50 to 70:30.

  The molecular weight is a mass average molecular weight and is usually in the range of 1,000 to 20,000, preferably 1,000 to 15,000, and more preferably 1,000 to 10,000. The mass average molecular weight of the resin can be controlled within a desired range by adjusting the synthesis conditions. In addition, the narrower the molecular weight distribution, the higher the photosensitivity, so that the resin obtained by synthesis is solid-liquid extracted with an organic solvent having an appropriate solubility, or the resin is dissolved in a good solvent and placed in a poor solvent. The molecular weight distribution may be controlled by dripping, or by dropping a poor solvent and performing solid-liquid or liquid-liquid extraction. Specific examples of this novolak resin include EP4000B (Asahi Organic Materials Industry: trade name), EP4020G (Asahi Organic Materials Industry: trade name), EP4050G (Asahi Organic Materials Industry: trade name), EP4080G (Asahi Organic Materials Industry: product). Name).

  Next, the polyhydroxystyrene resin and derivatives thereof will be described in detail. Specific examples of the polyhydroxystyrene resin and derivatives thereof include, for example, poly-o-hydroxystyrene, poly-m-hydroxystyrene, poly-p-hydroxystyrene, poly-α-methyl-o-hydroxystyrene, poly-α. -Methyl-m-hydroxystyrene, poly- [alpha] -methyl-p-hydroxystyrene, or a partially acetylated product, a silylated product thereof or the like. The mass average molecular weight of these polyhydroxystyrene resins or derivatives thereof is usually in the range of 3,000 to 100,000, particularly preferably 4,000 to 20,000.

  When novolac resin, resol resin, polyhydroxystyrene resin and derivatives thereof are mixed with 10 to 300 parts by mass, preferably 50 to 200 parts by mass, with respect to the above-mentioned alkali-soluble resin (a), high sensitivity to electron beams is obtained. Become. It is preferable that it is 300 mass parts or less from a viewpoint of wet spreading property and heat resistance.

[Photoacid generator (b)]
As the photoacid generator (b) contained in the photosensitive resin composition of the present invention, a compound that makes it possible to apply the photosensitive resin composition as a positive type or a negative type for the intended use can be used. When the photosensitive resin composition is used as a positive type, (b) a quinonediazide compound, an onium salt, a halogen-containing compound, etc. can be used as the photoacid generator, but solvent solubility and storage stability In view of the above, a quinonediazide compound is preferable.

  Examples of the onium salt include iodonium salts, sulfonium salts, phosphonium salts, ammonium salts, diazonium salts, and the like, and onium salts selected from the group consisting of diaryliodonium salts, triarylsulfonium salts, and trialkylsulfonium salts are preferable.

Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds, and trichloromethyltriazine is preferable from the viewpoint of increasing sensitivity.
As the quinonediazide compound, a naphthoquinonediazide compound (NQD compound) is preferable, and a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure is particularly preferable. The naphthoquinonediazide structure includes 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and 1,2-naphthoquinonediazide-5-sulfonic acid ester of the polyhydroxy compound. At least one NQD compound selected from the group consisting of:

The NQD compound is obtained by subjecting a naphthoquinone diazide sulfonic acid compound to sulfonyl chloride with chlorosulfonic acid or thionyl chloride according to a conventional method, and subjecting the obtained naphthoquinone diazide sulfonyl chloride to a polyhydroxy compound. For example, a polyhydroxy compound and a predetermined amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride in a solvent such as dioxane, acetone, tetrahydrofuran, etc. The NQD compound can be obtained by reacting in the presence of a basic catalyst for esterification, and washing the resulting product with water and drying.
Examples of preferable NQD compounds include those represented by the following general formula group.

{Wherein Q is a hydrogen atom or the following group of formulas:

The naphthoquinone diazide sulfonate group represented by any of the above, but not all Q are hydrogen atoms at the same time. }
Further, a naphthoquinone diazide sulfonyl ester compound containing a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule can be used, and a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound can be used. Can also be used in combination.

1-50 mass parts is preferable with respect to 100 mass parts (b) of all alkali-soluble resins, and, as for the compounding quantity with respect to the whole alkali-soluble resin of a photo-acid generator, 5-30 mass parts is more preferable. If the blending amount of the photoacid generator is 1 part by mass or more, the patterning property of the resin is good, and if it is 50 parts by mass or less, the tensile elongation rate of the cured film is good and the development residue (scum) in the exposed part is high. Few.
In addition, it can utilize as a negative type by combining the photosensitive resin composition of this invention with (d) crosslinking agent mentioned later. In that case, examples of the (b) photoacid generator include the following compounds.

A) Trichloromethyl-s-triazines Tris (2,4,6-trichloromethyl) -s-triazine, 2-phenyl-bis (4,6-trichloromethyl) -s-triazine, 2- (3-chlorophenyl) -Bis (4,6-trichloromethyl) -s-triazine, 2- (2-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4 6-trichloromethyl) -s-triazine, 2- (3-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloromethyl) ) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) Bis (4,6-trichloromethyl-s-triazine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4,6 -Trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (3,4,5-trimethoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl) -bis (4 , 6-Trichloromethyl) -s-triazine, 2- (3-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methylthio-β Styryl) - bis (4,6-trichloromethyl) -s-triazine.

