JP2009242756A - Photosensitive resin composition, polymer compound, method for producing pattern, and electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of forming a hardened pattern or a hardened film, which is excellent in sensitivity, resolution and heat resistance. <P>SOLUTION: The photosensitive resin composition is characterized by including: a polymer compound (a) obtained by reacting a monomer represented by general formula (1); and a photosensitive agent (b) (wherein T<SB>1</SB>represents an oxygen atom and/or a sulfur atom; Ar<SB>1</SB>and Ar<SB>2</SB>represent a bivalent to hexavalent 6-30C organic group which may be substituted by a substituent; R<SB>1</SB>represents a hydrogen atom or a silyl group, which may be same or different; X<SB>1</SB>represents a leaving group, which may be same or different; Y represents an acidic group or a group including an acidic group protected by an acid-decomposable group; a plurality of Ys included in the polymer compound may have one or more types; and each a is an integer of 0 to 4 and a≥1 is satisfied). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a surface protective film of a semiconductor device, an interlayer insulating film, a photosensitive resin composition used as an interlayer insulating film for a display device, a method for producing a heat-resistant pattern using the photosensitive resin composition, and a pattern It is related with the device which has.

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. (For example, Patent Document 1)
For example, as a positive photosensitive resin, there is a system using a polyphenylene oxide resin obtained by oxidative coupling polymerization using a copper catalyst (Patent Document 2).
JP 2004-133088 A JP 2000-275842 A

It has been found that the polyphenylene oxide disclosed in Patent Document 2 needs to improve the heat resistance of the resin. Although this factor has not been clarified, since it is synthesized by oxidative coupling polymerization using a copper catalyst, there is a possibility that the catalyst may remain in the resin. .
The present invention provides a photosensitive resin composition capable of forming a cured pattern or a cured film excellent in sensitivity, resolution, and heat resistance. Moreover, this invention provides the manufacturing method of the pattern which is excellent in a sensitivity, the resolution, and heat resistance by using the said photosensitive resin composition, and the pattern of a favorable shape is obtained. The present invention also provides a highly reliable electronic device by forming a pattern having a good shape and characteristics.

  It has been found that the above problems are solved by the following <1> to <6> configurations.

<1> A photosensitive resin composition comprising a polymer compound (a) obtained by reacting a monomer represented by the following general formula (1) and a photosensitive agent (b).

(Here, T ₁ represents an oxygen atom and / or a sulfur atom. Ar ₁ and Ar ₂ represent a bivalent to hexavalent organic group having 6 to 30 carbon atoms and may be substituted by a substituent. R ₁ represents a hydrogen atom or a silyl group, and each may be different or the same X ₁ represents a leaving group, and each may be different or the same Y may be an acidic group or Represents a group containing an acidic group protected by an acid-decomposable group, wherein the plurality of Y contained in the polymer compound may be one type or two or more types, a is an integer of 0 to 4; ≧ 1.)

<2> The photosensitive resin composition according to <1>, wherein the photosensitive agent is a compound that generates an acid by light.
<3> The photosensitive resin composition according to <1> or <2>, further comprising (c) a crosslinking agent.

<4> A polymer compound obtained by reacting the monomer represented by the general formula (1).

<5> The photosensitive resin composition according to any one of the above <1> to <3> is developed using a step of coating and drying on a substrate, a step of exposing, an alkaline aqueous solution and / or an organic solvent. A method for producing a pattern including a process.
<6> An electronic device having a pattern obtained by the production method according to <5>.

  The compound of the present invention has sufficient solubility in a general-purpose coating solvent in the field of electronic device production, and the composition using the compound is uniform and does not precipitate insoluble matter, and is obtained by using the composition. The pattern is excellent in sensitivity, resolution and heat resistance, and has a good shape. The obtained pattern has high heat resistance, high mechanical strength, good surface shape, 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) Polymer compound obtained by reacting the monomer represented by the general formula (1) The polymer compound of the present invention is obtained by reacting the monomer represented by the general formula (1). Preferably, it can also be obtained by reacting with the monomer represented by the general formula (2).

In the above formula, T ₁ and T ₂ represent an oxygen atom and / or a sulfur atom. Ar _1, Ar ₂ represents a divalent to hexavalent organic group having 6 to 30 carbon atoms, it may be substituted by a substituent. R ₁ and R ₂ represent a hydrogen atom or a silyl group, and each may be different or the same. X ₁ and X ₂ represent a leaving group, and each may be different or the same. Y represents a group containing an acidic group protected with an acidic group or an acid-decomposable group. The plurality of Y contained in the polymer compound may be one type or two or more types. Each a is an integer of 0 to 4, and a ≧ 1.

In the general formula (1), T ₁ and T ₂ represent an oxygen atom and / or a sulfur atom, preferably an oxygen atom. Ar ₁ represents a 2 to 8 valent organic group having 6 to 30 carbon atoms, preferably having an aromatic ring and / or an aliphatic group, more preferably a 2 to 7 valent organic group having 6 to 24 carbon atoms. And having an aromatic ring and / or an aliphatic group, particularly preferably a divalent to hexavalent organic group having 6 to 20 carbon atoms having an aromatic ring and / or an aliphatic group.

