JP2010256834A - Chemically amplified positive photoresist composition and method for manufacturing resist pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chemically amplified positive photoresist composition which provides a resist having high storage stability and high sensitivity to i rays, and a method for manufacturing a resist pattern. <P>SOLUTION: The chemically amplified positive photoresist composition contains a component (A) generating an acid by light and a resin component (B) increasing alkali-solubility by an acid. The component (A) is a sulfonium salt expressed by formula (A-1) wherein: R<SP>1</SP>to R<SP>6</SP>each represent alkyl, -OH, alkoxy, alkylcarbonyl, aryl carbonyl, alkoxycarbonyl, aryloxy carbonyl, arylthio carbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbon, aryloxy, alkyl sulfinyl, aryl sulfinyl, alkylsulfonyl, arylsulfonyl, hydroxy (poly)alkyleneoxy, amino, cyano, nitroglycerine, or halogen; m<SP>1</SP>, m<SP>4</SP>, and m<SP>6</SP>each is 0 to 5; and m<SP>2</SP>, m<SP>3</SP>, and m<SP>5</SP>is 0 to 4. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  In the present invention, light or radiation is irradiated to generate an acid in the exposed area, and the reaction of the generated acid as a catalyst changes the solubility in the developer of the far ultraviolet light or radiation irradiated area and the non-irradiated area. The present invention relates to a chemically amplified positive photoresist composition for forming a pattern on a substrate, and a method for producing a resist pattern using the composition. More specifically, the present invention relates to the manufacture of circuit boards, CSPs (chip size packages) mounted on circuit boards, micro electro mechanical system (MEMS) elements, small machines incorporating MEMS elements (micromachines), and high-density mounting. The present invention relates to a chemically amplified positive photoresist composition suitably used for forming connection terminals such as bumps and metal posts, wiring patterns, etc., and a method for producing a resist pattern in the manufacture of electronic parts such as through electrodes. is there.

  Photofabrication, which is currently the mainstream of precision microfabrication technology, is the application of a photosensitive resin composition to the surface of a workpiece to form a coating film, which is then patterned using photolithography technology. A generic term for technologies for manufacturing various precision parts such as semiconductor packages by performing chemical forming, electrolytic etching, and / or electroforming mainly composed of electroplating as a mask.

  In recent years, with the miniaturization of electronic devices, high-density mounting of semiconductor packages has progressed, and multi-pin thin-film mounting and miniaturization of packages, and improvement in mounting density based on two-dimensional and three-dimensional mounting technologies using flip chip methods. It is illustrated. As connection terminals for such high-density mounting technology, for example, protruding electrodes (mounting terminals) such as bumps protruding on the package, metal posts that connect the rewiring extending from the peripheral terminals on the wafer and the mounting terminals, etc. It is arranged with high accuracy on the substrate.

  There is a positive photosensitive resin composition (see Patent Document 1) having a naphthoquinonediazide group-containing compound as a material used for photofabrication as described above, but it is an exposure light source generally used in a photolithography process. There is a problem that sensitivity to i-line (365 nm) is low.

A chemically amplified positive resist composition (see Patent Document 2) using an oxime sulfonate compound as an acid generator has been proposed as a photosensitive resin composition with the above problems improved. This is because the acid is generated from the photoacid generator by irradiation (exposure), and the diffusion of the acid and the acid catalytic reaction are promoted by the heat treatment after the exposure, thereby improving the solubility of the base resin in the resin composition in the alkali. The base resin that was insoluble in alkali before exposure is solubilized in alkali, and is called a positive photoresist.
However, since the above resist composition has poor storage stability, the management of the storage temperature of the resist composition is complicated and has practical problems.

  Further, a chemically amplified positive resist composition using a triarylsulfonium salt compound as a photoacid generator is also known (Non-patent Documents 1, 2, and Patent Documents 3 and 4), but has good storage stability. However, the sensitivity to i-line is not sufficient.

JP 2002-258479 A JP 2000-66385 A JP 2003-231673 A JP 2002-193925 A

M.J.O'Brien, J.V.Crivello, SPIE Vol. 920, Advances in Resist Technology and Processing, p42 (1988). H.ITO, SPIE Vol.920, Advances in Resist Technology and Processing, p33, (1988).

  The present invention has been made in view of the above problems, and has a chemically amplified positive photoresist composition and a resist that have good storage stability and can provide a resist with high sensitivity to i-line. An object is to provide a method for manufacturing a pattern.