A) Diaryl iodonium compounds diphenyl iodonium tetrafluoroborate, diphenyl iodonium tetrafluorophosphate, diphenyl iodonium tetrafluoroarsenate, diphenyl iodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxyphenyl Phenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4- Meto Xiphenylphenyliodonium-p-toluenesulfonate, bis (4-ter-butylphenyl) iodonium tetrafluoroborate, bis (4-ter-butylphenyl) iodonium hexafluoroarsenate, bis (4-ter-butylphenyl) iodonium Trifluoromethanesulfonate, bis (4-ter-butylphenyl) iodonium trifluoroacetate, bis (4-ter-butylphenyl) iodonium-p-toluenesulfonate, and the like.

C) Triarylsulfonium salts Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfo NATO, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium tri Fluoroacetate, 4- Methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethane Sulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate, 4-phenylthiophenyl diphenyl-p-toluene sulfonate and the like.

  Among these compounds, trichloromethyl-S-triazines include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4-chlorophenyl) -bis (4, 6-trichloromethyl) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4-methoxy-β-styryl) -bis (4,6- Trichloromethyl) -S-triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -S-triazine and the like, and diaryl iodonium salts include diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethane sulfone. Nato, 4-methoxyphenylphenyliodonium trifluoromethane For example, sulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, and triarylsulfonium salts include triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenyl. Suitable examples include sulfonium trifluoroacetate, 4-phenylthiophenyl diphenyl trifluoromethanesulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate, and the like.

D) Diazoketone compound Examples of the diazoketone compound include 1,3-diketo-2-diazo compound, diazobenzoquinone compound, diazonaphthoquinone compound, and the like, and specific examples include 1,2-naphthoquinonediazide-4 of phenols. -A sulfonic acid ester compound can be mentioned.

E) Sulfone compounds Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds and α-diazo compounds of these compounds. Specific examples include 4-trisphenacylsulfone, mesitylphenacyl. Examples include sulfone and bis (phenacylsulfonyl) methane.

F) Sulfonic acid compound Examples of the sulfonic acid compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Preferred examples include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, o-nitrobenzyl p-toluene sulfonate, and the like.

G) Sulfonimide compound Specific examples of the sulfonimide compound include, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N -(Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like can be mentioned.

C) Oxime ester compound 2- [2- (4-Methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (trade name “Ciba Specialty Chemicals”) "Irgacure PAG121"), [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals trade name "Irgacure PAG103"), [ 2- (n-octanesulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals trade name “Irgacure PAG108”), α- (n- Octansulphonil Shiimino) -4-methoxybenzyl cyanide (Ciba Specialty Chemicals tradename "CGI725"), and the like.

I) Diazomethane compounds Specific examples of the diazomethane compounds include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, and the like.
In particular, from the viewpoint of sensitivity, the oxime ester compound group is particularly preferable.

  The blending amount of (b) the photoacid generator in the case of using a negative photosensitive resin composition in combination with (d) a cross-linking agent described later is 0.1 to 100 mass with respect to 100 mass parts of the total alkali-soluble resin. Part. If the blending amount is 0.1 parts by mass or more, a sensitivity improvement effect can be sufficiently obtained, and if the blending amount is 100 parts by mass or less, mechanical properties after curing are good. The blending amount is preferably 1 to 40 parts by mass.

[Solvent (c) which is a ketone compound having a vapor pressure at 25 ° C. of 50 to 500 Pa]
In the present invention, the alkali-soluble resin containing polyhydroxyamide as component (a) and the photoacid generator as component (b) are dissolved in a solvent to form a varnish and used as a photosensitive resin composition. At that time, a ketone compound having a vapor pressure of 50 to 500 Pa at 25 ° C. is used as a solvent.

  The ketone compound solvent has a lighter density than that of γ-butyllactone widely used in photosensitive resin compositions, and has a similar solubility in the alkali-soluble resin (a). Therefore, it can be set as the photosensitive resin composition with a light density by using a ketone compound as a solvent. The present inventors have found that when a spin coating film is formed, a coating film can be formed with a smaller coating mass by using a light-sensitive photosensitive resin composition. For this reason, the solvent is preferably a ketone compound having a low density, and a ketone compound having a density of 0.9 or less at 25 ° C. is preferable from the viewpoint of reducing the discharge mass when forming the spin coat film.

  Further, it is preferable to use a ketone compound having a vapor pressure at 25 ° C. of 50 to 500 Pa from the viewpoint of the uniformity of the coating film. When a ketone compound with a vapor pressure of 50 Pa or less is used, the solvent component does not easily evaporate during pre-baking, so the solvent remains in the film after pre-baking, and is strongly affected by temperature unevenness of the hot plate used during pre-baking and exhaust non-uniformity, The film thickness uniformity of the pre-baked coating is poor. When a ketone compound having a vapor pressure of 500 Pa or more is used, the solvent component is volatilized during spin coating, resulting in poor film thickness uniformity.

  Specifically, the solvent (c) is preferably a ketone compound having 7 or more carbon atoms, such as diisobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, 5-methyl-3-heptanone, 2-methyl. -3-heptanone, 6-methyl-2-heptanone, 2-methyl-4-heptanone, 3-methyl-4-heptanone, 2-octanone, 3-octanone, 4-octanone, 5-methyl-2-octanone, 2 -Nonanone, 3-nonanone, 4-nonanone, 5-nonanone, 2-hexylcyclopentanone are mentioned.