Ar ₁ preferably represents a structure in the general formula (1a) or (1b) including the following (Y) a.

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 (for example, a benzene ring, a naphthalene ring, etc.), and a fat having 3 to 30 carbon atoms. Represents a group carbon ring (cyclopropane ring, cyclobutane ring, cyclopentane ring, etc.), 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. Y and a represent the same meaning as Y and a in the general formula (1). When a is 1 to 4, a number of M, L ₁ and L ₂ , or a group as L ₃ is substituted with a Y.

In the general formula (1), R ₁ and R ₂ represent a hydrogen atom and a silyl group (a silyl group having 1 to 10 carbon atoms, such as triethoxysilyl, methyldiethoxysilyl, trivinylsilyl, etc.), and are the same. Or different. Preferably, it is a silyl group having a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a silyl group having a hydrocarbon group having 1 to 3 carbon atoms, particularly preferably a hydrogen atom. is there.

Ar _{1 in the} general formula (1) may have a substituent other than R ₁ , R ₂ , and Y. Examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or Iodine atom), linear, 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 (C2-C10 alkynyl groups such as ethynyl and phenylethynyl), aryl groups (C6-C10 aryl groups such as phenyl, 1-naphthyl and 2-naphthyl), acyl groups ( An acyl group having 1 to 10 carbon atoms, such as acetyl and benzoyl), an aryloxy group (an aryloxy group having 6 to 10 carbon atoms, such as phenoxy), arylsulfonyl Group (C6-C10 arylsulfonyl 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 such as triethoxysilyl, methyldiethoxysilyl, trivinylsilyl, etc.), alkoxycarbonyl group (C2-C10 alkoxycarbonyl group such as methoxycarbonyl), carbamoyl group (carbon Examples of the carbamoyl group of formula 1 to 10 include carbamoyl, N, N-dimethylcarbamoyl and the like. These substituents may be further substituted with another substituent.

  Although the specific example of a monomer represented by General formula (1) below is shown, it is not limited to these.

Ar _{2 in the} general formula (2) represents a divalent to octavalent organic group having 6 to 30 carbon atoms, preferably having an aromatic ring and / or an aliphatic group, more preferably 2 having 6 to 24 carbon atoms. A 7 to 7 valent organic group having an aromatic ring and / or an aliphatic group, and particularly preferably a 2 to 6 valent organic group having 6 to 20 carbon atoms having an aromatic ring and / or an aliphatic group. Is.

Preferably, Ar ₂ represents a structure in the general formula (2a) or (2b) including (Y) b shown below.

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

In the general formula (2), X ₁ and X ₂ each represent a leaving group, and each may be the same or different. X1 and X2 are preferably a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a group containing a nitrogen atom such as a nitro group, a mesyl group, a tosyl group, etc., more preferably a fluorine atom, chlorine An atom, a bromine atom, an iodine atom, a nitro group, and a tosyl group, more preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a nitro group, and particularly preferably a fluorine atom, a chlorine atom, and a nitro group. is there.

Ar _{2 in the} general formula (2) may have a substituent other than X ₁ , X ₂ , and Y, and examples of the substituent include those listed as the substituent of the group represented by Ar ₁ The same.

  Although the specific example of a monomer represented by General formula (2) below is shown, it is not limited to these.

In the general formulas (1) and (2), Y represents a group containing an acidic group protected with an acidic group or an acid-decomposable group, and specifically represented by the general formula (y1).
-A- (B-PG) _n (y1)
In the formula, A represents an (n + 1) -valent linking group, PG represents a hydrogen atom or an acid-decomposable group, and B represents a partial structure of an acidic group in which a site exhibiting acidity is protected by the acid-decomposable group PG. n represents an integer of 1 to 2.
The acidic group generated by the decomposition (elimination) of PG preferably has a pKa of 15 or less, more preferably 2-12. Specific examples of the acidic group (BH) generated by decomposition (elimination) of PG include —OH, —COOH, —SO ₃ H, —SO ₂ NH ₂ , —C (CF ₃ ) ₂ —OH, and the like. Preferred are —OH, —COOH, —SO ₂ NH ₂ , and —C (CF ₃ ) ₂ —OH, and more preferred are —OH and —COOH.

The n + 1-valent linking group as A is a single bond, an alkylene group having 1 to 20 carbon atoms, an aryl group (an aryl group having 6 to 10 carbon atoms such as phenyl, 1-naphthyl, 2-naphthyl, etc.), an acyl group ( An acyl group having 1 to 10 carbon atoms, such as acetyl and benzoyl), an aryloxy group (an aryloxy group having 6 to 10 carbon atoms, such as phenoxy), an arylsulfonyl group (an arylsulfonyl group having 6 to 10 carbon atoms, Phenylsulfonyl, etc.), —O—, —S—, —SO ₂ —, —CO—, —CONH—, —COO—, —N (R ₁₀ ) —, or a divalent group formed by a combination thereof. Represents an n + 1 valent group obtained by removing n-1 hydrogen atoms, and R ₁₀ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms.

