JP2009086356A - Photosensitive resin composition, pattern manufacturing method using the composition, and electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition of excellent film property reducing coloring and the change of film strength with the lapse of time, and a highly reliable electronic device having a pattern with excellent shape and a characteristic. <P>SOLUTION: The present invention relates to the photosensitive resin composition containing (a) a polyimide resin having a specified repetition unit, (b) a compound generating a sulfonic acid when irradiated with light, and (c) a crosslinking agent having an alkoxymethyl or acyloxymethyl group on a nitrogen atom, a pattern manufacturing method using the composition, and the electronic device having the pattern. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention uses a positive type high heat resistant photosensitive resin composition used as a surface protective film for semiconductor devices, an interlayer insulating film, an interlayer insulating film for display devices, and the positive type high heat resistant photosensitive resin composition. The present invention relates to a method for producing a cured relief pattern having heat resistance and a semiconductor device containing the relief pattern.

A polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like is used for a surface protective film and an interlayer insulating film of a semiconductor device. This polyimide resin is generally provided in the form of a photosensitive polyimide precursor composition. By applying, patterning with actinic rays, development, thermal imidization treatment, etc., a surface protective film and interlayer insulation are formed on a semiconductor device. A film or the like can be easily formed, and the process can be significantly shortened as compared with the conventional non-photosensitive polyimide precursor composition.
However, the photosensitive polyimide precursor composition needs to use a large amount of an organic solvent such as N-methyl-2-pyrrolidone as a developing solution in the development process. Solvent measures have been demanded. In response to this, recently, various proposals have been made on heat-resistant photosensitive resin materials that can be developed with an alkaline aqueous solution, as with photoresists.
In particular, a method in which a composition obtained by mixing an alkaline aqueous solution-soluble hydroxypolyimide (polyimide having a hydroxyl group in a polymer chain) with a photoactive component such as a photosensitive diazoquinone compound as a positive photosensitive resin composition has recently attracted attention. Has been.

  The development mechanism of this positive photosensitive resin is that the photosensitive diazoquinone compound in the unexposed area is insoluble in the alkaline aqueous solution, but the photosensitive diazoquinone compound undergoes a chemical change upon exposure to become an indenecarboxylic acid compound. It makes use of being soluble in an alkaline aqueous solution. By utilizing the difference in the dissolution rate with respect to the developer between the exposed portion and the unexposed portion, it is possible to form a relief pattern only in the unexposed portion (for example, see Patent Document 1).

On the other hand, as a technology that separates the photosensitive and insoluble areas of the unexposed area, the semiconductor photoresist field generates a catalytic amount of acid during exposure, and the subsequent heating process generates alkali-insoluble groups during exposure. Many chemically amplified photosensitive compositions that convert to an alkali-soluble group by a chemical reaction using an acid as a catalyst have been applied. Also in this technical field, a chemically amplified photosensitive composition is disclosed (for example, see Patent Document 2). These photosensitive compositions are known to be highly sensitive.
Recently, in order to reduce damage to devices due to high-temperature heating, low-temperature curing (low-temperature curing) is required, and those having high chemical resistance even under low-temperature curing conditions are disclosed (for example, patent documents) 3).

However, with the recent development of semiconductor technology, especially with the progress of miniaturization and thinning, demands for reliability and durability of a cured film formed from a photosensitive resin composition remaining in a device are further increased.
Japanese Patent Laid-Open No. 11-84645 JP 2003-337415 A JP 2007-16214 A

  The present invention provides a composition excellent in film physical properties with little coloration and film strength change with time. In addition, the present invention provides a highly reliable electronic device by having a pattern having a good shape and characteristics.

  It has been found that the above problems are solved by the following <1> to <5> configurations.

<1> (a) a resin containing a repeating unit represented by the general formula (1), (b) a compound that generates sulfonic acid by light irradiation, and (c) an alkoxymethyl group or an acyloxymethyl group on a nitrogen atom The photosensitive resin composition containing the crosslinking agent which has.

(R ¹ represents a C 4-30 tetravalent organic group. R ² represents a C 2-30 bivalent organic group. E represents a group having an acidic group. When there are a plurality of groups, they may be the same or different. R and s are integers of 0 to 4, but r + s> 0.)

<2> (b) The photosensitive resin composition as described in <1> above, wherein the compound that generates sulfonic acid by light irradiation is an imide sulfonate compound, an oxime sulfonate compound, or a nitrobenzyl sulfonate compound.

<3> The photosensitive resin composition according to <1> or <2>, further comprising (d) a compound that generates an acid by heat.

<4> A method for producing a pattern comprising a step of applying the composition according to any one of the above <1> to <3> on a supporting substrate and drying, a step of exposing, and a step of developing using an alkaline aqueous solution.
<5> An electronic device having a pattern obtained by the production method according to <5>.

  The pattern obtained by using the photosensitive resin composition of the present invention has high reliability such as no coloration and no change in film strength over time, and can be used as a surface protective film / interlayer insulating film in electronic devices and the like. .

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

(A) Resin containing a repeating unit represented by the general formula (1) (hereinafter also referred to as the resin of the present invention)

(R ¹ represents a C 4-30 tetravalent organic group. R ² represents a C 2-30 bivalent organic group. E represents a group having an acidic group. When there are a plurality of groups, they may be the same or different. R and s are integers of 0 to 4, but r + s> 0.)

R _{1 in the} general formula (1) represents a 4 to 8 valent organic group having 2 to 30 carbon atoms, preferably having an aromatic ring and / or an aliphatic group, more preferably 4 having 4 to 24 carbon atoms. A 7 to 7-valent organic group having an aromatic ring and / or an aliphatic group, and a 4- to 6-valent organic group having 4 to 20 carbon atoms having an aromatic ring and / or an aliphatic group is particularly preferable. Is.

R ₁ is preferably a structure in the general formula (1a) or (1b) containing (E) r shown below.

Here, L ₁ , L ₂ , and L ₃ are a heterocyclic ring having 5 to 30 carbon atoms, an aromatic carbocyclic ring having 6 to 30 carbon atoms (which may be a condensed ring, such as a benzene ring or a naphthalene ring), and the number of carbon atoms 3 to 30 aliphatic carbocycles (cyclopropane ring, cyclobutane ring, cyclopentane ring, etc.) are represented, and L ₁ and L ₂ may be the same or different. M represents a divalent linking group, for example, a single bond, an alkylene group having 1 to 20 carbon atoms (which may have a substituent, such as methylene, ethylene, hexafluoroisopropylidene, etc.), -O-,- _{S -, - SO 2 -,} - CO -, - N (R 11) -, or a group formed by combining _{these, R 11} is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or carbon atoms 1, 10 acyl groups are represented. E and r represent the same meaning as E and r in the general formula (1). In addition, when r is 1 to 4, r Es are substituted for any of M, L ₁ and L ₂ , or a group as L ₃ .

R _{1 in the} general formula (1) may have a substituent other than the E group, and examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom), a straight chain, Branched and cyclic alkyl groups (C1-C20, preferably C1-C10 alkyl groups such as methyl, t-butyl, cyclopentyl, cyclohexyl, adamantyl, biadamantyl, diamantyl, etc.), alkynyl groups (carbon number) 2-10 alkynyl group, ethynyl, phenylethynyl, etc.), aryl group (6-C10 aryl group, phenyl, 1-naphthyl, 2-naphthyl, etc.), acyl group (acyl group having 1-10 carbon atoms) Group, acetyl, benzoyl, etc.), aryloxy group (C6-C10 aryloxy group, phenoxy, etc.), arylsulfonyl group (C6-C10 aryl group). Reelsulfonyl group, phenylsulfonyl, etc.), alkoxy group (C1-C10 alkoxy group, methoxy group, ethoxy group, propoxy group, etc.), nitro group, cyano group, silyl group (C1-C10 silyl) Group, triethoxysilyl, methyldiethoxysilyl, trivinylsilyl, etc.), alkoxycarbonyl group (C2-C10 alkoxycarbonyl group, methoxycarbonyl etc.), carbamoyl group (C1-C10 carbamoyl group) , Carbamoyl, N, N-dimethylcarbamoyl, etc.). These substituents may be further substituted with another substituent.