  Among them, a compound selected from the group consisting of a cyclic structure having 7 to 9 carbon atoms and a linear structure ketone having 7 or more carbon atoms not having a branched structure is preferable. Among them, 2-heptanone, 2-octanone, 2-Nonano is preferable from the viewpoint that the film thickness uniformity of the coating film after pre-baking is improved and the density of the photosensitive resin composition is lowered, and the discharge mass at the time of coating film creation by spin coating can be reduced. -Octanone is most preferred.

In the present invention, in addition to the ketone compound having a vapor pressure of 50 to 500 Pa at 25 ° C., the density of the photosensitive resin composition does not exceed 1.1 g / cm ^3. Can be used by mixing one or more of them.

  Examples of such a solvent include N-methyl-2-pyrrolidone, γ-butyrolactone (hereinafter also referred to as “GBL”), N, N-dimethylacetamide (hereinafter also referred to as “DMAc”), dimethylimidazolinone, Tetramethylurea, dimethylsulfoxide, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3- Methoxypropionate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether Le, a propylene glycol monomethyl ether acetate.

  Of these solvents, non-amide solvents are preferred because they have little effect on chemically amplified photoresists. Specific preferred examples include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. From the viewpoint of high solubility in the alkali-soluble resin (a) and prevention of precipitation of the photoacid generator (b) after the lapse of time, it is most often used in combination with the solvent (c) in which γ-butyrolactone is a ketone compound. preferable.

  When the solvent (c), which is a ketone compound, contains 10 to 65% by mass of γ-butyllactone, the film thickness uniformity of the pre-baked film of the photosensitive resin composition is improved. When the content ratio of γ-butyl lactone is 15 to 50% by mass, it is more preferable from the viewpoint of coexistence of film thickness uniformity of the pre-baked film and reduction of discharge mass at the time of forming the spin coat film.

  The addition amount of the total solvent when forming the photosensitive resin is (mass of total alkali-soluble resin) / [(mass of total alkali-soluble resin) + (mass of total solvent)] = 0.2 to 0.5 It is preferable that it is the addition amount which becomes. The above-mentioned (mass of total alkali-soluble resin) includes, in addition to the alkali-soluble resin (a), for example, when an alkali-soluble resin such as a novolak resin is contained in the photosensitive resin composition, the mass of the novolak resin is also included. Means. Further, (mass of all solvents) means that when a solvent other than the solvent (c) which is a ketone compound is used, the mass of the solvent is also included. When it is in the range of 0.2 to 0.5, the viscosity of the photosensitive resin composition becomes an appropriate viscosity, and a film thickness required for a normal semiconductor protective film (3 μm to 20 μm in the final cured film) is spin-coated. It is possible to create the rotation at an appropriate rotational speed (500 rpm to 5000 rpm). A thickness of 0.3 to 0.45 is more preferable because adjustment of the coating thickness is facilitated.

The density of the photosensitive resin composition, 0.95 g / cm ³ should be ~1.10g / cm ³ is a necessary in view of the discharge mass reduction when creating spin-coated film, a ketone compound solvent (c ) Is contained in the photosensitive resin composition. More preferably, the range of 0.95g / cm ³ ~1.08g / cm ³ is preferred from the viewpoint of the uniformity of the discharge mass reduction and coating film.

[(D) Crosslinking agent]
In the present invention, when the photosensitive resin composition is used in a positive type, for use in a negative type for the purpose of improving the chemical resistance of the film after heat curing (photosensitive resin layer), For the purpose of increasing the chemical resistance of the film after thermosetting and for the purpose of pattern formation, (d) a crosslinking agent can be preferably used.

(d) The crosslinking agent comprises an aromatic compound having a methylol group and / or an alkoxymethyl group, a compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group, an epoxy compound, an oxetane compound, and an allyl compound. At least one compound selected from the group can be used.
Among these crosslinking agents, at least one compound selected from the group consisting of an aromatic compound having a methylol group and / or an alkoxymethyl group, and a compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group is present. From the viewpoint of chemical resistance after thermosetting.
As an aromatic compound having a methylol group and / or an alkoxymethyl group, the following general formula:

(In the formula, R ₃₁ is a hydroxyl group, m ₃₁ is an integer of 0 to 3. R ₃₂ is an organic group having 1 to 30 carbon atoms, and m ₃₂ is an integer of 0 to 3. R ₃₃ is A hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and m ₃₃ is an integer of 1 to 6.)
What has the structure represented by these is preferable.

  Specific examples of the aromatic compound having a methylol group and / or an alkoxymethyl group include the following compounds.

  Examples of the compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group include the following general formula:

(In the formula, R ₃₄ and R ₃₅ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ₃₆ is an organic group having 1 to 30 carbon atoms.)
What has the structure represented by these is preferable.

  More specifically, as a compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group, more specifically, melamine resin, benzoguanamine resin, glycoluril resin, hydroxyethylene urea resin, urea resin, glycol urea resin, alkoxymethylated melamine Mention may be made of resins, alkoxymethylated benzoguanamine resins, alkoxymethylated glycoluril resins, and alkoxymethylated urea resins.