  As a result of repeated studies to achieve the above object, the present inventors have found that the above-mentioned problems can be solved by a sulfonium salt photoacid generator having a specific structure. It came to be completed. That is, the present invention provides the following.

1. A chemically amplified positive photoresist composition comprising:
A component (A) that is a compound that generates an acid upon irradiation with light or radiation, and a component (B) that is a resin whose solubility in alkali is increased by the action of an acid,
The component (A) is represented by the following general formula (A-1):

[In the formula (A-1), R ^{1 to} R ⁶ are each an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, or an acyloxy group. Group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, substituted an amino group, a cyano group, a nitro group or a halogen atom, m ¹ ~m ^6, represents the number of R ¹ to R ⁶ each, m ^1, m ⁴ and m ⁶ is an integer of 0 to 5, m ² , M ³ and m ⁵ are integers from 0 to 4, and X ⁻ represents a monovalent polyatomic anion. A chemically amplified positive photoresist composition comprising a sulfonium salt represented by the following formula:
2. 2. The chemically amplified positive photoresist composition as described in 1 above, wherein R ^{1 to} R ⁶ are independently selected from a methyl group, a methoxy group, and an acetyl group.
3. R ¹ , R ³ , R ⁴ and R ⁶ are each independently a methyl group or a methoxy group, m ¹ , m ³ , m ⁴ and m ⁶ are all 1, and m ² and m ⁵ are both 3. The chemically amplified positive photoresist composition as described in 1 or 2 above, which is a sulfonium salt of 0.
4). 4. The chemically amplified positive photoresist composition as described in any one of 1 to 3 above, wherein m ^{1 to} m ⁶ are all 0.
5). Wherein X ^{_{-, MY a -, (Rf)}} b PF 6-b -, R 7 c BY 4-c -, R 7 c GaY 4-c -, R 8 SO 3 -, (R 8 SO 2) 3 C ^- or _{^{(R 8 SO 2) 2 N}} - anion (here represented by, M is a phosphorus atom, a boron atom, an arsenic atom or an antimony atom, Y is a halogen atom, Rf is fluorine least 80 mol% of hydrogen atoms An alkyl group substituted with an atom, P is a phosphorus atom, F is a fluorine atom, R ⁷ is a phenyl group in which at least one hydrogen atom is substituted with a halogen atom, a trifluoromethyl group, a nitro group or a cyano group, B Is a boron atom, Ga is a gallium atom, R ⁸ is an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, a is an integer of 4 to 6, b 1 represents an integer of 1 to 5, and c represents an integer of 1 to 4. Chemically amplified positive photoresist composition according to any one of stone 4.
6). X ⁻ is SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B _{^{-, (C 6 F 5)}} 4 Ga -, ((CF 3) 2 C 6 H 3) 4 Ga -, trifluoromethanesulfonic acid anion, nonafluorobutanesulfonic acid anion, benzenesulfonic acid anion, p- toluenesulfonic acid 6. The method according to any one of 1 to 5 above, which comprises at least one selected from the group consisting of an anion, (CF ₃ SO ₂ ) ₃ C ⁻ , and (CF ₃ SO ₂ ) ₂ N ⁻ . Chemically amplified positive photoresist composition.
7). The component (B) contains at least one resin selected from the group consisting of a novolak resin (B1), a polyhydroxystyrene resin (B2), and an acrylic resin (B3). 7. The chemically amplified positive photoresist composition as described in any one of 6 above.
8). 8. The chemically amplified positive photoresist composition as described in any one of 1 to 7 above, further comprising an alkali-soluble resin (C) and an acid diffusion controller (D).
9. A laminating step of laminating a 10 to 150 μm-thick photoresist layer made of the chemically amplified positive photoresist composition according to any one of 1 to 8 above on a support to obtain a photoresist laminate;
An exposure step of selectively irradiating light or radiation to the photoresist laminate;
A development step of developing the photoresist laminate after the exposure step to obtain a resist pattern;
A method for producing a resist pattern, comprising:

  According to the chemical amplification type positive photoresist composition of the present invention, it is possible to obtain a resist pattern having good storage stability and high sensitivity to light or radiation, particularly i-line.

  Hereinafter, embodiments of the present invention will be described in detail. In the present specification, the term “alkyl group” includes a cycloalkyl group in addition to a linear alkyl group and a branched alkyl group.

The chemically amplified positive photoresist composition of the present invention is described below.
(A) It contains a compound that generates an acid upon irradiation with light or radiation, and (B) a resin whose solubility in alkali is increased by the action of the acid.