R _{2 in the} general formula (1) represents a divalent to hexavalent organic group having 2 to 30 carbon atoms, preferably having an aromatic ring and / or an aliphatic group, more preferably 2 having 2 to 24 carbon atoms. A pentavalent organic group having an aromatic ring and / or an aliphatic group, particularly preferably a divalent to tetravalent organic group having 2 to 20 carbon atoms having an aromatic ring and / or an aliphatic group. Is.

R ₂ preferably represents a structure in the general formula (1c) or (1d) containing (E) s shown below.

Here, L ₄ , L ₅ , and L ₆ have the same meaning as L ₁ , L ₂ , and L ₃ described above. E and s represent the same meaning as E and s in the general formula (1). In addition, when s is 1 to 4, any of M, L ₄ and L ₅ , or the group as L ₆ is s
E's are substituted.

R _{2 in the} general formula (1) may have a substituent other than the E group, and examples of the substituent are the same as those exemplified as the substituent of the group represented by R ₁ .

The repeating unit represented by the general formula (1) is composed of an acid component having at least four carboxyl groups with R ₁ as a nucleus and a diamine component having at least two amino groups with R ₂ as a nucleus.

  Examples of the acid component include pyromellitic acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid anhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid anhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid anhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic acid anhydride, 4, 4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 1,2,5,6-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 2,3,5 , 6-pyridinetetracarboxylic anhydride, 3,4,9,10-perylenetetracarboxylic anhydride and other aromatic tetracarboxylic anhydrides, cyclobutanetetracarboxylic anhydride, cyclopentane Tetracarboxylic acid anhydride, cyclohexane tetracarboxylic acid anhydrides, aliphatic tetracarboxylic acid anhydrides such as and the like. Preferably, pyromellitic acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid anhydride, 2,2 ′, 3, 3'-biphenyltetracarboxylic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 1,2,5, 6-naphthalenetetracarboxylic acid anhydride, cyclobutanetetracarboxylic acid anhydride, cyclopentanetetracarboxylic acid anhydride, cyclohexanetetracarboxylic acid anhydride, more preferably pyromellitic acid anhydride, 3,3 ′, 4,4 '-Biphenyltetracarboxylic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, cyclobutanetetracarboxylic acid , Cyclopentanetetracarboxylic acid anhydride, cyclohexanetetracarboxylic acid anhydride, particularly preferably 4,4 ′-(hexafluoroisopropylidene) diphthalic acid anhydride, cyclobutanetetracarboxylic acid anhydride, cyclohexanetetracarboxylic acid It is an acid anhydride.

  Examples of the diamine component include bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis ( 3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, Hydroxyl group-containing diamine such as 3,5-diaminobenzoic acid, carboxyl group-containing diamine such as 3-carboxy-4,4′-diaminodiphenyl ether, and sulfonic acid such as 3-sulfonic acid-4,4′-diaminodiphenyl ether Diamine, dithiohydroxyphenylenedia Or the like can be mentioned down. Preferably, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, 3,5-diaminobenzoic acid Acid, 3-carboxy-4,4′-diaminodiphenyl ether, more preferably bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis ( 3-amino-4-hydroxyphenyl) propane and 3,5-diaminobenzoic acid, particularly preferably bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) ) Sulphone, 3,5-diaminobenzoic acid.

In the general formula (1), E represents a group having an acidic group, specifically represented by the general formula (1a).
-A- (B) _n (E1)
In the formula, A represents an n + 1 valent linking group, and B represents an acidic group. As an acidic group, it is preferable that pKa is 15 or less, More preferably, it is 2-12. Examples of acidic _{groups, -OH, -COOH, -SO 3 H} , -SO 2 NH 2, -C (CF 3) 2 -OH and the like, preferably, -OH, -COOH, -SO ₂ NH ₂ , and —C (CF ₃ ) ₂ —OH, and more preferably —OH and —COOH.
n represents an integer of 1 to 3, preferably 1 or 2, and most preferably 1.

The n + 1-valent linking group represented by A is a single bond, an alkylene group having 1 to 20 carbon atoms, —O—, —S—, —SO ₂ —, —CO—, —N (R ₁₀ ) —, or An n + 1 valent group obtained by removing n-1 arbitrary hydrogen atoms of a divalent group formed by combining these, R ₁₀ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Represents an acyl group.

  The resin containing the repeating unit represented by the general formula (1) is not particularly limited in molecular weight, but in terms of alkali dissolution rate, film physical properties and the like, the mass average molecular weight is preferably 1,000 to 500,000, 3,000 to 300,000 is more preferable, and 5,000 to 200,000 is particularly preferable. In the present invention, the molecular weight is measured by gel permeation chromatography and can be determined using a standard polystyrene calibration curve.

  An example of the method for producing the resin (polyimide resin) of the present invention is as follows. In the organic solvent, the diamine compound and tetracarboxylic dianhydride are reacted at −20 to 50 ° C. for several minutes to several days, thereby polyamic acid. Next, a polyimide resin is obtained by heating or treatment with a dehydrating ring-closing agent. Examples of organic solvents that can be used in the synthesis reaction of the polyamic acid include amide solvents such as N, N-dimethylacetamide and N-methyl-2-pyrrolidinone, fragrances such as benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, and pyridine. Examples include group solvents, halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane and 1,1,2,2-tetrachloroethane, ether solvents such as tetrahydrofuran, dioxane and diglyme. In particular, when an amide solvent such as N, N-dimethylacetamide or N-methyl-2-pyrrolidinone is used, a high molecular weight polyamic acid can be obtained.

  The polyamic acid obtained as described above is then dehydrated and closed to obtain a polyimide resin. A known method can be used as a method for dehydrating and ring-closing, and for example, a thermal cyclization method by refluxing with toluene, xylene or the like can be used. Since this polyimide resin contains toluene, xylene and the like used for dehydration, the polyimide resin solution is poured into a poor solvent such as water and methanol, re-precipitated, and further dried to obtain polyimide resin powder. To do. This is dissolved in a desired organic solvent to obtain a solution of the soluble polyimide resin used in the present invention.

  The molecular weight of the polyimide resin of the present invention in this method is limited by the amount charged with the diamine compound, and a high molecular weight polyimide resin can be produced when equimolar amounts are used.

The boiling point of the organic solvent used for the polymerization reaction is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 150 ° C. or higher.
The concentration of the solute in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 20% by mass.

The photosensitive resin composition of the present invention may contain a resin in which some of the acidic groups of the resin containing the repeating unit represented by the general formula (1) are protected for the purpose of adjusting solubility. Examples of the protecting group in this case include an alkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, and an alkoxycarbonyl group having 2 to 10 carbon atoms. The protecting group may be an acid-decomposable protecting group or a tertiary alkyl group (a tertiary alkyl group having 4 to 15 carbon atoms, preferably 4 to 13 carbon atoms, such as a t-butyl group, t-butyl group, An amyl group, a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, a 1-ethylcyclohexyl group), an alkoxyalkyl group (an alkoxyalkyl group having 2 to 10 carbon atoms such as methoxymethyl, 1-ethoxyethyl, tetrahydropropylene- 2-yl group), a silyl group (a silyl group having 3 to 15 carbon atoms, such as trimethylsilyl, triethylsilyl, t-butyldimethylsilyl) and the like.
The content of the resin other than the resin including the repeating unit represented by the general formula (1) is 10 parts by mass or less, preferably 5 with respect to 100 parts by mass of the resin including the repeating unit represented by the general formula (1). It is 3 parts by mass or less, more preferably 3 parts by mass or less.