The acid-decomposable group represented by PG is not particularly limited as long as it can generate an acidic group by the action of an acid, but it is an acid-decomposable ether, ester, acetal, ketal, and heteroatom contained in the acidic group. Groups that can form silyl ethers or silyl esters are typical.
As the acid-decomposable group represented by PG, 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, a t-amyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-ethylcyclohexyl group) and those represented by the following general formulas (y2), (y3) and (y4) are preferable.

In the general formula (y2), R ₂₀ represents an alkyl group (an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl), and R ₂₁ and R ₂₂ are A hydrogen atom or an alkyl group (an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, for example, methyl, ethyl, propyl) is represented. When R ₂₀ and R ₂₁ are both alkyl groups, they may be bonded to each other to form a carbocycle.
In the general formula (y3), R ₂₃ represents an aryl group (an aryl group having 6 to 20 carbon atoms, such as phenyl or naphthyl), and R ₂₄ represents an alkyl group (having 1 to 10 carbon atoms, preferably 1 carbon atom). Represents an alkyl group of ˜4, for example, methyl, ethyl, propyl). The aryl group represented by R ₂₃ may have a substituent, and preferred substituents are the same as those exemplified as the substituent of the group represented by R ₁ .
In the general formula (y4), R _{25 to} R ₂₇ are alkyl groups (C1-C10, preferably C1-C4 alkyl groups such as methyl, ethyl, propyl) or aryl groups (C6 -20 aryl groups, for example phenyl, naphthyl).

  Specific examples of preferable PG include t-butyl group, t-amyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-ethylcyclohexyl group, methoxymethyl group, ethoxyethyl group and other alkoxyalkyl groups, tetrahydro Examples include pyranyl group, tetrahydrofuranyl group, alkoxy-substituted tetrahydropyranyl group, alkoxy-substituted tetrahydrofuranyl group, benzyl group, p-methoxybenzyl group, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group and the like.

  In general formula (1) and (2), a represents the integer of 0-4, Preferably the integer of 0-3 is represented, More preferably, the integer of 0-2 is represented. However, a> 0, and a is preferably an integer of 1 to 4, more preferably an integer of 2 to 4, and particularly preferably 2 and 3.

  The molecular weight of the compound of the present invention is not particularly limited, but in terms of alkali dissolution rate, film physical properties and the like, the weight average molecular weight is preferably 1,000 to 500,000, more preferably 3,000 to 300,000. 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.

  The polymer compound of the present invention includes, for example, a compound having two phenolic hydroxyl groups, which is a monomer represented by the general formula (1), and a leaving group chlorine, which is a monomer represented by the general formula (2). It can be obtained by polymerizing a compound having two atoms in a reaction solvent in the presence of an inorganic salt. An example of this reaction is shown below.

  The polymerization of the monomer of the general formula (1) and / or (2) is preferably performed in a solvent. The solvent used in the polymerization reaction of the monomer of the general formula (1) and / or (2) can dissolve the raw material monomer at a necessary concentration, and does not adversely affect the characteristics of the film formed from the obtained polymer. Any material can be used. For example, alcohol solvents such as water, methanol, ethanol, propanol, etc., ketone solvents such as acetone, alcohol acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, Ester solvents such as methyl benzoate, ether solvents such as dibutyl ether, anisole and tetrahydrofuran, toluene, xylene, mesitylene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene, isopropylbenzene, 1,4-diisopropyl Benzene, t-butylbenzene, 1,4-di-t-butylbenzene, 1,3,5-triethylbenzene, 1,3,5-tri-t-butylbenzene, 4-t-butyl-o Aromatic hydrocarbon solvents such as toxylene, 1-methylnaphthalene, 1,3,5-triisopropylbenzene, amide solvents such as N-methylpyrrolidinone, dimethylacetamide, carbon tetrachloride, dichloromethane, chloroform, 1,2- Halogen solvents such as dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, and aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane can be used.

  Among these, more preferred solvents are tetrahydrofuran, γ-butyrolactone, anisole, toluene, xylene, mesitylene, isopropylbenzene, t-butylbenzene, 1,3,5-tri-t-butylbenzene, 1-methylnaphthalene, 1, Amide solvents such as 3,5-triisopropylbenzene, N-methylpyrrolidinone, dimethylacetamide, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, particularly preferably Amide solvents such as N-methylpyrrolidinone and dimethylacetamide. These may be used alone or in admixture of two or more.

  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 general formula (1) and / or (2) used in the production of the polymer of the present invention acts as an alkali metal salt in the actual reaction. Therefore, the alkali metal salt of the general formula (1) and / or (2) can be separately synthesized and used, or the reaction can be carried out before forming the polymerization reaction or simultaneously forming the salt. Examples of the alkali metal salt include lithium, sodium, potassium, and the like, and potassium and sodium are particularly preferable. Examples of the metal compound used for forming the alkali salt include hydroxides, carbonates, bicarbonates, and the like, and hydroxides and carbonates are particularly preferable. Accordingly, potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate are preferred for forming the alkali salt of the general formula (1) and / or (2).
The inorganic salts used in the present invention may be used alone or in combination of two or more.
The amount of these alkali metal salts used varies depending on the type, and also varies depending on the substrate, but is 1 to 8 times mol based on the amount of the monomer represented by the general formula (1) and / or (2). A range is preferred. More preferably, it is the range of 2-4 times mole. When the amount of the alkali metal salt is not more than 1 mol per mol of the amount of the general formula (1) and / or (2), the alkali metal salt of the general formula (1) and / or (2) can be sufficiently formed. Therefore, it is difficult to obtain a high molecular weight polymer. Further, an excess amount of 8 times mole or more is not economically advantageous.