<(A) Compound that generates acid upon irradiation with light or radiation>
The above-mentioned “(A) compound capable of generating an acid upon irradiation with light or radiation” (hereinafter referred to as “component (A)”), which is used in the chemically amplified positive photoresist composition of the present invention. Is a photoacid generator and generates acid directly or indirectly by light or radiation.

  Specifically, the component (A) has the following general formula (A-1):

[In the formula (A-1), R ^{1 to} R ⁶ are each an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, or an acyloxy group. Group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, substituted an amino group, a cyano group, a nitro group or a halogen atom, m ¹ ~m ^6, represents the number of R ¹ to R ⁶ each, m ^1, m ⁴ and m ⁶ is an integer of 0 to 5, m ² , M ³ and m ⁵ are integers from 0 to 4, and X ⁻ represents a monovalent polyatomic anion. ] The sulfonium salt shown by this.

In formula (A-1), among R ^{1 to} R ⁶ , the alkyl group is a linear alkyl group having 1 to 18 carbon atoms (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n- Octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.), a branched alkyl group having 1 to 18 carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, Neopentyl, tert-pentyl, isohexyl and isooctadecyl), and cycloalkyl groups having 3 to 18 carbon atoms (such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and 4-decylcyclohexyl). Of these, a methyl group is particularly preferred.

Among R ^{1 to} R ⁶ , the alkoxy group is a linear or branched alkoxy group having 1 to 18 carbon atoms (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyl). Oxy, decyloxy, dodecyloxy, octadecyloxy, etc.). Of these, a methoxy group is particularly preferred.

Among R ^{1 to} R ⁶ , the alkylcarbonyl group is a linear or branched alkylcarbonyl group having 2 to 18 carbon atoms (acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3 -Methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl and the like). Of these, an acetyl group is particularly preferred.

Among R ^{1 to} R ⁶ , examples of the arylcarbonyl group include arylcarbonyl groups having 7 to 11 carbon atoms (such as benzoyl and naphthoyl).

Among R ^{1 to} R ⁶ , the alkoxycarbonyl group is a linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms (methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, octadecyloxycarbonyl, etc.).

Among R ^{1 to} R ⁶ , examples of the aryloxycarbonyl group include aryloxycarbonyl groups having 7 to 11 carbon atoms (such as phenoxycarbonyl and naphthoxycarbonyl).

Among R ^{1 to} R ⁶ , examples of the arylthiocarbonyl group include arylthiocarbonyl groups having 7 to 11 carbon atoms (such as phenylthiocarbonyl and naphthoxythiocarbonyl).

Among R ^{1 to} R ⁶ , the acyloxy group is a linear or branched acyloxy group having 2 to 19 carbon atoms (acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, octadecylcarbonyloxy and the like).

Among R ^{1 to} R ⁶ , the arylthio group is an arylthio group having 6 to 20 carbon atoms (phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenyl. Thio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4 -Hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4- [4- (phenylthio) benzoyl] phenylthio, 4- [4- (phenylthio) phenoxy] phenylthio, 4 -[4- (phenylthio) phenyl] Enylthio, 4- (phenylthio) phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthio Phenylthio, 4- (4-methylthiobenzoyl) phenylthio, 4- (2-methylthiobenzoyl) phenylthio, 4- (p-methylbenzoyl) phenylthio, 4- (p-ethylbenzoyl) phenylthio 4- (p-isopropylbenzoyl) Phenylthio and 4- (p-tert-butylbenzoyl) phenylthio) and the like.

Among R ^{1 to} R ⁶ , the alkylthio group is a linear or branched alkylthio group having 1 to 18 carbon atoms (methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, Pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, isooctadecylthio and the like.

Among R ^{1 to} R ⁶ , examples of the aryl group include aryl groups having 6 to 10 carbon atoms (such as phenyl, tolyl, dimethylphenyl, and naphthyl).

Among R ^{1 to} R ⁶ , the heterocyclic hydrocarbon group includes a heterocyclic hydrocarbon group having 4 to 20 carbon atoms (thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, Benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthenyl, phenoxazinyl, phenoxathinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, etc. Is mentioned.

Among R ^{1 to} R ⁶ , examples of the aryloxy group include aryloxy groups having 6 to 10 carbon atoms (such as phenoxy and naphthyloxy).

Among R ^{1 to} R ⁶ , the alkylsulfinyl group is a linear or branched alkylsulfinyl group having 1 to 18 carbon atoms (methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec- Butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, isooctadecylsulfinyl, etc.).