  Among these, alkoxymethylated melamine resins, alkoxymethylated benzoguanamine resins, alkoxymethylated glycoluril resins, and alkoxymethylated urea resins are known methylolated melamine resins, methylolated benzoguanamine resins, or methylols of methylolated urea resins. It can be obtained by converting the group into an alkoxymethyl group. Examples of the kind of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group.

  Specific examples of compounds in which the N-position is substituted with a methylol group and / or an alkoxymethyl group include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (manufactured by Mitsui Cytec Co., Ltd.), Nicarax MX-270, -280, -290, Nicarak MS-11, Nicarac MW-30, -100, -300,- 390, -750 (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

  Moreover, the monomer of the said resin can also be used as (d) crosslinking agent, for example, the following compound, hexamethoxymethyl melamine, dimethoxymethyl urea etc. can be mentioned.

  The epoxy compound is a compound having a three-membered cyclic ether structure, and specific examples thereof include bisphenol A type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, glycidylamine type epoxy resin, polysulfide type epoxy resin. However, it is not limited to these.

  An oxetane compound is a compound having a 4-membered cyclic ether structure, and is capable of a cationic ring-opening polymerization reaction or an addition reaction with carboxylic acid, thiol, or phenol. Specific examples of the oxetane compound 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 -Oxetanylmethyl) ether, poly [ 3-[(3-ethyl-3-oxetanyl) methoxy] propyl] silasesquioxane] derivatives, oxetanyl silicate, phenol novolac oxetane, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, Examples include, but are not limited to, OXT121 (Toagosei: trade name), OXT221 (Toagosei: trade name), and the like.

  From the viewpoint of heat resistance, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4′-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, and OXT121 (Toagosei Co., Ltd.) : Product name) is preferable.

  Specific examples of allyl compounds include allyl alcohol, allyl anisole, benzoic acid allyl ester, cinnamic acid allyl ester, N-allyloxyphthalimide, allyl phenol, allyl phenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate , Diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimelliate (TRIAM705 manufactured by Wako Pure Chemical Industries, Ltd.), pyromerit Examples include triallyl acid (TRIAM805 manufactured by Wako Pure Chemical Industries, Ltd.), triallyl oxydiphthalate, triallyl phosphate, triallyl phosphite, and triallyl citrate. However, it is not limited to these. From the viewpoint of sensitivity, triallyl trimellitic acid (TRIAM705 manufactured by Wako Pure Chemical Industries, Ltd.) and triallyl pyromellitic acid (TRIAM805 manufactured by Wako Pure Chemical Industries, Ltd.) are preferable.

  (d) The crosslinking agent can be used alone or in admixture of two or more, and the blending amount is preferably 1 to 100 parts by mass with respect to 100 parts by mass of (a) alkali-soluble resin, More preferably, it is 3-50 mass parts. When the blending amount is 1 part by mass or more, crosslinking proceeds well and the patterning property becomes good. When the blending amount is 100 parts by mass or less, the mechanical properties after curing are kept good.

[Solubility Accelerator (e)]
In the present invention, the dissolution accelerator (e) can be preferably used. Examples of the dissolution accelerator include carboxylic acid compounds and phenolic compounds.
Examples of carboxylic acid compounds include 3-phenyl lactic acid, 4-hydroxyphenyl lactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2- ( 1-naphthyl) propionic acid, mandelic acid, atrolactic acid, acetylmandelic acid, α-methoxyphenylacetic acid, 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4 -Hydroxy-3-methoxymandelic acid, 2-methoxy-2- (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, 4-hydroxymandelic acid, 3, 4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, Mandelic acid, atrolactic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, hexyl dihydroxybenzenecarboxylate, octyl dihydroxybenzenecarboxylate, dodecyl dihydroxybenzenecarboxylate, tri Hexyl hydroxybenzenecarboxylate hexyl gallate and phloroglucinol carboxylate hexyl, octyl trihydroxybenzenecarboxylate octyl gallate and phloroglucinol carboxylate, dodecyl trihydroxybenzenecarboxylate dodecyl and fluorate Logucinol carboxylate dodecyl, trihydroxybenzenecarboxylate hexadecyl hexadecyl gallate and phloroglucinol carboxylate hex Sadecyl and the like can be mentioned.

As the phenol compound, a ballast agent used for the photosensitive diazoquinone compound, and a linear phenol compound such as paracumylphenol, bisphenols, resorcinol, or MtrisPC, MtetraPC (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) Non-linear phenolic compounds such as TrisP-HAP, TrisP-PHBA, TrisP-PA (made by Honshu Chemical Industry Co., Ltd .: trade name), compounds in which 2 to 5 hydrogen atoms of the phenyl group of diphenylmethane are substituted with hydroxyl groups, 2 , Compounds in which 1 to 5 hydrogen atoms of the phenyl group of 2-diphenylpropane are substituted with hydroxyl groups. By adding the phenol compound, the adhesion of the relief pattern during development can be improved and the generation of residues can be suppressed. In addition, a ballast agent means the phenol compound currently used as a raw material for the above-mentioned photosensitive diazoquinone compound which is a phenol compound in which a part of the phenolic hydrogen atom is converted to naphthoquinonediazide sulfonic acid ester.
When adding a phenol compound, 0-50 mass parts is preferable with respect to 100 mass parts of all alkali-soluble resins, and 1-30 mass parts is preferable. If the addition amount is 50 parts by mass or less, the heat resistance of the film after thermosetting is good.