  The actual polymerization reaction in the production of the polymer of the present invention can be carried out in various forms shown below. For example, (I) in the presence of a polymerization solvent, a monomer of general formula (1) and / or (2), an alkali metal salt and an azeotropic dehydration solvent are added, and an alkali metal salt of general formula (1) and / or (2) is added. (II) In the presence of a polymerization solvent, the monomer of the general formula (1) and / or (2), an alkali metal salt, and an azeotropic dehydration solvent are added. A method of performing polymerization while carrying out boiling dehydration to produce an alkali metal salt of a monomer of the general formula (1) and / or (2), (III) an alkali metal of a monomer of the general formula (1) and / or (2) A method in which a salt is separately formed and polymerized in the presence of a polymerization solvent. (IV) An aqueous solution of an alkali metal salt of the monomer represented by formula (1) and / or (2) is added to the polymerization solvent, and an azeotropic solvent is further added to perform polymerization. How to do It is below.

  As is apparent from the examples of the polymerization methods described above, azeotropic dehydration uses an azeotropic solvent azeotropic with water as necessary. Examples include aromatic hydrocarbons such as benzene, toluene and xylenes, as well as halogenated aromatic hydrocarbons such as chlorobenzene and o-dichlorobenzene, which are particularly limited if azeotroped with water. is not. The amount of azeotropic solvent used can be determined from the amount of water present in the reaction system and the azeotropic composition. In dehydration using an azeotropic solvent, water is distilled together with the azeotropic solvent, the distillate is cooled and condensed, and water and the azeotropic solvent are separated into two layers. If the separated azeotropic solvent layer is refluxed to the reaction system, the azeotropic solvent is effectively used, so that dehydration can be completed without using a large excess of azeotropic solvent. The time required for azeotropic dehydration also varies depending on the amount of water present in the reaction system, the amount of azeotropic solvent to be used, etc., but in terms of practical use, it is preferably performed within 10 hours, and further completed within 5 hours. More preferably.

Optimum conditions for the polymerization reaction in the present invention vary depending on the type and concentration of the solvent, but the reaction temperature is preferably 0 ° C to 230 ° C, more preferably 100 ° C to 230 ° C, and particularly preferably 140 ° C to At 200 ° C., the reaction time is preferably 1 to 50 hours, more preferably 2 to 40 hours, particularly preferably 3 to 30 hours.
Moreover, it is preferable to make it react under inert gas atmosphere (for example, nitrogen, argon, etc.) in order to suppress the oxidative decomposition of a polymer. It is also preferred to polymerize under light-shielding conditions to suppress unwanted photoreactions.

  The monomers represented by the general formula (1) and / or (2) may be used individually by 1 type each when synthesizing a compound, or one type may be used for one type and two or more types may be used for the other type. Well, you may use 2 or more types, respectively.

(B) Photosensitizer The photosensitizer of the present invention refers to a compound that imparts the function of forming an image by exposure to the photosensitizer and / or gives the trigger. Specific examples include compounds that generate an acid upon exposure (photoacid generator), photosensitive quinonediazide compounds, and dihydropyridine compounds. Two or more of these photosensitizers can be used in combination. Moreover, a sensitizer etc. can also be used together for sensitivity adjustment.

(B1) Photoacid generator The photoacid generator is used as a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecolorant for dyes, a photochromic agent, or a microresist. Known compounds that generate an acid upon irradiation with actinic rays or radiation and mixtures thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates. Preferred photosensitizers include imide sulfonate, oxime sulfonate, and o-nitrobenzyl sulfonate, which are compounds that generate sulfonic acid.

  Further, a group that generates an acid upon irradiation with actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the resin, such as US Pat. No. 3,849,137, German Patent No. 3914407, JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, JP-A 62-153853, JP-A The compounds described in 63-146029 and the like can be used.

  Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712 and the like can also be used.

  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. 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.

Among the compounds that generate an acid upon irradiation with actinic rays or radiation, a preferable compound (photoacid generator) is a pKa as strong as 2 or less as a generated acid, an alkyl or an alkyl substituted with a sulfonic acid or an electron withdrawing group. Aryl carboxylic acids and disulfonylimides substituted with electron withdrawing groups are preferred. 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.
Examples of the photoacid generator include imide sulfonate compounds and oxime sulfonates.
Preferred imide sulfonate compounds as photoacid generators include compounds of the following general formula.

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) Represents one of the following.

(1) Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
(2) Form a monocyclic or polycyclic ring that may contain one or more heteroatoms together with C ₁ and C ₂ .
(3) A condensed aromatic ring containing C ₁ and C ₂ is formed.
(4) Represents a residue containing N-sulfonyloxyimide.

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.

  Preferred examples of the oxime sulfonate compound as the photoacid generator include compounds of the following general formula (PA-6).

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 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.

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.