(B) Compound that generates sulfonic acid by light irradiation (b) of the present invention is a compound that generates sulfonic acid by light irradiation. The repeating unit represented by the general formula (1) is represented by the presence or absence of light irradiation. It is a compound which can control the solubility with respect to the developing solution of the resin which has.
For example, a compound that generates sulfonic acid in a compound that generates acid by light (b ′) described below can be used.
Preferred embodiments of (b) include (b-1) N-hydroxyimide sulfonate compounds (also referred to as imide sulfonate compounds), (b-2) oxime sulfonate compounds, (b-3) nitrobenzyl sulfonate compounds, and the like. it can.

(B-1) Imidosulfonate compound As an imidesulfonate compound, the compound of the following general formula can be mentioned.

In the formula, C ₁ (carbon atom) and C ₂ (carbon atom) are bonded by a single bond or a double bond, and R ₅₁ or R ₅₂ may be the same or different, and the following (1) to (4) (1) each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group (2) a monocyclic or polycyclic ring that may contain one or more heteroatoms together with C ₁ and C ₂ Form. (3) Represents a residue containing (4) N-sulfonyloxyimide, which forms a condensed aromatic ring containing C ₁ and C ₂ .
R ₅₃ represents an alkyl group, a halogenated alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a camphor group.

In the general formula (PA-5), when R ₅₁ and R ₅₂ correspond to the case of (1), the alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, Examples thereof include alkyl groups having 1 to 4 carbon atoms such as tert-butyl group. Examples of the cycloalkyl group include those having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group. Examples of the aryl group include those having 6 to 14 carbon atoms such as phenyl group, tolyl group, xylyl group, mesityl group, and naphthyl group. When R ₅₁ and R ₅₂ correspond to the case of (2), for example, the following partial structures can be given.

When R ₅₁ and R ₅₂ correspond to the case of (3), for example, the following partial structures can be given.

When R ₅₁ and R ₅₂ correspond to the case of (4), so-called at least two N-sulfonyloxyimide residues are a single bond at the R ₅₁ and R ₅₂ portions having the partial structures of (1) to (3) above. Or the thing couple | bonded with the following bivalent organic groups can be mention | raise | lifted. However, the following linking groups are used alone or in combination of two or more.
[Divalent organic group]: -O -, - S -, - SO -, - SO 2 -, - NH -, - CO -, - CO 2 -, - NHSO 2 -, - NHCO -, - NHCO 2 −

_Examples of the alkyl group for R ₅₃ include linear or branched alkyl groups having 1 to 20 carbon atoms. Preferred is a linear or branched alkyl group having 1 to 16 carbon atoms, and more preferred is one having 1 to 12 carbon atoms. In the case of an alkyl group having 21 or more carbon atoms, sensitivity and resolving power decrease, which is not preferable. Examples of the halogenated alkyl group include those in which one or two or more hydrogen atoms of the alkyl group are halogenated. Examples of the halogen atom to be substituted include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferred are a fluorine atom, a chlorine atom and a bromine atom, and particularly preferred is a fluorine atom. However, the halogen atom to be substituted may be plural types per molecule. Examples of the cyclic alkyl group include cycloalkyl groups having 3 to 12 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group, and polycyclic substituents such as norbornyl group, adamantyl group, and tricyclodecanyl group. I can give you. Examples of the alkenyl group include linear or branched alkenyl groups having 1 to 20 carbon atoms. Preferred is a linear or branched alkenyl group having 1 to 16 carbon atoms, and more preferred is one having 1 to 12 carbon atoms. In the case of an alkenyl group having 21 or more carbon atoms, sensitivity and resolving power decrease, which is not preferable.

_Examples of the aryl group of R ₅₃ include a phenyl group and a naphthyl group, and examples of the aralkyl group include a benzyl group. Examples of the substituent of the aryl group and the aralkyl group include a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a tert-butyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a phenyl group, a toluyl group, Aryl group such as xylyl group, mesityl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, sec-butoxy group, tert-butoxy group and other lower alkoxy groups, vinyl group, allyl group, propenyl group, butenyl group, etc. And an acyl group such as alkenyl group, formyl group and acetyl group, and halogen atoms such as hydroxy group, carboxy group, cyano group, nitro group, fluorine atom, chlorine atom, bromine atom and iodine atom. Preferably, a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, cyclohexyl group, phenyl group, toluyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, sec-butoxy Group, lower alkoxy group such as tert-butoxy group, halogen atom such as cyano group, nitro group, fluorine atom, chlorine atom, bromine atom and iodine atom. Two or more kinds of substituents on the aryl group and the aralkyl group may be used.

  Specific examples of these compounds are shown below, but are not limited thereto.

(B-2) Oxime sulfonate compound As an oxime sulfonate compound, the compound of the following general formula (PA-6) can be mentioned.

In General Formula (PA-6), R ₆₁ and R _{62 each} represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, or a substituent which may have a substituent having 1 to 16 carbon atoms. Represents an aryl group, a heteroaryl group, or a cyano group, which may have R ₆₁ and R ₆₂ are an alkylene chain, alkenylene chain, alkynylline chain, which may have a substituent having 2 to 8 carbon atoms, or phenylene, freelen, thienylene, which may have a substituent, It may be bonded to R ₆₁ or R _{62 of the} compound represented by another general formula (PA-6) via a linking chain containing —O—, —S—, —N—, and —CO—. .
R ₃ is an alkyl group, cycloalkyl group optionally having a substituent having 1 to 16 carbon atoms,
An aryl group which may have a substituent is represented.

In the general formula (PA-6), R ₆₁ and R ₆₂ are an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, substituted, which may have a substituent having 1 to 16 carbon atoms. An aryl group, a heteroaryl group or a cyano group which may have a group is represented. R ₆₁ and R ₆₂ are an alkylene chain, alkenylene chain, alkynylline chain, which may have a substituent having 2 to 8 carbon atoms, or phenylene, freelen, thienylene, which may have a substituent, It may be bonded to R ₆₁ or R _{62 of the} compound represented by another general formula (PA-6) via a linking chain containing —O—, —S—, —N—, and —CO—. . That is, the compound represented by the general formula (PA-6) includes those having two or three oxime sulfonate structures via a linking chain.
R ₆₃ represents an alkyl group, a cycloalkyl group, or an aryl group which may have a substituent, which may have a substituent having 1 to 16 carbon atoms.

Examples of the alkyl group having 1 to 16 carbon atoms in R _{61 to} R ₆₃ include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, t-amyl group, n-hexyl group, n-octyl group, i-octyl group, n-decyl group, undecyl group, dodecyl group, hexadecyl group and other alkyl groups, trifluoromethyl group, perfluoropropyl group, perfluorobutyl group, perfluoro-t- Examples thereof include a butyl group, a perfluorooctyl group, a perfluoroundecyl group, and a 1,1-bistrifluoromethylethyl group.

Examples of the alkenyl group in R ₆₁ and R ₆₂ include allyl group, methallyl group, vinyl group, methylallyl group, 1-butenyl group, 3-butenyl group, 2-butenyl group, 1,3-pentadienyl group, 5-hexenyl group, A 2-oxo-3-pentenyl group, a decapentaenyl group, a 7-octenyl group and the like can be mentioned.

Examples of the alkynyl group for R ₆₁ and R ₆₂ include an ethynyl group, a propargyl group, a 2-butynyl group, a 4-hexynyl group, a 2-octynyl group, a phenylethynyl group, a cyclohexylethynyl group, and the like.

Examples of the cycloalkyl group in R _{61 to} R ₆₃ include those having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.

Examples of the cycloalkenyl group for R ₆₁ and R ₆₂ include a cyclobutenyl group, a cyclohexenyl group, a cyclopentadienyl group, and a bicyclo [4.2.4] dodec-3,7-dien-5-yl group.

Examples of the aryl group in R _{61 to} R ₆₃ include those having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group, which may have a substituent.

The above substituents include alkyl groups, cycloalkyl groups, alkoxy groups, halogen atoms (fluorine atoms, chlorine atoms, iodine atoms), cyano groups, hydroxy groups, carboxy groups, nitro groups, aryloxy groups, alkylthio groups, aralkyls. And groups represented by the following general formula (1A).
Here, the alkyl group and the cycloalkyl group have the same meanings as described above. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group. Examples of the aralkyl group include a benzyl group, a naphthylmethyl group, a furyl group, and a thienyl group.