Among R ^{1 to} R ⁶ , examples of the arylsulfinyl group include arylsulfinyl groups having 6 to 10 carbon atoms (such as phenylsulfinyl, tolylsulfinyl and naphthylsulfinyl).

Among R ^{1 to} R ⁶ , the alkylsulfonyl group is a linear or branched alkylsulfonyl group having 1 to 18 carbon atoms (methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec- Butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl, octadecylsulfonyl, etc.).

Among R ^{1 to} R ⁶ , examples of the arylsulfonyl group include arylsulfonyl groups having 6 to 10 carbon atoms (phenylsulfonyl, tolylsulfonyl (tosyl group), naphthylsulfonyl, etc.) and the like.

Among R ^{1 to} R ⁶ , examples of the hydroxy (poly) alkyleneoxy group include a hydroxy (poly) alkyleneoxy group represented by the following formula (1).

[In Formula (1), AO represents an ethyleneoxy group and / or a propyleneoxy group, and q represents an integer of 1 to 5. ]

Among R ^{1 to} R ^6, the optionally substituted amino group includes an amino group (—NH ₂ ) and a substituted amino group having 1 to 15 carbon atoms (methylamino, dimethylamino, ethylamino, methylethylamino, diethylamino). , N-propylamino, methyl-n-propylamino, ethyl-n-propylamino, n-propylamino, isopropylamino, isopropylmethylamino, isopropylethylamino, diisopropylamino, phenylamino, diphenylamino, methylphenylamino, ethyl Phenylamino, n-propylphenylamino, isopropylphenylamino, etc.).

Among R ^{1 to} R ⁶ , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ^{1 to} R ⁶ are independent of each other, and therefore may be the same or different from each other.

m ^{1 to} m ⁶ each represent the number of R ^{1 to} R ⁶ , and m ¹ , m ⁴ and m ⁶ are integers of 0 to 5, preferably 0 to 3, more preferably 0 to 2, particularly preferably. Is 0 or 1. M ² , m ³ and m ⁵ are integers of 0 to 4, preferably 0 to 3, more preferably 0 to 2, particularly preferably 0 or 1. When m ^{1 to} m ⁶ are in these preferred ranges, the sensitivity of the sulfonium salt of the component (A) in the present invention is further improved.

  Among the components (A) of the present invention, those containing a cation having the following structure are particularly preferred from the viewpoint of sensitivity.

In Formula (A-1), X ⁻ is generated by irradiating the sulfonium salt of the component (A) in the present invention with light (visible light, ultraviolet light, far ultraviolet light) or radiation (electron beam, X-ray, etc.). An anion corresponding to acid (HX). X ⁻ is not limited except that it is a monovalent polyatomic anion, but MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ⁷ _c BY _4-c ⁻ , R ⁷ _c GaY _{4 ^{-c -, R 8 SO 3 -}} , (R 8 SO 2) 3 C - or _{^{(R 8 SO 2) 2 N}} - anion represented by are preferred.

M represents a phosphorus atom, a boron atom, or an antimony atom.
Y represents a halogen atom (a fluorine atom is preferred).

Rf represents an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms) in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms. Examples of the alkyl group to be Rf by fluorine substitution include linear alkyl groups (such as methyl, ethyl, propyl, butyl, pentyl and octyl), branched chain alkyl groups (such as isopropyl, isobutyl, sec-butyl and tert-butyl) and And cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and the like. The ratio of hydrogen atoms of these alkyl groups substituted by fluorine atoms in Rf is preferably 80 mol% or more, more preferably 90%, based on the number of moles of hydrogen atoms that the original alkyl group had. % Or more, particularly preferably 100%. When the substitution ratio by fluorine atoms is in these preferred ranges, the sensitivity of the sulfonium salt of component (A) in the present invention is further improved. Particularly preferred Rf is CF ₃ −, CF ₃ CF ₂ −, (CF ₃ ) ₂ CF—, CF ₃ CF ₂ CF ₂ −, CF ₃ CF ₂ CF ₂ CF ₂ −, (CF ₃ ) ₂ CFCF ₂ −. , CF ₃ CF ₂ (CF ₃ ) CF— and (CF ₃ ) ₃ C—. The b Rf's are independent of each other, and therefore may be the same as or different from each other.

  P represents a phosphorus atom, and F represents a fluorine atom.