(F) Other additives To the photosensitive resin composition of the present invention, a surfactant, a stabilizer, an adhesion aid for improving adhesion to a silicon wafer, a dye, and the like are added as necessary. Is also possible.

The surfactant is more specifically described. Examples of the surfactant include polypropylene glycol, polyglycols such as polyoxyethylene lauryl ether, and nonionic surfactants made of derivatives thereof. Further, fluorine-based surfactants such as Fluorard (manufactured by Sumitomo 3M: trade name), Mega-Fac (manufactured by Dainippon Ink & Chemicals, Inc .: trade name), or Lumiflon (trade name, manufactured by Asahi Glass Co., Ltd.) are exemplified. Furthermore, organosiloxane surfactants such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name), DBE (manufactured by Chisso Corporation: trade name), or granol (manufactured by Kyoeisha Chemical Co., Ltd .: trade name) are listed. 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.
The addition amount in the case of adding a surfactant is preferably 0 to 10 parts by mass and more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the (a) alkali-soluble resin. When the addition amount is 10 parts by mass or less, the heat resistance of the film after thermosetting is good.

  Examples of the adhesion assistant include t-butyl novolak, aluminum compounds, titanium coupling agents, epoxy polymers, and various silane coupling agents such as epoxy silane.

  Specific preferred examples of the silane coupling agent include 3-methacryloxypropyltrialkoxysilane, 3-methacryloxypropyl dialkoxyalkylsilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxy. Reaction of alkylsilane, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane with acid anhydride or acid dianhydride, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane The thing which converted the amino group into the urethane group and the urea group is mentioned. In this case, the alkyl group includes a methyl group, an ethyl group, a butyl group, the acid anhydride includes maleic anhydride, phthalic anhydride, the acid dianhydride includes pyromellitic dianhydride, 3, 3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, etc., urethane group is t-butoxycarbonylamino group, urea group is phenylaminocarbonylamino Group and the like.

  The addition amount in the case of adding an adhesion assistant is preferably 0 to 30 parts by mass and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the alkali-soluble resin. If the addition amount is 30 parts by mass or less, the heat resistance of the film after thermosetting is good.

<Curing relief pattern and method for manufacturing semiconductor device>
Next, the manufacturing method of the cured relief pattern of the present invention will be specifically described below.
(1) A step of forming the photosensitive resin composition on a substrate in the form of a layer or a film;
The photosensitive resin composition of the present invention is applied to a substrate such as a silicon wafer, a ceramic substrate, or an aluminum substrate by spin coating using a spin coater, or a coater such as a die coater or roll coater. This is dried at 50 to 140 ° C. using an oven or a hot plate to remove the solvent. The spin coating method using a spin coater is most preferable from the viewpoint of obtaining a coating film having a uniform film thickness.

(2) a step of exposing the photosensitive resin composition;
Next, the substrate obtained above is exposed to actinic radiation through a mask using a contact aligner or a stepper, or directly irradiated with a light beam, an electron beam or an ion beam.

(3) A step of developing the photosensitive resin composition after the exposure to form a relief pattern;
Next, development can be performed by selecting from methods such as dipping, paddle, and rotary spraying. By developing, an exposed portion (in the case of positive type) or an unexposed portion (in the case of negative type) can be eluted and removed from the applied photosensitive resin resin composition to obtain a relief pattern. Developers include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide. An aqueous solution such as a quaternary ammonium salt such as quaternary ammonium salt and an aqueous solution to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added as required can be used. In these, the tetramethylammonium hydroxide aqueous solution is preferable, The density | concentration of this tetramethylammonium hydroxide becomes like this. Preferably, it is 0.5-10 mass%, More preferably, it is 1-5 mass%.

(4) A step of heating the relief pattern to form a cured relief pattern;
Finally, the obtained relief pattern is cured 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, more preferably 15 minutes to 4 hours. The atmosphere is preferably in an inert gas such as nitrogen or argon.

  Examples of semiconductor device applications include those having a cured film provided on top of a semiconductor element, wherein the cured film is a cured relief pattern comprising a cured film of the above-described photosensitive resin composition. . Examples of the cured film include a passivation film on a semiconductor element, a protective film such as a buffer coat film formed by forming a cured film of the above-described photosensitive resin composition on the passivation film, and a circuit formed on the semiconductor element. Examples thereof include an insulating film such as an interlayer insulating film formed by forming a cured film of the above-described photosensitive resin composition, an α-ray blocking film, a planarizing film, a protrusion (resin post), a partition wall, and the like.

  The photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films for display devices, and light emitting elements. .

[Reference Example 1] Synthesis of polyhydroxyamide In a separable flask having a volume of 2 L, 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (hereinafter also referred to as 6FAP) 197.8 g (0 .54 mol), 75.9 g (0.96 mol) of pyridine, and 692 g of DMAc were mixed and stirred at room temperature (25 ° C.) to dissolve them. To the obtained mixture, a mixed solution in which 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic anhydride was separately dissolved in 88 g of GBL was dropped 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 flask 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. The characteristic absorption of imide groups at 1385 cm ⁻¹ and 1772 cm ⁻¹ appeared. confirmed.