In the formula (1A), R ₆₁ and R ₆₂ have the same meanings as R ₆₁ and R ₆₂ in formula (PA-6).

  Specific examples of the compound represented by the general formula (PA-6) are shown below, but the present invention is not limited thereto.

  Specific examples of more preferable oxime sulfonate compounds include the following (z66) to (z70).

(B-3) Nitrobenzyl sulfonate compound As the nitrobenzyl sulfonate compound, a compound represented by formula (TA-9) can be exemplified.

(Z in this formula is alkyl group, aryl group, alkylaryl group, halogen-substituted alkyl group, halogen-substituted aryl group, halogen-substituted alkylaryl group, nitro-substituted aryl group, nitro-substituted An alkylaryl group, an aryl group having a nitro substituent and a halogen substituent, an alkylaryl group having a nitro substituent and a halogen substituent, and the formula C ₆ H ₄ SO ₃ CHR′C ₆ H _4-m Q _m (NO ) is selected from groups having _2, R 'are selected from hydrogen atoms and methyl groups, and nitro substituted aryl groups, each Q is a hydrocarbon group, hydrocarbonoxy carboxy group, NO _2, halogen atoms and organosilicon Independently selected from the group, the value of m is 0, 1 or 2, provided that Q is not an acidic group, R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, An acyl group having 1 to 4 carbon atoms.)

  Specific examples of the compound represented by the general formula (TA-9) include the following compounds.

  In the photosensitive resin composition of the present invention, the compounding amount of the compound that generates sulfonic acid by light irradiation is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the total resin of the present invention, and 2 to 20 Part by mass is more preferable.

  The compounds that generate sulfonic acid upon irradiation with light can be used singly or in combination of two or more.

(B ′) Compound that generates acid by light In the photosensitive resin composition of the present invention, for the purpose of improving sensitivity and resolution, the following compound that generates acid by light (also referred to as a photoacid generator) is added. May be.
Photoacid generator includes photoinitiator for photocationic polymerization, photoinitiator for photoradical polymerization, photodecoloring agent for dyes, photochromic agent, irradiation of actinic ray or radiation used for micro resist, etc. The known compounds that generate an acid and mixtures thereof can be appropriately selected and used.

For example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, diazodisulfone and disulfone can be mentioned.
Among the compounds that generate an acid upon irradiation with actinic rays or radiation, preferred compounds (photoacid generators) include pKa as strong as 2 or less as a generated acid, alkyl or arylcarboxylic acid substituted with sulfonic acid or an electron withdrawing group. Acid, disulfonylimide substituted with an electron withdrawing group, and the like are preferable. Examples of the electron withdrawing group include a halogen atom such as an F atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation, compounds represented by the following general formulas (ZI), (ZII), and (ZIII) can be exemplified.

In general formulas (ZI) to (ZIII),
R ₂₀₁ to R ₂₀₇ each independently represent an organic group.
The number of carbons in the organic group R ₂₀₁ to R ₂₀₇ generally has 1 to 30, preferably 1 to 20.
Two members out of R _{201 to} R ₂₀₃ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
X ⁻ represents a non-nucleophilic anion, preferably sulfonate anion, carboxylate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion, BF ⁴⁻ , PF ⁶⁻ , SbF ^{6− and the} like. An organic anion having a carbon atom is preferable.

  Preferable organic anions include organic anions represented by the following general formula.

In the above general formula,
Rc ₁ represents an organic group.
Examples of the organic group for Rc ₁ include those having 1 to 30 carbon atoms, and preferably an alkyl group, a cycloalkyl group, an aryl group, or a plurality thereof, which may be substituted, is a single bond, —O—, — _{CO 2 -, - S -,} - SO 3 -, - SO 2 N (Rd 1) - can be exemplified linked group a linking group such as.
Rd ₁ represents a hydrogen atom or an alkyl group.
Rc ₃ , Rc ₄ and Rc ₅ each independently represents an organic group.
Examples of the organic group of Rc ₃ , Rc _4, and Rc ₅ include the same organic groups as those preferred for Rc ₁ , and preferably a perfluoroalkyl group having 1 to 4 carbon atoms.
Rc ₃ and Rc ₄ may combine to form a ring.
Examples of the group formed by combining Rc ₃ and Rc ₄ include an alkylene group, a cycloalkylene group, and an arylene group. Preferably, it is a C2-C4 perfluoroalkylene group.
The organic group of Rc ₁ and Rc _{3 to} Rc ₅ is preferably an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved. Further, Rc ₃ and Rc ₄ are preferably bonded to form a ring, whereby the acidity of the acid generated by light irradiation is increased, and the sensitivity is improved, which is preferable.

  As the specific substituent, it is preferable that at least one of the aryl groups of the triarylsulfonium salt has an electron-withdrawing group as a substituent, and the total Hammett value of the substituents bonded to the aryl skeleton is 0.18 or more. Larger is preferred.

Here, the electron-withdrawing group means a substituent having a Hammett value (Hammet substituent constant σ) larger than 0. In the present invention, from the viewpoint of increasing sensitivity, the sum of Hammett values of substituents bonded to the aryl skeleton in the specific photoacid generator is preferably 0.18 or more, more preferably greater than 0.46. Preferably, it is more preferably larger than 0.60.
The Hammett value represents the degree of electron withdrawing property of a cation having a triarylsulfonium salt structure, and there is no particular upper limit from the viewpoint of increasing sensitivity, but from the viewpoint of reactivity and stability. , More than 0.46 and less than 4.0, more preferably more than 0.50 and less than 3.5, and particularly preferably more than 0.60 and less than 3.0.

In addition, the Hammett value in the present invention uses the numerical value described in Naoki Inamoto, edited by Chemistry Seminar 10 Hammett's Rule-Structure and Reactivity (1983, published by Maruzen Co., Ltd.).
Examples of the electron-withdrawing group introduced into the aryl skeleton include a trifluoromethyl group, a halogen atom, an ester group, a sulfoxide group, a cyano group, an amide group, a carboxyl group, and a carbonyl group. The Hammett values of these substituents are shown below. A trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), a halogen atom [eg, —F (m: 0.34, p: 0.06), —Cl (m: 0. 37, p: 0.23), - Br (m: 0.39, p: 0.23), - I (m: 0.35, p: 0.18) ], an ester group (e.g., -COCH ₃ , O: 0.37, p: 0.45), a sulfoxide group (for example, —SOCH ₃ , m: 0.52, p: 0.45), a cyano group (—CN, m: 0.56, p: 0.66), an amide group (for example, —NHCOCH ₃ , m: 0.21, p: 0.00), a carboxyl group (—COOH, m: 0.37, p: 0.45), a carbonyl group (— CHO, m: 0.36, p: (043)) and the like. The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value, and (m: 0.50) is the Hammett value of 0.50 when the substituent is introduced at the meta position. Indicates that there is.

Among these substituents, nonionic substituents such as a halogen atom and a halogenated alkyl group are preferable from the viewpoint of hydrophobicity. Among them, —Cl is preferable from the viewpoint of reactivity, and imparts hydrophobicity. from the _{viewpoint, -F, -CF 3, -Cl,} -Br are preferable.

These substituents may be introduced into any one of the three aryl skeletons of the triarylsulfonium salt structure, or may be introduced into two or more aryl skeletons. Moreover, the substituent introduced into each of the three aryl skeletons may be one or plural. In the present invention, the sum of Hammett values of substituents introduced into these aryl skeletons is preferably more than 0.18, more preferably more than 0.46. The number of substituents to be introduced is arbitrary. For example, only one substituent having a particularly large Hammett value (for example, a Hammett value exceeding 0.46 alone) may be introduced into one position of an aryl skeleton having a triarylsulfonium salt structure. Moreover, for example, a plurality of substituents introduced and the sum of the Hammett values exceeding 0.46 may be introduced.