R ⁷ represents a phenyl group in which a part of hydrogen atoms is substituted with at least one element or electron withdrawing group. Examples of such one element include a halogen atom, and include a fluorine atom, a chlorine atom and a bromine atom. Examples of the electron withdrawing group include a trifluoromethyl group, a nitro group, and a cyano group. Of these, a phenyl group in which one hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferable. The c R ^{7 s} are independent of each other, and therefore may be the same as or different from each other.

  B represents a boron atom, and Ga represents a gallium atom.

R ⁸ represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the alkyl group and the perfluoroalkyl group are linear or branched. Alternatively, the aryl group may be unsubstituted or may have a substituent.

S represents a sulfur atom, O represents an oxygen atom, C represents a carbon atom, and N represents a nitrogen atom.
a represents an integer of 4 to 6.
b is preferably an integer of 1 to 5, more preferably 2 to 4, and particularly preferably 2 or 3.
c is preferably an integer of 1 to 4, more preferably 4.

Examples of the anion represented by MY _a ⁻ include SbF ₆ ⁻ , PF ₆ ^{− and} BF ₄ ⁻ .

Examples of the anion represented by (Rf) _b PF _6-b ⁻ include (CF ₃ CF ₂ ) ₂ PF ₄ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , and ((CF ₃ ) ₂ CF) ₂ PF _{4. ^{-, ((CF 3) 2}} CF) 3 PF 3 -, (CF 3 CF 2 CF 2) 2 PF 4 -, (CF 3 CF 2 CF 2) 3 PF 3 -, ((CF 3) 2 CFCF 2) ^{_{2 PF 4 -, ((CF}} 3) 2 CFCF 2) 3 PF 3 -, (CF 3 CF 2 CF 2 CF 2) 2 PF 4 - or _{(CF 3 CF 2 CF 2 CF} 2) 3 PF 3 - etc. Can be mentioned. Of these, (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CF) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CF) ₂ PF ₄ ⁻ , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ⁻ or ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ⁻ is preferred.

The anion represented _{by, (C 6 F 5) 4} B - - R 7 c BY 4-c, ((CF 3) 2 C 6 H 3) 4 B -, (CF 3 C 6 H 4) 4 ^{_{B -, (C 6 F 5}} ) 2 BF 2 -, C 6 F 5 BF 3 - or _{(C 6 H 3 F 2)} 4 B - , and the like. Of these, (C ₆ F ₅ ) ₄ B ⁻ or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ⁻ is preferable.

The anion represented _{by, (C 6 F 5) 4} Ga - - R 7 c GaY 4-c, ((CF 3) 2 C 6 H 3) 4 Ga -, (CF 3 C 6 H 4) 4 ^{_{Ga -, (C 6 F 5}} ) 2 GaF 2 -, C 6 F 5 GaF 3 - or _{(C 6 H 3 F 2)} 4 Ga - an anion, and the like represented. Of _{these, (C 6 F 5) 4} Ga - or _{((CF 3) 2 C 6} H 3) 4 Ga - anion represented by are preferred.

Examples of the anion represented by R ⁸ SO ₃ ^— include trifluoromethane sulfonate anion, pentafluoroethane sulfonate anion, heptafluoropropane sulfonate anion, nonafluorobutane sulfonate anion, pentafluorophenyl sulfonate anion, p-toluene. Examples include sulfonate anion, benzenesulfonate anion, camphorsulfonate anion, methanesulfonate anion, ethanesulfonate anion, propanesulfonate anion and butanesulfonate anion. Of these, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, benzenesulfonate anion or p-toluenesulfonate anion is preferred.

Examples of the anion represented by (R ⁸ SO ₂ ) ₃ C ⁻ include (CF ₃ SO ₂ ) ₃ C ⁻ , (C ₂ F ₅ SO ₂ ) ₃ C ⁻ , and (C ₃ F ₇ SO ₂ ) ₃ C ^−. or _{(C 4 F 9 SO 2)} 3 C - , and the like.

Examples of the anion represented by (R ⁸ SO ₂ ) ₂ N ⁻ include (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , and (C ₃ F ₇ SO ₂ ) ₂ N ^−. or _{(C 4 F 9 SO 2)} 2 N - , and the like.