より好ましいオキシムスルホネート化合物の具体例としては、下記（ｚ６６）〜（ｚ７０）が挙げられる。

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

  In the photosensitive resin composition of the present invention, the blending amount of the photoacid generator is preferably 0.5 to 30 parts by mass and more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin.

  An acid generator can be used individually by 1 type or in combination of 2 or more types.

(B2) Quinonediazide photosensitizer The o-quinonediazide photosensitizer can be obtained, for example, by subjecting o-quinonediazidesulfonyl chlorides to a hydroxy compound, an amino compound or the like 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.

  As the reaction solvent, solvents such as dioxane, 1,3-dioxolane, acetone, methyl ethyl ketone, tetrahydrofuran, chloroform, N-methylpyrrolidone, γ-butyrolactone and the like are used. Examples of the dehydrochlorinating agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine, 4-dimethylaminopyridine and the like.

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

  Examples of quinonediazide photosensitizers include compounds having the following structures.

(Wherein D is independently H or any of the following groups)

  However, at least 1 D should just be said quinonediazide group in each compound.

(B3) Sensitizer In the composition of the present invention, it is preferable to add a sensitizer in order to promote the decomposition in 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 (eg, anthraquinone), squalium (eg, , Squalium), coumarins (for example, 7-diethylamino 4-methylcoumarin). Among these, an anthracene derivative is particularly preferable as a sensitizer.

  Preferable specific examples include (C-1) to (C-26) shown below, but are not limited thereto.

  As the sensitizer as described above, a commercially available one may be used, or it 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 photosensitizer.

(C) Crosslinking agent In this invention, a crosslinking agent is used as a modifier. Here, the cross-linking agent is a material that cross-links with a polymer by an acid. , Urea compounds, phenolic compounds or phenolic ether compounds, and compounds containing double bonds such as epoxy compounds, thioepoxy compounds, isocyanate compounds, azide compounds, or alkenyl ether groups. In this respect, methylol-based crosslinking agents and melamine / glycoluril-based crosslinking agents are preferably used.
Moreover, the compound containing the (c1) alkoxymethyl group or acyloxymethyl group shown below, and the compound containing (c2) methacryloyl group or acryloyl group are preferable.

(C1) Compound containing alkoxymethyl group or acyloxymethyl group A compound containing an alkoxymethyl group or acyloxymethyl group may be added to the composition of the present invention. This compound is known to prevent pattern melting and heat shrinkage during curing without impairing lithography performance. Further, it is known that chemical resistance can be improved when applied to a low-temperature curing process.
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 compound containing an alkoxymethyl group or an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is bonded directly to (CL-1) a phenol derivative and (CL-2) a nitrogen atom (CL- 3) The compound couple | bonded with the aromatic carbon atom of the triazine derivative (melamine type) can be mentioned.
Examples of the (CL-1) compound include compounds represented by the following general formula.

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 each 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 of (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 (CL-2) include compounds represented by the following general formula.

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 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.

  A melamine compound can be mentioned as a compound of (CL-3). 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.

  As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available product or a compound synthesized by a known method may be used.

(C2) Compound containing methacryloyl group or acryloyl group The composition of the present invention may be used by mixing with a compound containing methacryloyl group or acryloyl group for the purpose of improving film 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 which are subjected to addition reaction of ethylene oxide or propylene oxide and then (meth) acrylated, are disclosed in JP-B-48-41708, JP-B-50-6034, JP-A-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.

  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, 3-15 mass parts is more preferable.

(D) Thermal acid generator In this invention, in order to improve the film | membrane physical property etc. in low temperature hardening, you may mix a thermal acid generator.
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, alkyl substituted with an electron withdrawing group or 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. Of these, N-hydroxyimide sulfonate compounds, oxime sulfonates, and o-nitrobenzyl sulfonates are preferred.

In the present invention, it is also preferable to use a sulfonic acid ester that does not substantially generate an acid by exposure to exposure light and generates an acid by heat.
The fact that acid is not substantially generated by exposure light exposure can be determined by no change in the spectrum by measuring IR spectrum and NMR spectrum before and after exposure of the compound.
The molecular weight of the sulfonate ester is generally 230 to 1000, preferably 230 to 800.
For example, the sulfonate ester represented by the following general formula (TA-10) can be given.

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-20) can be more preferably used from the viewpoint of heat resistance.

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). -Phenyl, 1,4-phenylene, naphthylene, etc.), ether groups, carbonyl groups, ester groups, amide groups, and any hydrogen atoms of divalent groups such as a combination of these groups are removed. And h-valent groups. The 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 it is a C4-C20 cyclic alkyl group, More preferably, it is a C5-C15 cyclic alkyl group. 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 a general formula of nitrobenzyl sulfonate which is preferable as a thermal acid generator, a compound represented by the general formula (TA-9) can be exemplified.