Next, the flask was cooled to 8 ° C. with a water bath, and a mixed solution in which 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride was separately dissolved in 398 g of GBL was dropped 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 dropping, the reaction solution was dropped into 12 l of water under high-speed stirring to disperse and precipitate the polymer. The purified precipitate was recovered, washed with water as appropriate, dehydrated and then vacuum dried to obtain polyhydroxyamide (P-1). The mass average molecular weight of the thus synthesized hydroxypolyamide according to gel permeation chromatography (GPC) was 14,000 in terms of polystyrene. The analysis conditions for GPC are described below.
Column: Showa Denko Co., Ltd. Trade name: Shodex 805/804/803 in series Separation: Tetrahydrofuran 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko brand name Shodex RI SE-61

[Reference Example 2] Synthesis of polyhydroxyamide In a three-necked flask with a capacity of 300 mL equipped with a vertical stirrer made of Teflon (registered trademark), the following structure:

TMOM-BP (Honshu Chemical: trade name) 21.7 g (0.06 mol), 9.48 g (0.12 mol) of pyridine and 130 g of GBL were mixed and stirred at 0 ° C., and bis (chlorocarbonyl) tricyclo was separately added to 142 g of GBL. [5,2,1,0 ^2,6] those dissolved 47.5 g (0.18 mol) decane was added dropwise from the dropping funnel. The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 16 ° C.

  After the dropwise addition, the reaction solution stirred for 1 hour was separately added using a dropping funnel in a separable flask having a capacity of 2 L equipped with a vertical stirrer made of Teflon (registered trademark) and 51.2 g (0.14 mol) of 6FAP. , 15.0 g (0.19 mol) of pyridine, 307 g of GBL and 102 g of DMAc were mixed and stirred at room temperature (25 ° C.), dissolved, and the reaction vessel was immersed in a vessel obtained by adding dry ice to methanol and cooled to −15 ° C. It was dripped. The reaction system was maintained at -15 to 0 ° C. and took 45 minutes, and was dropped into the reaction vessel. After completion of the dropwise addition, the reaction vessel was immersed in an ice bath and kept at 0 to 10 ° C. and stirred for 1 hour. Further, 7.12 g (0.09 mol) of pyridine was added. Thereafter, the reaction solution was returned to room temperature, 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 9.49 g (0.12 mol) of pyridine were added, and 50 The reaction solution was immersed in a hot water bath at 50 ° C. and stirred for 18 hours.

Ethanol was added to the reaction solution to precipitate a polymer, and then recovered and dissolved in 626 g of GBL. Subsequently, ion exchange was performed with 62.1 g of a cation exchange resin (manufactured by Organo, Amberlyst A21) and 59.6 g of an anion exchange resin (manufactured by Organo, Amberlyst 15). This solution is dropped into 12 L of ion-exchanged water under high-speed stirring, and the polymer is dispersed and precipitated, recovered, appropriately washed with water, dehydrated and then vacuum-dried to obtain an alkali-soluble heavy having a PBO precursor structure and a crosslinking group-containing structure. A powder of coalesced (P-2) was obtained.
The weight average molecular weight (Mw) by GPC of the alkali-soluble polymer synthesized in this way was a single sharp curve of 13200 in terms of polystyrene, and was a single composition.

Reference Example 3 Synthesis of Polyhydroxyamide In a 2 L separable flask equipped with a Teflon (registered trademark) vertical stirrer, 6FAP 51.2 g (0.14 mol), pyridine 15.0 g (0.19 mol) ), GBL307 g and DMAc 102 g were added, mixed and stirred at room temperature (25 ° C.) to dissolve, and the reaction vessel was immersed in a vessel in which dry ice was added to methanol and cooled to −15 ° C. Separately, a mixed solution prepared by dissolving 26.56 g (0.09 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride in 132 g of GBL was dropped from the dropping funnel. The reaction system was maintained at -15 to 0 ° C. and took 45 minutes, and was dropped into the reaction vessel. (Reaction solution 1)
Separately, TMOM-BP (Honshu Chemical: trade name) 10.9 g (0.03 mol), 4,4-biphenol 0 was placed in a 300 mL three-necked flask equipped with a Teflon (registered trademark) vertical stirrer. .93 g (0.005 mol) 9.48 g (0.12 mol) of pyridine and 130 g of GBL were mixed and stirred at 0 ° C., and bis (chlorocarbonyl) tricyclo [5,2,1,0 ^2,6 ] was separately added to 142 g of GBL. A solution in which 23.75 g (0.09 mol) of decane was dissolved was dropped from a dropping funnel. The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 16 ° C. It stirred for 1 hour after dripping. (Reaction solution 2)

  (Reaction solution 2) was added dropwise to (reaction solution 1) using a dropping funnel. The time required for the dropping was 40 minutes, and the maximum reaction temperature was 6 ° C. After the completion, the reaction vessel was immersed in an ice bath and kept at 0 to 10 ° C. and stirred for 1 hour. Further, 7.12 g (0.09 mol) of pyridine was added. Thereafter, the reaction solution was returned to room temperature, 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 9.49 g (0.12 mol) of pyridine were added, and 50 The reaction solution was immersed in a hot water bath at 50 ° C. and stirred for 18 hours.