The monovalent polyatomic ^{_{anion, MY a -, (Rf)}} b PF 6-b -, R 7 c BY 4-c -, R 7 c GaY 4-c -, R 8 SO 3 -, (R 8 In addition to anions represented by SO ₂ ) ₃ C ⁻ or (R ⁸ SO ₂ ) ₂ N ⁻ , perhalogenate ions (ClO ₄ ⁻ , BrO ₄ ⁻ etc.), halogenated sulfonate ions (FSO ₃ ⁻ , ClSO) ₃ ^- and the like), sulfate ion ^{_{(CH 3 SO 4 -, CF}} 3 SO 4 -, HSO 4 - , etc.), carbonate ions (HCO ₃ ^-, CH ₃ CO ₃ ^-, etc.), aluminate ions (AlCl ₄ ^-, AlF ₄ ^-, etc.), hexafluoro bismuthate ions (BiF ₆ ^-), carboxylate ion _{^{(CH 3 COO -, CF 3}} COO -, C 6 H 5 COO -, CH 3 C 6 H 4 COO -, C 6 F 5 _{^{COO -, CF 3 C 6 H}} 4 COO - , etc.), an aryl boronic acid ions _{(B (C 6 H 5)} 4 -, CH 3 CH 2 CH 2 _{H 2 B (C 6 H 5} ) 3 - , etc.), thiocyanate ion (SCN ^-) and nitrate ion (NO ₃ ^-) and the like can be used.

Of the counter anions of the sulfonium salt of component (A), SbF ₆ ⁻ , PF ₆ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ⁻ , trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, benzenesulfonate anion Alternatively, p-toluenesulfonate anion, (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , is preferable in terms of improving the resolution and pattern shape of the resist. (CF ₃ CF ₂ ) ₃ PF ₃ ^- , (C ₆ F ₅ ) ₄ B ^- or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ^- are particularly preferred because they are more compatible with the resist composition.

  As the component (A), any of the sulfonium salts represented by the general formula (A-1) may be used alone, or two or more kinds may be used in combination. Moreover, you may use together with another conventionally well-known photo-acid generator.

  Other acid generators include, for example, onium salt compounds, sulfone compounds, sulfonate ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, triazine compounds, nitrobenzyl compounds. In addition, organic halides, disulfone and the like can be mentioned.

Examples of the onium salt compounds include iodonium salts, sulfonium salts other than the sulfonium salts represented by the general formula (A-1) of the present invention, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts, and the like. .
Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof.
Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
Moreover, as said imide sulfonate compound, the compound represented by following General formula (2) can be mentioned, for example.

[In the general formula (2), R ⁹ represents a monovalent organic group, and R ¹⁰ represents a divalent organic group. ]

  Moreover, as said disulfonyl diazomethane, the compound represented by following General formula (3) can be mentioned, for example.

[In the general formula (3), each R ¹¹ is independently a linear or branched monovalent aliphatic hydrocarbon group, cycloalkyl group, linear or branched monovalent monovalent group. A halogen-substituted aliphatic hydrocarbon group, a halogen-substituted cycloalkyl group, an aryl group, a halogenated aryl group and the like are shown. ]

  Moreover, as said disulfonylmethane compound, the compound represented by following General formula (4) can be mentioned, for example.

[In the general formula (4), each R ¹² is independently a linear or branched monovalent aliphatic hydrocarbon group, cycloalkyl group, aryl group, aralkyl group or hetero atom 1 V and W are each independently an aryl group, a hydrogen atom, a linear or branched monovalent aliphatic hydrocarbon group, or another monovalent organic group having a hetero atom And at least one of V and W is an aryl group, or V and W are connected to each other to form a monocyclic or polycyclic ring having at least one unsaturated bond, or W are interconnected to form the following formula (i)

[In the formula (i), V ′ and W ′ are independent from each other, and a plurality of V ′ and W ′ may be the same or different, and may be a hydrogen atom, a halogen atom, a straight chain Or a branched alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, or V ′ and W ′ bonded to the same or different carbon atoms are connected to each other to form a carbocyclic structure. X is an integer of 2-10. ) Is formed. ]

  Examples of the oxime sulfonate compound include compounds represented by the following general formula (5-1) or general formula (5-2).

[In General Formula (5-1) and General Formula (5-2), R ¹³ and R ¹⁴ each independently represent a monovalent organic group, and two R ¹³ in General Formula (5-2) And the two R ¹⁴ groups may be the same or different. ]
Specific examples of the oxime sulfonate compound include α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2. , 6-dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (methylsulfonyloxyimino) -1-phenyl Acetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile, [2- ( Propylsulfonyloxyimino) -2,3-dihydroxythiophene-3-ylidene] (o-tolyl) acetonitrile, and those represented by the following chemical formula.