(Z in this formula is an alkyl group having 1 to 30 carbon atoms, an aryl group, an alkylaryl group, a halogen-substituted alkyl group having 1 to 30 carbon atoms, a halogen-substituted aryl group, or a halogen-substituted alkylaryl group. , A nitro-substituted aryl group having 6 to 30 carbon atoms, a nitro-substituted alkylaryl group, an aryl group having 6 to 30 carbon atoms and a halogen substituent, and an alkylaryl having a nitro substituent and a halogen substituent group, and, is selected from groups having the formula _{C 6 H 4 SO 3 CHR'C 6} H 4-m Q m (NO) 2, R is a hydrogen atom, a nitro-substituted methyl group, and 6 to 30 carbon atoms Each Q is independently selected from a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbonoxy group, NO ₂ , a halogen atom and an organosilicon group, and the value of m is 0, 1 Or 2, where Q is not an acidic group)
Specific examples of the compound represented by the general formula (TA-9) include the following compounds.

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.
The addition amount of the sulfonic acid ester of the present invention is 100 mass of the total amount of the polymer compound (a) obtained by reacting the monomer represented by the general formula (1) with the monomer represented by the following general formula (2). 1-20 mass parts is preferable with respect to a part, 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, 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 physical properties cannot be obtained. Therefore, it is not preferable that the solvent having a boiling point not lower than the curing temperature (high boiling point solvent) is 30% by mass or more in the solvent. The amount of the high-boiling solvent added is 30% by mass or less, preferably 20% by mass or less, and 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, but are not limited to, spray coating, spin coating, offset printing, 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>

<Monomer (a-2) Synthesis Example 1>
4-fluorobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 25.0 g (157.7 mmol) and methyl o-anisate (manufactured by Tokyo Chemical Industry Co., Ltd.) 26.2 g (157.7 mmol) were cooled in an ice bath. However, 56.3 g (346.9 mmol) of iron (III) chloride (manufactured by Aldrich) was added thereto. Then, reaction was performed at room temperature for 2 hours, and it poured into 2 L of distilled water, and the depositing solid was separated by filtration. 20 g of this solid was dissolved in 150 mL of methylene chloride, and 69.5 g (277.5 mmol) of boron tribromide (manufactured by Aldrich) was added at −40 ° C., followed by reaction at room temperature for 2 hours. After completion of the reaction, extraction with methylene chloride and distilled water was performed, and washing with distilled water was performed three times to obtain 16.0 g of the desired product (a-2). (Yield 89%)

Synthesis example 1
<Synthesis of polyethersulfone having an alkali-soluble group>
After adding 25.0 g (45.1 mmol) of monomer (a-2) and 13.7 g (99.2 mmol) of potassium carbonate to 195 ml of N-methyl-2-pyrrolidinone and 97 ml of toluene, and stirring at 150 ° C. for 4 hours, Toluene was distilled off. Furthermore, the polymerization solution was obtained by reacting at 180 ° C. for 16 hours. After completion of the reaction, the inorganic salt was filtered off from the polymerization solution and poured into an aqueous hydrochloric acid solution to precipitate a polymer. The precipitated solid was washed with water and dried under reduced pressure at 50 ° C. to obtain 21 g of Resin (A-1). The number average molecular weight of the resin (A-1) was 8,000 as calculated from the ¹ HNMR spectrum (manufactured by BRUKER).
20.0 g of the obtained resin (A-1) was charged into a 0.2 liter flask, 80 g of THF was added to dissolve the flask, and the flask was cooled to 0 ° C. After dropwise addition of 7.88 g (83.3 mmol) of 2-chloroethyl methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.09 g (8.33 mmol) of pyridinium p-toluenesulfonate was added and stirred at room temperature for 1 hour. Then, 8.43 g (83.3 mmol) of triethylamine was added dropwise and stirred for 1 hour. This reaction solution was poured into 1 liter of distilled water, and the precipitate was collected and washed, and then dried under reduced pressure to obtain a resin (A-2). The proportion of protected acidic groups was 62%.

Example 1
<Preparation of positive photosensitive resin composition>
85 parts by mass of synthesized resin (A-2), 2,3,4-tris [-2-diazo-1 (2H) -naphthalenone-4-sulfonyloxy] benzophenone (NQD-1) (Toyo Gosei Co., Ltd.) 5 parts by mass) was dissolved in 200 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), and then filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm to obtain a photosensitive resin composition.

<Characteristic evaluation>
This photosensitive resin composition was applied onto a 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 5 μm extraction pattern was resolved on the silicon wafer.

Separately, the photosensitive resin composition was similarly applied onto a silicon wafer and heated in the order of 200 ° C. for 30 minutes, 250 ° C. for 30 minutes, and 300 ° C. for 30 minutes to cure the resin. The obtained coating film was peeled off, and the heat resistance (5% mass reduction temperature) was examined by SDT Q600 (manufactured by TA Instruments).
The 5% mass reduction temperature is determined by measuring the mass of the film up to 500 ° C. at a rate of temperature increase of 10 ° C./min in a nitrogen stream, and assuming that the mass at room temperature (23 ° C.) is 100. The temperature at which the temperature reached 95 was defined as “5% mass reduction temperature”.
The results are shown in Table 1.