  Ethanol was added to the reaction solution to precipitate a polymer, and then recovered and dissolved in 626 g of GBL. Subsequently, ion exchange was performed with 62.1 g of a cation exchange resin (manufactured by Organo, Amberlyst A21) and 59.6 g of an anion exchange resin (manufactured by Organo, Amberlyst 15). This solution is dropped into 12 L of ion-exchanged water under high-speed stirring, and the polymer is dispersed and precipitated, recovered, appropriately washed with water, dehydrated and then vacuum-dried to obtain an alkali-soluble heavy having a PBO precursor structure and a crosslinking group-containing structure. A powder (P-3) was obtained.

  The weight-average molecular weight (Mw) by GPC of the alkali-soluble polymer thus synthesized was a single sharp curve of 11300 in terms of polystyrene, and was a single composition.

[Reference Example 4] Synthesis of polyamic acid In a 0.5 liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a Dimroth condenser tube, 295.0 g of N-methyl-2-pyrrolidone, 2-octanone 55. 3 g, 36.9 g of diethyl ketone, 26.21 g of 4,4′-diaminodiphenyl ether, 14.70 g of bis (3-aminophenoxyphenyl) sulfone, LP7100 (trade name, 1,3-bis, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.49 g of (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane) was added and dissolved with stirring. Next, 50.02 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added to this solution, and the mixture was stirred at 25 ° C. for 8 hours and then at 60 ° C. for 8 hours for reaction. The polyamic acid solution thus obtained was dropped into 5 L of ion-exchanged water under high-speed stirring, the polymer was dispersed and precipitated, recovered, appropriately washed with water, dehydrated and then vacuum dried to obtain an alkali having a polyamic acid structure. A soluble polymer (P-3) powder was obtained. The weight-average molecular weight (Mw) by GPC of the alkali-soluble polymer thus synthesized was a single sharp curve of 26400 in terms of polystyrene, and was a single composition.

[Reference Example 5] Synthesis of soluble PI To a four-necked flask equipped with a stirring bar, a Dean-Stark trap with a ball, and a nitrogen introduction tube, 32.96 g of 6FAP (90 mmol was added, 196 g of NMP and 40 g of toluene were added, and room temperature was added. Next, 31.02 g (100 mmol) of 3,3,4,4-oxydiphthalic dianhydride was added and stirred at room temperature for 2 hours, then heated and stirred at 180 ° C. and 180 rpm for 3 hours, During the reaction, water as a by-product was distilled azeotropically with toluene, and the water accumulated at the bottom of the reflux tube was removed every 30 minutes.The weight of the polyimide polymer thus produced in terms of polystyrene The average molecular weight was 24400. This reaction solution was dropped into 5 L 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. To obtain a powder of the alkali-soluble polymer (P-5) having a soluble polyimide structure in an organic solvent subjected to.

<Preparation of photosensitive resin composition>
[Examples 1 to 13, Comparative Examples 1 to 7]
(P-1) to (P-5) as alkali-soluble resins obtained in Reference Examples 1 to 5 above, and cresol novolac resin EP4080G (Asahi Organic Materials Corporation: trade name) (P-6) (B) a compound PAC1 having the following structural formula as a photoacid generator,

(In the formula, 83% of the total number is represented by the following formula:

The remaining 17% are hydrogen atoms. )

(c) The following (C-1) to (C-7) ketone compounds and GBL as a solvent are combined in parts by mass shown in Table 1 to adjust the photosensitive resin composition, and the pores are 0.2 μm. It filtered with the filter made from polyethylene, and prepared the photosensitive resin composition of Examples 1-13 and Comparative Examples 1-7. The solvent and vapor pressure used are shown below.
γ-Butyl lactone (vapor pressure at 25 ° C 425Pa)
(C-1) Diisobutylketone (Vapor pressure at 21 ° C 239Pa)
(C-2) 2-heptanone (vapor pressure at 25 ° C. 279 Pa)
(C-3) 2-octanone (vapor pressure at 25 ° C. 229 Pa)
(C-4) 2-nonanone (vapor pressure at 25 ° C: 86 Pa)
(C-5) Cyclohexanone (vapor pressure at 25 ° C 665Pa)
(C-6) Acetone (vapor pressure at 25 ° C 2470Pa)
(C-7) Propylene glycol monomethyl ether acetate (vapor pressure at 20 ° C., 3800 Pa)

<Method for measuring density of photosensitive resin composition>
3 cm ³ disposable over monkey syringe up the photosensitive resin composition 2.5 cm ³ measure was weighed mass by precision balance its mass. The density of the photosensitive resin composition was calculated from the following (Formula 1).
Mass density (g / cm ³⁾ = photosensitive resin composition of 2.5 cm ³ of the photosensitive resin composition ^{(g) /2.5 (cm 3)} ··· ( Equation 1)

<Measurement method of resin solid content concentration>
The solid content concentration of the photosensitive resin composition was calculated from the following (Formula 2) from the total polymer mass and the total solvent mass when adjusting the photosensitive resin composition.
Resin solid content concentration of photosensitive resin composition (%) = (mass of total alkali-soluble resin (g)) / [(mass of total alkali-soluble resin (g)) + (mass of total solvent (g))]. .. (Formula 2)