  Moreover, as said hydrazine sulfonate compound, the compound represented by General formula (6-1) or General formula (6-2) can be mentioned, for example.

[In General Formula (6-1) and General Formula (6-2), R ¹⁵ represents a monovalent organic group, and two R ¹⁵ in General Formula (6-2) are the same or different from each other. May be. ]

  As other conventionally known photoacid generators, one or more of the group of onium compounds, sulfonimide compounds, diazomethane compounds and oxime sulfonate compounds are preferred.

  When such a conventionally known photoacid generator is used in combination, the use ratio may be arbitrary, but usually other photoacids are used with respect to 100 parts by mass of the sulfonium salt represented by the general formula (A-1). The generating agent is 10 to 900 parts by mass, preferably 25 to 400 parts by mass.

  The content of the component (A) is preferably 0.05 to 5% by mass in the solid content of the chemically amplified positive photoresist composition.

<(B) Resin whose solubility in alkali is increased by the action of acid>
The “(B) resin whose solubility in alkali is increased by the action of an acid” used in the chemically amplified positive photoresist composition for thick film of the present invention (referred to as “component (B)” in this specification). ) Is at least one resin selected from the group consisting of novolak resin (B1), polyhydroxystyrene resin (B2), and acrylic resin (B3), or a mixed resin or copolymer thereof.

[Novolac resin (B1)]
As the novolac resin (B1), a resin represented by the following general formula (b1) can be used.

In the general formula (b1), R ^1b represents an acid dissociable, dissolution inhibiting group, R ^2b and R ^3b each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is in parentheses. Represents the number of repeating units in the structure.

Furthermore, as the acid dissociable, dissolution inhibiting group represented by R ^1b , a linear, branched or cyclic group having 1 to 6 carbon atoms represented by the following general formula (b2) or (b3) Are preferably an alkyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

In the general formulas (b2) and (b3), R ^4b and R ^5b each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ^6b represents Represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and R ^7b represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. , O is 0 or 1.

  Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, and isopentyl. Group, neopentyl group, and the like, and examples of the cyclic alkyl group include cyclopentyl group and cyclohexyl group.

  Here, specific examples of the acid dissociable, dissolution inhibiting group represented by the general formula (b2) include a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group, an isopropoxyethyl group, and an n-butoxyethyl group. , Isobutoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group, etc. Specific examples of the acid dissociable, dissolution inhibiting group represented by the general formula (b3) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group. Examples of the trialkylsilyl group include those having 1 to 6 carbon atoms in each alkyl group such as trimethylsilyl group and tri-tert-butyldimethylsilyl group.

[Polyhydroxystyrene resin (B2)]
As the polyhydroxystyrene resin (B2), a resin represented by the following general formula (b4) can be used.

In the general formula (b4), R ^8b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ^9b represents an acid dissociable, dissolution inhibiting group, and n represents the number of repeating units in the structure in parentheses. To express.

  Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, and isopentyl. Group, neopentyl group, and the like, and examples of the cyclic alkyl group include cyclopentyl group and cyclohexyl group.

Examples of the acid dissociable, dissolution inhibiting group represented by R ^9b, it is possible to use the same acid dissociable, dissolution inhibiting groups as those exemplified in the above general formula (b2) and (b3).

  Further, the polyhydroxystyrene resin (B2) can contain other polymerizable compounds as structural units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anionic polymerizable compounds. For example, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl Methacrylic acid derivatives having a carboxyl group and an ester bond such as phthalic acid and 2-methacryloyloxyethylhexahydrophthalic acid; (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate Alkyl esters; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) ) (Meth) acrylic acid aryl esters such as acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methyl Vinyl group-containing aromatic compounds such as hydroxystyrene and α-ethylhydroxystyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugated diolefins such as butadiene and isoprene; Nitrile groups such as acrylonitrile and methacrylonitrile Polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

[Acrylic resin (B3)]
As the acrylic resin (B3), resins represented by the following general formulas (b5) to (b10) can be used.

In the general formulas (b5) to (b7), R ^{10b to} R ^17b are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a carbon number. Represents a linear or branched fluorinated alkyl group of 1 to 6, X ^b forms a hydrocarbon ring of 5 to 20 carbon atoms with the carbon atom to which it is bonded, Y ^b is Represents an aliphatic cyclic group or an alkyl group which may have a substituent, n represents the number of repeating units of the structure in parentheses, p is an integer of 0 to 4, and q is 0 or 1 .