Synthesis example 2
Resin (B-1) was synthesized by replacing 25.0 g (96.1 mmol) of monomer (a-2) in Synthesis Example 1 with 25.0 g (90.4 mmol) of (a-1). The number average molecular weight of the resin (B-1) is GPC manufactured by Tosoh Corporation (apparatus: HLC-8220, column temperature: 40 ° C., flow rate: 0.3 ml / min, column: TSK-GEL; SUPER-AW series, Solvent: NMP solution with LiBr concentration of 10 mmol / L, number average molecular weight was 7,700 as a result of measurement. Using 2-chloroethyl methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) (83.3 mmol) for (B-1), a protective group introduction reaction was carried out in the same manner as in Synthesis Example 1 to obtain resin (B-2). Obtained. The proportion of protected acidic groups was 61%.

Example 2
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the resin (A-2) in the photosensitive resin composition of Example 1 was changed to the resin (B-2). Evaluation was performed in the same manner as above.

Synthesis example 3
Resin (C-1) was synthesized by replacing 25.0 g (96.1 mmol) of monomer (a-2) in Synthesis Example 1 with 25.0 g (107.7 mmol) of (a-6), and (C-1 ), 2-chloroethyl methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) (94.3 mmol) was used to carry out a protective group introduction reaction in the same manner as in Synthesis Example 1 to obtain a resin (C-2). The proportion of protected acidic groups was 57%.

Example 3
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the resin (A-2) in the photosensitive resin composition of Example 1 was changed to the resin (C-2). Evaluation was performed in the same manner as above.

Synthesis example 4
Resin (D-1) was synthesized by replacing 25.0 g (96.1 mmol) of diphenol monomer (a-2) in Synthesis Example 1 with 25.0 g (100.5 mmol) of (a-5), and (D -1) was subjected to a protective group introduction reaction in the same manner as in Synthesis Example 1 using 2-chloroethyl methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) (94.3 mmol) to obtain a resin (D-2). . The proportion of protected acidic groups was 62%.

Example 4
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the resin (A-2) in the photosensitive resin composition of Example 1 was changed to the resin (D-2). Evaluation was performed in the same manner as above.

Synthesis example 5
Resin (E-1) was synthesized by replacing 25.0 g (96.1 mmol) of monomer (a-2) in Synthesis Example 1 with 25.0 g (70.9 mmol) of (a-23), and (E-1) Using 2-chloroethyl methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) (60.2 mmol), a protective group was introduced in the same manner as in Synthesis Example 1 to obtain a resin (E-2). The proportion of protected acidic groups was 58%.

Example 5
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the resin (A-2) in the photosensitive resin composition of Example 1 was changed to the resin (E-2). Evaluation was performed in the same manner as above.

Synthesis Example 6
Resin (F-1) was synthesized by replacing 25.0 g (96.1 mmol) of monomer (a-2) in Synthesis Example 1 with 25.0 g (77.1 mmol) of (a-26), and (F-1) Using 2-chloroethyl methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) (65.8 mmol), a protective group introduction reaction was carried out in the same manner as in Synthesis Example 1 to obtain a resin (F-2). The proportion of protected acidic groups was 58%.
Example 6
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the resin (A-2) in the photosensitive resin composition of Example 1 was changed to the resin (F-2). Evaluation was performed in the same manner as above.

Synthesis example 7
Resin (G-1) was synthesized by replacing 25.0 g (96.1 mmol) of monomer (a-2) in Synthesis Example 1 with 25.0 g (67.9 mmol) of (a-25). The number average molecular weight of the resin (G-1) is GPC manufactured by Tosoh Corporation (apparatus: HLC-8220, column temperature: 40 ° C., flow rate: 0.3 ml / min, column: TSK-GEL; SUPER-AW series, It was 8,500 as a result of measuring by solvent: NMP solution of LiBr density | concentration of 10 mmol / L, and a number average molecular weight (standard polystyrene conversion). Using 2-chloroethyl methyl ether (57.5 mmol) for (G-1), a protective group introduction reaction was carried out in the same manner as in Synthesis Example 1 to obtain a resin (G-2). The proportion of protected acidic groups was 60%.

Example 7
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the resin (A-2) in the photosensitive resin composition of Example 1 was changed to the resin (G-2). Evaluation was performed in the same manner as above.

Example 8
Resin (B-2) 85 parts by mass, 2,3,4-tris [-2-diazo-1 (2H) -naphthalenone-4-sulfonyloxy] benzophenone (NQD-1) 5 parts by mass, crosslinking agent HMOM-TPHAP 10 parts by mass (made by Honshu Chemical Industry Co., Ltd.) were dissolved in 200 parts by mass of PGMEA, and then filtered through a 0.2 μm PTFE filter to obtain a photosensitive resin composition. Using this, the same evaluation as in Example 1 was performed.

Example 9
Except that the crosslinking agent HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) in the photosensitive resin composition of Example 8 was changed to Nicalac N2702 (manufactured by Sanwa Chemical Co., Ltd.), the same procedure as in Example 8 was performed. A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1.

Example 10
Equivalent mass of photoacid generator 2,3,4-tris [-2-diazo-1 (2H) -naphthalenone-4-sulfonyloxy] benzophenone (NQD-1) in the photosensitive resin composition of Example 8 A photosensitive resin composition was prepared in the same manner as in Example 8 except that the triarylsulfonium salt PAG-1 was changed, and evaluated in the same manner as in Example 1.

Example 11
Except that the crosslinking agent HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) in the photosensitive resin composition of Example 10 was changed to Nicarak N2702 (manufactured by Sanwa Chemical Co., Ltd.), the same procedure as in Example 10 was performed. A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1.