As described above, since the Hammett value of the substituent varies depending on the position of introduction, the sum of Hammett values in the specific photoacid generator according to the present invention is determined by the type of substituent, the introduction position, and the number of introductions. become.
The Hammett value is usually expressed in the m-position and p-position, but in the present invention, the substituent effect at the o-position is calculated as the same value as the p-position as an index of electron withdrawing. Preferred substitution positions are preferably m-position and p-position, and most preferably p-position, from the viewpoint of synthesis.
Preferred in the present invention is a sulfonium salt that is tri- or more substituted with a halogen atom, and most preferred is a sulfonium salt that is tri-substituted with a chloro group, specifically, each of the three aryl skeletons. A halogen atom, most preferably a triarylsulfonium salt structure in which —Cl is introduced, is preferable, and a structure in which —Cl is substituted at the p-position is more preferable.

  Examples of the sulfonate anion contained in the triarylsulfonium salt contained in the composition of the present invention include an arylsulfonate anion and an alkanesulfonate anion, which are substituted with a fluorine atom or an organic group having a fluorine atom. Anions are preferred.

  Compounds having a triarylsulfonium salt structure are disclosed in, for example, J. Org. Am. Chem. Soc. 112 (16), 1990; 6004-6015, J.A. Org. Chem. 1988; It can be easily synthesized by the methods described in 5571-5573, WO02 / 081439A1 pamphlet, or European Patent (EP) No. 1113005.

  Although a specific example is given below, it is not limited to these.

In the photosensitive resin composition of the present invention, it is preferable to add a sensitizer in order to promote the decomposition in the combination with the sulfonium salt. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with sulfonium, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the polymerization initiator undergoes a chemical change and decomposes to generate radicals, acids or bases.
Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.
Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange,
Chloroflavin, acriflavine), anthraquinones (e.g., anthraquinone), squarics (e.g., squalium), coumarins (e.g., 7-diethylamino 4-methylcoumarin). Among these, an anthracene derivative is particularly preferable as a sensitizer. These sensitizers may be commercially available or may be synthesized by a known synthesis method.

  The addition amount of the sensitizer is preferably 20 to 200 parts by mass, and more preferably 30 to 150 parts by mass with respect to 100 parts by mass of the sulfonium salt.

(B ″) Quinonediazide photosensitizer In the photosensitive resin composition of the present invention, an o-quinonediazide photosensitizer may be added. Examples of the o-quinonediazide photosensitizer include o-quinonediazidesulfonyl chlorides, hydroxy compounds, and amino compounds. It can be obtained by subjecting a compound or the like to a condensation reaction in the presence of a dehydrochlorinating agent.

  Examples of the o-quinonediazide sulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4-sulfonyl chloride. However, naphthoquinone-1,2-diazide-4-sulfonyl chloride is preferable in terms of sensitivity.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and 2,3,4-trihydroxybenzophenone. 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4, 3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro -1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2, -a] indene, tris (4-hydroxyphenyl) methane, and tris (4-hydroxyphenyl) ethane can be used.

  Examples of amino compounds include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl sulfide. , O-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino 4,4′-dihydroxybiphenyl, 4,4′-diamino 3,3′-dihydroxybiphenyl, bis (3-amino-4 -Hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxy) Phenyl) hexafluoropropane, bi (4-amino-3-hydroxyphenyl) hexafluoropropane can be used.

  The o-quinonediazide sulfonyl chloride and the hydroxy compound and / or amino compound may be blended so that the total of hydroxy group and amino group is 0.5 to 1 equivalent with respect to 1 mol of o-quinonediazide sulfonyl chloride. preferable. A preferred ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 1/1 to 1 / 0.9. A preferable reaction temperature is 0 to 40 ° C., and a preferable reaction time is 1 to 24 hours.

  Examples of the quinonediazide photosensitizer include compounds described in [0078] to [0082] of JP-A-2007-199606.

In the photosensitive resin composition of the present invention, the compounding amount of the quinonediazide photosensitizer is based on the difference in dissolution rate between the exposed part and the unexposed part, and the allowable range of sensitivity, with respect to 100 parts by mass of the total resin of the present invention. 1 to 25 parts by mass is preferable, and 5 to 20 parts by mass is more preferable.
0.1-15 mass parts is preferable with respect to 100 mass parts of total amounts of resin of this invention, and, as for the compounding quantity of photosensitizers other than a quinonediazide photosensitizer, 0.5-10 mass parts is more preferable.

(C) Crosslinking agent having alkoxymethyl group or acyloxymethyl group on nitrogen atom The photosensitive resin composition of the present invention comprises (c) a crosslinking agent having an alkoxymethyl group or acyloxymethyl group on a nitrogen atom (hereinafter, crosslinking agent). (Also referred to as (c)). Examples of the crosslinking agent having an alkoxymethyl group or an acyloxymethyl group on the nitrogen atom include a glycoluril-based crosslinking agent and a melamine-based crosslinking agent.

(C1) Glycoluril-based / melamine-based cross-linking agent The cross-linking agent of the present invention is preferably a glycoluril-based cross-linking agent or a melamine-based cross-linking agent from the viewpoint of suppressing coloration or change in film strength over time.
The alkoxymethyl group or acyloxymethyl group of the compound preferably has 2 to 5 carbon atoms, and more preferably 2 or 3 carbon atoms. In the case of an alkoxymethyl group, 2 carbon atoms are particularly preferred, and in the case of an acyloxymethyl group, 3 carbon atoms are particularly preferred.
1-10 are preferable, as for the total of the alkoxymethyl group and acyloxymethyl group which the said compound has, More preferably, it is 2-8, Most preferably, it is 3-6.
The molecular weight of the compound is preferably 1500 or less, and more preferably 180 to 1200.
Examples of the crosslinking agent having an alkoxymethyl group or an acyloxymethyl group on a nitrogen atom in the present invention include (c1a) a compound in which an alkoxymethyl group or an acyloxymethyl group is bonded to a nitrogen atom of a urea structure, and (c1b) a triazine derivative (melamine). And the compound bonded to the aromatic amine atom of (system).

  Examples of the compound (c1a) include compounds represented by the following general formula (CL-1).

In the formula, R represents an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, R ₁₀₁ and R ₁₀₂ represent a monovalent organic group, and R ₁₀₁ and R ₁₀₂ are bonded to each other to form 5 An ˜8 membered ring may be formed.
Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, a compound in which 1 to 4 of the methylol groups of tetramethylolglycoluril are methoxymethylated, or a mixture thereof, tetramethylolglycoluril Or a mixture thereof in which 1 to 4 of the methylol groups are acyloxymethylated. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, or a mixture thereof, tetramethoxyethyl urea, and the like.

Specific examples of the compound having an alkoxymethyl group represented by (CL-1) include the following structures.
In addition, the compound which has an acyloxymethyl group can mention the compound which changed the alkoxymethyl group of the following compound into the acyloxymethyl group.
The compound having an alkoxymethyl group or acyloxymethyl in the molecule is not limited to the following compounds.

  Examples of the compound (c1b) include compounds represented by the following general formula (CL-2).

In the formula, R represents an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, and Ra is decomposed by the action of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or an acid. And a group that generates an alkali-soluble group.
Specific examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, and a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, Examples thereof include compounds in which 1 to 6 methylol groups of hexamethylolmelamine are acyloxymethylated, or a mixture thereof.

  1-20 mass parts is preferable with respect to 100 mass parts of resin of this invention, and, as for the addition amount of a crosslinking agent (c), 3-15 mass parts is more preferable. As the crosslinking agent having an alkoxymethyl group or an acyloxymethyl group on the nitrogen atom, a commercially available one may be used, or one synthesized by a known method may be used. The crosslinking agent having an alkoxymethyl group or an acyloxymethyl group on the nitrogen atom in the present invention may be used in combination of two or more.