<Evaluation of wetting spread and film thickness uniformity of photosensitive resin composition>
[Calculation of film thickness after pre-baking required to obtain 6 μm cured film after heat curing]
Dispense 2.5 g of a predetermined varnish at the center of an 8-inch silicon wafer with a spin coater (manufactured by Tokyo Electron: MARK-8, trade name) using the photosensitive resin compositions obtained in the above Examples and Comparative Examples. And spin coated. Pre-baking was performed on a hot plate at 125 ° C. for 180 seconds to form a pre-baked film. The film thickness was determined by measuring a 13-point film thickness at a pitch of 15 mm in the X direction with a film thickness measuring device (Dainippon Screen Mfg. Co., Ltd .: Lambda Ace, trade name) to obtain an average film thickness T1. This was heated in a nitrogen atmosphere using a temperature rising oven (VF200B manufactured by Koyo Thermo Systems Co., Ltd.) at 320 ° C. for 1 hour, and the cured film after heat curing was measured in the same manner. Asked. T2 / T1 × 100 was calculated as the remaining film ratio after curing. It was set that the pre-baked film was reduced by 10% at the time of development, and the film thickness after pre-baking necessary for producing a cured film of 6 μm was obtained from the result of the cure remaining film ratio. The results are shown in Table 2. The thicker the film thickness required after pre-baking, the more the required discharge mass of the photosensitive resin composition.

[Comparison of application area]
Dispensing the photosensitive resin compositions obtained in the above examples and comparative examples with a spin coater (manufactured by Tokyo Electron: MARK-8, trade name) with 0.9 g of a predetermined varnish at the center of an 8-inch silicon wafer. And spin coated. Perform pre-baking at 125 ° C. for 180 seconds on a hot plate, and adjust the rotation speed of the spin coater on the silicon wafer so that the final cured film thickness obtained above becomes 6 μm, A circular coating was formed. The film thickness was defined as an average value obtained by measuring a 13-point film thickness at a pitch of 15 mm in the X direction with a film thickness measuring device (Dainippon Screen Mfg. Co., Ltd .: Lambda Ace, trade name).

The diameter of this coating film was measured with a ruler (manufactured by Mitutoyo Corporation: ABS Digimatic Caliper, trade name), and the coating area was calculated by the following formula.
Application area (cm ² ) = [(measured diameter (cm) / 2) ² × 3.14]
As this value increases, a pre-baked film having a predetermined film thickness can be obtained with a smaller discharge mass by the spin coating method.
In this case, the coating area was evaluated as follows.
Coating area 700cm ² or more: ○
Application area less than 700 cm ² : ×

[In-plane uniformity]
From the measured film thickness, in-plane uniformity was determined from the following formula.
In-plane uniformity (%) =
[[(Maximum value of measured film thickness) − (minimum value of measured film thickness)] / (average film thickness)] × 100
In this case, the in-plane uniformity was evaluated as follows.
In-plane uniformity 5% or less: ○
In-plane uniformity exceeding 5%: ×

  From the results shown in Table 2, Examples 1 to 13 can obtain a pre-baked film having a predetermined film thickness with a smaller discharge mass by a spin coating method than the comparative example which is a conventional technique, and the film thickness is uniform. Excellent in properties.

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

Claims (8)

Alkali-soluble resin (a) including a structure having a repeating unit represented by the following general formula (1), photoacid generator (b), vapor pressure at 25 ° C. is 50 to 500 Pa, and density at 25 ° C. A photosensitive resin composition containing at least a solvent (c) which is a ketone compound having a viscosity of 0.9 or less, and the density of the photosensitive resin composition is 0.95 g / cm ^{3 to} 1.08 g / cm. ³ is a photosensitive resin composition.

(In the formula, X ₁ and Y ₁ each independently represent a divalent to tetravalent organic group having at least 2 carbon atoms, and R ₁ and R ₂ each independently represent 1 to 10 carbon atoms. N ₁ + n ₂ + n ₃ + n ₄ > 0, and m ₁ is an integer from 1 to 1000.}   The photosensitive resin composition according to claim 1, wherein (mass of total alkali-soluble resin) / [(mass of total alkali-soluble resin) + (mass of total solvent)] = 0.2 to 0.5.   3. The photosensitive resin according to claim 1, wherein the solvent includes the solvent (c) and γ-butyllactone, and the proportion of γ-butyllactone in the total solvent is in the range of 10 to 65% by weight. Composition.   Furthermore, the photosensitive resin composition of any one of Claims 1-3 containing a crosslinking agent (d).   Furthermore, the photosensitive resin composition as described in any one of Claims 1-4 which contains a carboxylic acid compound or a phenolic compound as a solubility promoter (e).   The photosensitive resin composition according to any one of claims 1 to 5, wherein the solvent (c) is at least one solvent selected from the group consisting of 2-nonanone, 2-octanone, and 2-heptanone.   The photosensitive resin composition according to any one of claims 1 to 6, wherein the photoacid generator (b) is a quinonediazide compound. Forming the photosensitive resin composition according to any one of claims 1 to 7 on a substrate in the form of a layer or a film;
Exposing the photosensitive resin composition;
A method for producing a cured relief pattern, comprising: developing a photosensitive resin composition after the exposure to form a relief pattern; and heating the relief pattern to form a cured relief pattern.