Example 12
The photoacid generator 2,3,4-tris [-2-diazo-1 (2H) -naphthalenone-4-sulfonyloxy] benzophenone (NQD-1) in the photosensitive resin composition of Example 8 was replaced with oxime sulfonate. A photosensitive resin composition was prepared in the same manner as in Example 8 except that the photoacid generator (z70) was changed, and evaluated in the same manner as in Example 1.

Example 13
Except that the crosslinking agent HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) in the photosensitive resin composition of Example 12 was changed to Nicarak N2702 (manufactured by Sanwa Chemical Co., Ltd.), the same procedure as in Example 12 was performed. A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1.

Example 14
85 parts by mass of resin (B-1) synthesized in Synthesis Example 2, photoacid generator 2,3,4-tris [-2-diazo-1 (2H) -naphthalenone-4-sulfonyloxy] benzophenone (NQD-1 ) 15 parts by mass and 10 parts by mass of a crosslinking agent HMOM-TPHAP (Honshu Chemical Industry Co., Ltd.) were dissolved in 200 parts by mass of PGMEA, and then filtered through a 0.2 μm PTFE filter to obtain a photosensitive resin composition. Thereafter, evaluation was performed in the same manner as in Example 1.

Example 15
Except that the crosslinking agent HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) in the photosensitive resin composition of Example 14 was changed to Nicalac N2702 (manufactured by Sanwa Chemical Co., Ltd.), the same procedure as in Example 14 was performed. A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1.

Example 16
The photoacid generator 2,3,4-tris [-2-diazo-1 (2H) -naphthalenone-4-sulfonyloxy] benzophenone (NQD-1) in the photosensitive resin composition of Example 14 was replaced with triaryl. A photosensitive resin composition was prepared in the same manner as in Example 14 except that the sulfonium salt was changed to PAG-1, and evaluated in the same manner as in Example 1.

Example 17
Except that the crosslinking agent HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) in the photosensitive resin composition of Example 16 was changed to Nicarak N2702 (manufactured by Sanwa Chemical Co., Ltd.), the same procedure as in Example 16 was performed. A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1.

Example 18
The photoacid generator 2,3,4-tris [-2-diazo-1 (2H) -naphthalenone-4-sulfonyloxy] benzophenone (NQD-1) in the photosensitive resin composition of Example 14 was replaced with oxime sulfonate. A photosensitive resin composition was prepared in the same manner as in Example 14 except that the photoacid generator (z70) was used, and evaluated in the same manner as in Example 1.

Example 19
Except for changing the crosslinking agent HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) in the photosensitive resin composition of Example 18 to Nicarak N2702 (manufactured by Sanwa Chemical Co., Ltd.), the same procedure as in Example 18 was performed. A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1.

Examples 20-25
A photosensitive resin composition was prepared in the same manner as in Examples 8 to 13 except that the resin (B-2) used in Examples 8 to 13 was changed to the resin (G-2). Evaluation was performed in the same manner.

Examples 26-31
A photosensitive resin composition was prepared in the same manner as in Examples 14 to 19 except that the resin (B-1) used in Examples 14 to 19 was changed to the resin (G-1). Evaluation was performed in the same manner.

Comparative Example 1
The polymer obtained in Example 1 was synthesized according to the method described in JP-A-2000-275842, and oxidized 2- (tetrahydropyran-2-yl) oxy-6-methylphenol and 2,6-dimethylphenol. A photosensitive resin composition was prepared in the same manner as in Example 1 except that the polymer was changed to the comparative polymer 1 which had been subjected to coupling polymerization and deprotected with hydrochloric acid, and evaluated in the same manner as in Example 1.

  The evaluation results of Examples 1 to 31 and Comparative Example 1 are shown in Table 1.

  Compared with the comparative examples, it can be seen that the examples using the film-forming composition of the present invention are superior in resolution.

Claims (6)

A photosensitive resin composition comprising a polymer compound (a) obtained by reacting a monomer represented by the following general formula (1) and a photosensitive agent (b).

(Here, T ₁ represents an oxygen atom and / or a sulfur atom. Ar ₁ and Ar ₂ represent a bivalent to hexavalent organic group having 6 to 30 carbon atoms and may be substituted by a substituent. R ₁ represents a hydrogen atom or a silyl group, and each may be different or the same X ₁ represents a leaving group, and each may be different or the same Y may be an acidic group or Represents a group containing an acidic group protected by an acid-decomposable group, wherein the plurality of Y contained in the polymer compound may be one type or two or more types, a is an integer of 0 to 4; ≧ 1.)   The photosensitive resin composition according to claim 1, wherein the photosensitive agent is a compound that generates an acid by light.   The photosensitive resin composition according to claim 1, further comprising (c) a crosslinking agent.   A polymer compound obtained by reacting the monomer represented by the general formula (1).   Manufacturing of the pattern including the process of apply | coating the photosensitive resin composition in any one of Claims 1-3 on a board | substrate, drying, the process of exposing, the process developed using alkaline aqueous solution and / or an organic solvent. Law.   An electronic device having a pattern obtained by the manufacturing method according to claim 5.