The photosensitive resin composition of the present invention can contain other crosslinking agents in addition to the crosslinking agent (c). As typical crosslinking agents that can be mixed, an alkoxymethyl group or an acyloxymethyl group is used. Examples thereof include a crosslinking agent directly on the aromatic carbocycle and a (meth) acrylate crosslinking agent.
100 mass% or less is preferable with respect to the addition amount of a crosslinking agent (c), and, as for the addition amount of crosslinking agents other than a crosslinking agent (c), 50 mass% or less is more preferable.

(C2) Crosslinking agent having an alkoxymethyl group or acyloxymethyl group directly on the aromatic carbocycle As a crosslinking agent having an alkoxymethyl group or acyloxymethyl group directly on the aromatic carbocycle, for example, a compound having the following general formula Can be mentioned.

In the formula, R represents an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, and Ra is decomposed by the action of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or an acid. And a group that generates an alkali-soluble group.
Rb independently represents an alkyl group, a cycloalkyl group or an alkenyl group, and A represents an m-valent linking group. Examples of the linking group include an alkylene group (eg, methylene, ethylene, propylene, etc.), a cycloalkylene group (eg, cyclohexylene, cyclopentylene, etc.), an arylene group (1,2-phenylene, 1,3-phenylene, 1,4- Phenylene, naphthylene, etc.), ether groups, carbonyl groups, ester groups, amide groups, and m-valent groups obtained by removing m-2 arbitrary hydrogen atoms in a divalent group obtained by combining these groups. When A is monovalent, a hydrogen atom, an alkyl group that is a monovalent group corresponding to the divalent group, an aryl group, and the like can be given.
p is 1, 2, q is 0-2, m is 1-8, preferably 2-6.

The group that decomposes by an acid as _Ra and generates an alkali-soluble group is a group that decomposes by the action of an acid and generates an alkali-soluble group such as a hydroxyl group or a carboxyl group. For example, it is eliminated by the action of an acid. group, or ^{_{-C (R 4) 2 -COOR 5}} (R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ is. represents a group capable of leaving by the action of acid).
When R ⁰ is a group capable of decomposing by the action of an acid to generate an alkali-soluble group, and R ⁰ is a group leaving by the action of an acid, R ⁰ itself is released by the action of the acid, thereby generating —OH; When R ⁰ is —C (R ⁴ ) ₂ COOR ⁵ , R ⁵ is released by the action of an acid to produce —COOH.
Examples of the group capable of leaving by the action of an acid include an acetal group and a tertiary ester group.
Specific examples of the acetal group include alkoxyalkyl groups such as methoxymethyl group and ethoxyethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, alkoxy-substituted tetrahydropyranyl group, alkoxy-substituted tetrahydrofuranyl group and the like.

  Specific examples of the ester group include a t-butyl group, a t-amyl group, a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, and a 1-ethylcyclohexyl group.

Specific examples of the compound having an alkoxymethyl group include the following structures.
In addition, the compound which has an acyloxymethyl group can mention the compound which changed the alkoxymethyl group of the following compound into the acyloxymethyl group.
The compound having an alkoxymethyl group or acyloxymethyl in the molecule is not limited to the following compounds.

These crosslinking agents may be commercially available or may be synthesized by a known method.
1-20 mass parts is preferable with respect to 100 mass parts of resin of this invention, and, as for the addition amount of these compounds, 3-15 mass parts is more preferable.

(C3) (Meth) acrylate-based crosslinking agent The composition of the present invention may be used by mixing a compound containing a methacryloyl group or an acryloyl group for the purpose of improving film physical properties.
The compound containing a methacryloyl group or an acryloyl group is a compound selected from the group consisting of acrylic acid esters and methacrylic acid esters. It has been found that the addition of this compound improves film properties. Therefore, a compound having two or more acryloyl groups or methacryloyl groups in one molecule, more preferably four or more functional groups is preferable.

  Preferred specific examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di ( (Meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanedio Such as rudi (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc. Polyfunctional alcohols obtained by addition reaction of ethylene oxide or propylene oxide and then (meth) acrylated, in Japanese Patent Publication Nos. 48-41708, 50-6034, 51-37193, etc. Described urethane acrylates; polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, etc .; epoxy resins and (meth) Such as multifunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  The amount of the compound containing a methacryloyl group or acryloyl group in the molecule of the present invention is preferably 0.5 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the resin of the present invention. More preferably, they are 1 mass part or more and 20 mass parts or less, Most preferably, they are 2 mass parts or more and 15 mass parts or less.

(D) Thermal acid generator A thermal acid generator can be added to the photosensitive resin composition of the present invention in order to further improve film physical properties and heat resistance.
The thermal acid generator of the present invention is a compound that generates an acid by heat, and is usually a compound having a thermal decomposition point in the range of 130 ° C to 250 ° C, preferably 150 ° C to 220 ° C. It is a compound that generates a low nucleophilic acid such as sulfonic acid, carboxylic acid, disulfonylimide and the like.
As the generated acid, sulfonic acid, an alkyl substituted with an electron withdrawing group or an arylcarboxylic acid having a strong pKa of 2 or less, disulfonylimide substituted with an electron withdrawing group, and the like are preferable. Examples of the electron withdrawing group include a halogen atom such as an F atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.
As the thermal acid generator, a photoacid generator that generates an acid by the above-described exposure can be applied. Examples include onium salts such as sulfonium salts and iodonium salts, N-hydroxyimide sulfonate compounds, oxime sulfonates, o-nitrobenzyl sulfonates, and the like.

The thermal acid generator of the present invention is preferably a compound that does not substantially generate an acid when exposed to exposure light and generates an acid when exposed to heat. It is preferable to use a compound which generates a sulfonic acid.
Whether or not an acid is substantially generated by exposure light exposure can be determined, for example, by the presence or absence of changes in the IR spectrum and NMR spectrum of the compound before and after the light irradiation.

For example, the sulfonate ester represented by the following general formula (TA-1) can be given.
R′—SO ₂ —O—R ″ (TA-1)
In the above formula, R ′ and R ″ are each independently a linear or branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent or a carbon number which may have 6 substituents. And an aryl group having a carbon number of from 20 to 20. Examples of the substituent include a hydroxyl group, a halogen atom, a cyano group, a vinyl group, and an acetylene group having a linear or cyclic alkyl group having 1 to 10 carbon atoms.
Preferable specific examples of the sulfonic acid ester include the following.

As the sulfonic acid ester, a compound represented by the following general formula (TA-2) is more preferable in terms of heat resistance.
The molecular weight of the sulfonate ester is generally 230 to 1000, preferably 230 to 800.

A represents an h-valent linking group.
R ₀ represents an alkyl group, an aryl group, an aralkyl group, or a cyclic alkyl group.
R _{0 ′} represents a hydrogen atom, an alkyl group, or an aralkyl group.
h represents an integer of 2 to 8.

The h-valent linking group as A includes, for example, an alkylene group (for example, methylene, ethylene, propylene, etc.), a cycloalkylene group (for example, cyclohexylene, cyclopentylene, etc.), an arylene group (1,2-phenylene, 1,3). -Phenylene, 1,4-phenylene, naphthylene, etc.), an ether group, a carbonyl group, an ester group, an amide group, and a group obtained by removing h-2 arbitrary hydrogen atoms from a divalent group obtained by combining these groups. Can be mentioned.
The h-valent linking group as A generally has 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.

The alkyl group for R ₀ and R _{0 ′} is generally an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. is there. Specific examples include methyl, ethyl, propyl, butyl, hexyl, octyl and the like.
The aralkyl group for R ₀ and R _{0 ′} is generally an aralkyl group having 7 to 25 carbon atoms, preferably an aralkyl group having 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 15 carbon atoms. is there. Specific examples include benzyl, toluylmethyl, mesitylmethyl, phenethyl and the like.
The cyclic alkyl group for R ₀ is generally a cyclic alkyl group having 3 to 20 carbon atoms, preferably a cyclic alkyl group having 4 to 20 carbon atoms, more preferably a cyclic alkyl group having 5 to 15 carbon atoms. is there. Specific examples include cyclopentyl, cyclohexyl, norbornyl, camphor group and the like.

  The linking group as A may further have a substituent. The substituent is an alkyl group (an alkyl group having 1 to 10 carbon atoms, specifically methyl, ethyl, propyl, butyl, hexyl). Octyl, etc.), aralkyl groups (aralkyl groups having 7 to 15 carbon atoms, specifically benzyl, toluylmethyl, mesitylmethyl, phenethyl, etc.), aryl groups (aryl groups having 6 to 10 carbon atoms, specifically Are phenyl, toluyl, xylyl, mesityl, naphthyl, etc.), an alkoxy group (the alkoxy group may be linear, branched or cyclic, and is an alkoxy group having 1 to 10 carbon atoms, specifically, Methoxy, ethoxy, linear or branched propoxy, linear or branched butoxy, linear or branched pentoxy, cyclopentyloxy, cyclohexyloxy, etc.) A reeloxy group (an aryloxy group having 6 to 10 carbon atoms, specifically phenoxy, toluyloxy, 1-naphthoxy, etc.), an alkylthio group (which may be linear, branched or cyclic, the number of carbon atoms) 1 to 10 alkylthio groups, specifically methylthio, ethylthio, linear or branched propylthio, cyclopentylthio, cyclohexylthio), arylthio groups (arylthio groups having 6 to 10 carbon atoms, specifically phenylthio , Toluoylthio, 1-naphthylthio, etc.), acyloxy groups (acyloxy groups having 2 to 10 carbon atoms, specifically acetoxy, propanoyloxy, benzoyloxy, etc.), alkoxycarbonyl groups (alkoxycarbonyl having 1 to 10 carbon atoms) Groups such as methoxycarbonyl, ethoxycarbonyl, Or branched propoxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, etc.), can be exemplified.

In the general formula (2), R ₀ is preferably an alkyl group or an aryl group. R _{0 ′} is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and most preferably a hydrogen atom.

  Examples of the sulfonic acid ester of the present invention include the following specific compounds, but are not limited thereto.

As the sulfonic acid ester of the present invention, a commercially available one may be used, or one synthesized by a known method may be used. The sulfonic acid ester of the present invention can be synthesized, for example, by reacting sulfonyl chloride or sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.
1-20 mass parts is preferable with respect to 100 mass parts of resin of this invention, and, as for the addition amount of a thermal acid generator, Most preferably, it is 2-15 mass parts.

(E) Adhesion promoter In the positive photosensitive resin composition of the present invention, an adhesion promoter such as an organosilicon compound, a silane coupling agent, and a leveling agent for imparting adhesion may be added as necessary. Examples of these are, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl. Trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, tris ( Acetylacetonate) aluminum, acetylacetate aluminum diisopropylate and the like. When using an adhesion promoter, 0.1 to 20 parts by mass is preferable with respect to 100 parts by mass of the resin of the present invention, and 0.5 to 10 parts by mass is more preferable.

(F) Solvent The solvent is not particularly limited as long as it can dissolve the composition of the present invention. However, in order to prevent the solvent from evaporating more than necessary at the time of coating and precipitating the solid content of the composition at the time of coating, Solvents with the above boiling points are preferred.
Preferred solvents include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl lactate, 3-methoxybutanol and cyclohexanone.
Further, a solvent having a high boiling point such as N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), propylene carbonate and the like may be used supplementarily.
However, if the solvent remains in the film after curing, sufficient film properties cannot be obtained. Therefore, it is not preferable to include a solvent having a boiling point equal to or higher than the curing temperature (high boiling point solvent) in excess of 30% by mass in the solvent. The addition amount of the high boiling point solvent is generally 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less.

(G) Pattern formation method As a method of forming a relief pattern using the photosensitive resin composition of the present invention, (1) the photosensitive resin composition of the present invention is coated on a suitable substrate, and (2) This coated substrate is baked (pre-baked), (3) exposed to actinic rays or radiation, (4) post-heated as necessary, (5) developed with aqueous developer, and (6) cured. A cured relief pattern can be formed.

  The coated and exposed substrate can also be baked at elevated temperatures prior to development. Further, the developed substrate may be rinsed before curing.

  Thus, with the photosensitive resin composition of this invention, it apply | coats on a semiconductor element so that the thickness after heat curing may become predetermined thickness (for example, 0.1-30 micrometers), prebaking, exposure, image development, and heat curing. Thus, a semiconductor device can be manufactured.

  Hereinafter, a method for forming a relief pattern will be described in more detail.

The photosensitive resin composition of the present invention is coated on a suitable substrate. The substrate is for example a semiconductor material such as a silicon wafer or a ceramic substrate, glass, metal or plastic. Coating methods include spray coating, spin coating, offset printing,
Examples include, but are not limited to, roller coating, screen printing, extrusion coating, meniscus coating, curtain coating, and dip coating.

  The coating film is pre-baked for a few minutes to half an hour at an elevated temperature of about 70-130 ° C., depending on the method, to evaporate the remaining solvent. Subsequently, the resulting dry film is exposed to actinic rays or radiation in a preferred pattern through a mask. As actinic rays or radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used. The most preferred radiation is one having wavelengths of 436 nm (g-line) and 365 nm (i-line).

  Advantageously, the coated and exposed substrate is heated to a temperature of about 70-130 ° C. following exposure to actinic rays or radiation. The coated and exposed substrate is heated in this temperature range for a short time, typically a few seconds to a few minutes. This stage of the method is commonly referred to in the art as post-exposure baking.

  The coating film is then developed with an aqueous developer and a relief pattern is formed. Examples of the aqueous developer include inorganic alkali (eg, potassium hydroxide, sodium hydroxide, aqueous ammonia), primary amine (eg, ethylamine, n-propylamine), secondary amine (eg, diethylamine, di-n-propyl). Amines), tertiary amines (eg, triethylamine), alcohol amines (eg, triethanolamine), quaternary ammonium salts (eg, tetramethylammonium hydroxide, tetraethylammonium hydroxide), and alkaline solutions such as mixtures thereof There is. The most preferred developer is one containing tetramethylammonium hydroxide. In addition, an appropriate amount of surfactant may be added to the developer. Development can be carried out by dipping, spraying, paddling, or other similar development methods.

  In some cases, the relief pattern is then rinsed using deionized water. Next, the relief pattern is cured in order to obtain a final pattern of resin having high heat resistance. Curing is carried out to form a film having high heat resistance, chemical resistance and film strength. Generally, it has been heat-cured at a temperature of about 300 to 400 ° C. On the other hand, with the composition of the present invention, a film having film physical properties equal to or higher than that of the conventional composition can be obtained at less than 300 ° C., more specifically at 200 ° C. to 250 ° C.

The following examples illustrate the invention and do not limit the scope thereof.
<Compound group used in Examples and Comparative Examples>

Example 1
<Synthesis of polyimide having alkali-soluble group>
In a 2 liter flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 717 ml of N-methyl-2-pyrrolidinone, 64.25 g of 1,2,3,4-cyclobutanetetracarboxylic anhydride (manufactured by Aldrich) ( 327.6 mmol), 120 g (327.6 mmol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (manufactured by Nippon Kayaku Co., Ltd.), and stirred for 6 hours at room temperature for reaction. Then, the polymerization solution was poured into 10 liters of distilled water and stirred for 1 hour. The precipitate was collected and washed, and then dried under reduced pressure to synthesize 150 g of hydroxyl group-containing polyamic acid (P-1).
80 g of the obtained (P-1) was charged into a 1 liter flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, and 320 ml of N-methyl-2-pyrrolidinone and 1.6 g of sulfuric acid were added, and the mixture was heated to 180 ° C. For 8 hours. After completion of the stirring, the solution was poured into 5 liters of distilled water, and the precipitate was collected, washed, and dried under reduced pressure to obtain 60 g of hydroxyl group-containing polyimide (P-2). The intrinsic viscosity of the obtained P-2 was 0.70 dL / g.

<Preparation of positive photosensitive resin composition>
85 parts by mass of synthesized polyimide (P-2), 20 parts by mass of oxime sulfonate photoacid generator (z66) (manufactured by Ciba Specialty Chemicals), 10 parts by mass of cross-linking agent Nicalac N2702 (manufactured by Sanwa Chemical Co., Ltd.) Was dissolved in 200 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), and then filtered through a 0.2 μm PTFE filter to obtain a photosensitive resin composition.

<Characteristic evaluation>
This photosensitive resin composition was applied on a 4-inch silicon wafer using a spin coater and then dried in an oven at 125 ° C. for 3 minutes to obtain a coating film having a thickness of 7 μm. This coating film was irradiated with i-line (365 nm) from a high-pressure mercury lamp through a glass mask, and then exposed to 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds to dissolve and remove the exposed area, and rinsed with pure water. did. As a result, it was confirmed that a 1 μm extraction pattern was resolved on the silicon wafer.

Separately, the photosensitive resin composition was similarly coated on a silicon wafer and was heated in an oven.
The resin was cured by heating in the order of 0 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 250 ° C. for 30 minutes. The obtained coating film was peeled off and stored under the following conditions, and color change and moisture absorption were measured.

Storage conditions: temperature 85 ° C., relative humidity 85%, color change for 24 hours: change in color compared with samples stored under the above conditions at 20 ° C. and relative humidity 50% Was visually observed.
Moisture absorption rate (%): When the mass of the sample before storage under the above conditions is A (mg) and the mass of the same sample immediately after storage under the above conditions is B (mg), the value calculated by the following formula is the moisture absorption Rate (%).
Moisture absorption (%) = [(BA) / A] × 100
The film obtained in Example 1 had almost no color change and a small moisture absorption rate.

Example 2
A photosensitive resin was prepared in the same manner as in Example 1 except that 5 parts by mass of a thermal acid generator (T-1) (relative to 85 parts by mass of polyimide) was further added to the photosensitive resin composition of Example 1. A composition was prepared and evaluated in the same manner as in Example 1.

Example 3
The same as Example 1 except that the crosslinker Nicalac N2702 (manufactured by Sanwa Chemical Co., Ltd.) in the photosensitive resin composition of Example 1 was changed to the crosslinker Nicalac MW30HM (manufactured by Sanwa Chemical Co., Ltd.). A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1.

Example 4
A photosensitive resin was prepared in the same manner as in Example 3 except that 5 parts by mass of a thermal acid generator (T-1) (relative to 85 parts by mass of polyimide) was further added to the photosensitive resin composition of Example 3. A composition was prepared and evaluated in the same manner as in Example 1.

Example 5
The photosensitivity was the same as in Example 1 except that the oxime sulfonate photoacid generator (z66) in the photosensitive resin composition of Example 1 was changed to an imide sulfonate photoacid generator (PG-1). A resin composition was prepared and evaluated in the same manner as in Example 1.

Example 6
A photosensitive resin was prepared in the same manner as in Example 5 except that 5 parts by mass of a thermal acid generator (T-1) (relative to 85 parts by mass of polyimide) was further added to the photosensitive resin composition of Example 5. A composition was prepared and evaluated in the same manner as in Example 1.

Example 7
Photosensitive resin composition in the same manner as in Example 5 except that the crosslinker Nicalac N2702 (manufactured by Sanwa Chemical Co., Ltd.) was changed to the crosslinker Nicalac MW30HM (manufactured by Sanwa Chemical Co., Ltd.). Was prepared and evaluated in the same manner as in Example 1.

Example 8
A photosensitive resin was prepared in the same manner as in Example 7 except that 5 parts by mass of a thermal acid generator (T-1) (relative value to 85 parts by mass of polyimide) was further added to the photosensitive resin composition of Example 7. A composition was prepared and evaluated in the same manner as in Example 1.

Example 9
Photosensitizing in the same manner as in Example 1 except that the oxime sulfonate photoacid generator (z66) in the photosensitive resin composition of Example 1 was changed to a nitrobenzyl sulfonate photoacid generator (N-1). An adhesive resin composition was prepared and evaluated in the same manner as in Example 1.

Example 10
A photosensitive resin was prepared in the same manner as in Example 9, except that 5 parts by mass of a thermal acid generator (T-1) (relative to 85 parts by mass of polyimide) was further added to the photosensitive resin composition of Example 9. A composition was prepared and evaluated in the same manner as in Example 1.

Example 11
The same as Example 9 except that the crosslinking agent Nicarak N2702 (manufactured by Sanwa Chemical Co., Ltd.) in the photosensitive resin composition of Example 9 was changed to the crosslinking agent Nicalac MW30HM (manufactured by Sanwa Chemical Co., Ltd.). A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1.

Example 12
A photosensitive resin was prepared in the same manner as in Example 11 except that 5 parts by mass of a thermal acid generator (T-1) (relative value to 85 parts by mass of polyimide) was further added to the photosensitive resin composition of Example 11. A composition was prepared and evaluated in the same manner as in Example 1.

Example 13
Example 1 except that the oxime sulfonate photoacid generator (z66) in the photosensitive resin composition of Example 1 was changed to an oxime sulfonate photoacid generator (z70) (manufactured by Ciba Specialty Chemicals). A photosensitive resin composition was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

Example 14
A photosensitive resin was prepared in the same manner as in Example 13 except that 5 parts by mass of a thermal acid generator (T-1) (relative value to 85 parts by mass of polyimide) was further added to the photosensitive resin composition of Example 13. A composition was prepared and evaluated in the same manner as in Example 1.

Comparative Example 1
The oxime sulfonate photoacid generator (z66) in the photosensitive resin composition of Example 1 was mixed with an equal part by weight of 2,3,4-tris [-2-diazo-1 (2H) -naphthalenone-4-sulfonyl. A photosensitive resin composition was prepared in the same manner as in Example 1 except that it was changed to oxy] benzophenone (NQD-1) (manufactured by Toyo Gosei Co., Ltd.), and evaluation was performed in the same manner as in Example 1. .

Comparative Example 2
Comparative example except that the cross-linking agent Nicarak N2702 (manufactured by Sanwa Chemical Co., Ltd.) in the photosensitive resin composition of Comparative Example 1 was changed to HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) of equal parts by mass. A photosensitive resin composition was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

Comparative Example 3
The oxime sulfonate photoacid generator (z66) in the photosensitive resin composition of Example 1 was changed to an equal part by weight of a triarylsulfonium salt (PAG-1), and the crosslinking agent Nicalak N2702 (Sanwa Chemical ( The photosensitive resin composition was prepared in the same manner as in Example 1 except that the product was changed to HMOM-TPHAP (made by Honshu Chemical Industry Co., Ltd.). And evaluated.

  The evaluation results of Examples 1 to 14 and Comparative Examples 1 to 3 are shown in Table 1.

Compared with the comparative example, it can be seen that the example using the film forming composition of the present invention has a small color change and moisture absorption under high temperature and high humidity conditions, and is excellent in durability.

Claims (5)

(A) a resin containing a repeating unit represented by the general formula (1), (b) a compound capable of generating a sulfonic acid upon irradiation with light, and (c) a crosslinking agent having an alkoxymethyl group or an acyloxymethyl group on the nitrogen atom. Containing photosensitive resin composition.
(R ¹ represents a C 4-30 tetravalent organic group. R ² represents a C 2-30 bivalent organic group. E represents a group having an acidic group. When there are a plurality of groups, they may be the same or different. R and s are integers of 0 to 4, but r + s> 0.)   (B) The photosensitive resin composition according to claim 1, wherein the compound that generates sulfonic acid upon irradiation with light is an imide sulfonate compound, an oxime sulfonate compound, or a nitrobenzyl sulfonate compound.   Furthermore, (d) the compound which generate | occur | produces an acid with a heat | fever is contained, The photosensitive resin composition of Claim 1 or 2 characterized by the above-mentioned.   The manufacturing method of the pattern including the process of apply | coating and drying the composition in any one of Claims 1-3 on a board | substrate, the process of exposing, and the process of developing using aqueous alkali solution.   An electronic device having a pattern obtained by the manufacturing method according to claim 4.