The linear or branched alkyl group having 1 to 6 carbon atoms in R ^{10b to} R ^17b is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert -A butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. are mentioned, As a cyclic alkyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. Further, the fluorinated alkyl group is one in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.

R ^11b is preferably a linear or branched alkyl group having 2 to 4 carbon atoms from the viewpoint of high contrast, good resolution, depth of focus, etc., and the above R ^13b , R ^14b , R ^16b and R ^17b are preferably a hydrogen atom or a methyl group.

X ^b above forms an aliphatic cyclic group having 5 to 20 carbon atoms together with the carbon atom to which it is bonded. Specific examples of such aliphatic cyclic groups include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Groups. In particular, a group obtained by removing one or more hydrogen atoms from cyclohexane or adamantane (which may further have a substituent) is preferable.

Furthermore, when the aliphatic cyclic group of ^Xb has a substituent on the ring skeleton, examples of the substituent include polar groups such as a hydroxyl group, a carboxy group, a cyano group, and an oxygen atom (═O). And a linear or branched lower alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (═O) is particularly preferable.

Y ^b is an optionally substituted aliphatic cyclic group or an alkyl group, and one or more hydrogen atoms from a polycycloalkane such as a monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. Examples include groups excluding atoms. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Groups and the like. In particular, a group obtained by removing one or more hydrogen atoms from adamantane (which may further have a substituent) is preferable.

Further, when the aliphatic cyclic group of Y ^b has a substituent on the ring skeleton, examples of the substituent include polar groups such as a hydroxyl group, a carboxy group, a cyano group, and an oxygen atom (═O). And a linear or branched lower alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (═O) is particularly preferable.

In addition, when Y ^b is an alkyl group, it is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 6 to 15 carbon atoms. Such an alkyl group is particularly preferably an alkoxyalkyl group, and examples of such an alkoxyalkyl group include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxy group. Ethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1 -Ethoxy-1-methylethyl group etc. are mentioned.

In general formula (b8), general formula (b9), and general formula (b10), R ^18b , R ^20b, and R ^21b each independently represent a hydrogen atom or a methyl group, and in general formula (b8) R ^19b is independently of each other a hydrogen atom, a hydroxyl group, a cyano group or a —COOR ^23b group (where R ^23b is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or a carbon atom) In the general formula (b10), each R ^22b is independently of each other a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof. Or 1-4 linear or branched alkyl groups, and at least one of R ^22b is the alicyclic hydrocarbon group or a derivative thereof, or any two R ^22b are mutually Combined, each of which is connected A divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof is formed together with a general carbon atom, and the remaining R ^22b is a linear or branched alkyl group having 1 to 4 carbon atoms. Alternatively, it represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof.

  Preferable specific examples of the acrylic resin represented by the general formula (b5) include those represented by the following general formulas (b5-1) to (b5-3).

In the above general formulas (b5-1) to (b5-3), R ^18b represents a hydrogen atom or a methyl group, and n represents the number of repeating units in the structure in parentheses.

  Preferable specific examples of the acrylic resin represented by the general formula (b6) include those represented by the following general formulas (b6-1) to (b6-28).

    Preferable specific examples of the acrylic resin represented by the general formula (b7) include those represented by the following general formulas (b7-1) to (b7-22).

  As a preferable repeating unit of the acrylic resin represented by the general formula (b8), for example, (meth) acrylic acid 3-hydroxyadamantan-1-yl, (meth) acrylic acid 3,5-dihydroxyadamantan-1-yl , (Meth) acrylic acid 3-cyanoadamantan-1-yl, (meth) acrylic acid 3-carboxyladamantan-1-yl, (meth) acrylic acid 3,5-dicarboxyladamantan-1-yl, (meth) acrylic Examples include units in which a polymerizable unsaturated bond is cleaved, such as acid 3-carboxyl-5-hydroxyadamantan-1-yl and (meth) acrylic acid 3-methoxycarbonyl-5-hydroxyadamantan-1-yl.

  As a preferable repeating unit of the acrylic resin represented by the general formula (b10), for example, 1-methyl-1-cyclopentyl (meth) acrylate, 1-ethyl-1-cyclopentyl (meth) acrylate, (meth) 1-methyl-1-cyclohexyl acrylate, 1-ethyl-1-cyclohexyl (meth) acrylate, 2-methyladamantyl-2-yl (meth) acrylate, 2-ethyladamantyl-2-yl (meth) acrylate , (Meth) acrylic acid 2-n-propyladamantyl-2-yl, (meth) acrylic acid 2-i-propyladamantyl-2-yl, (meth) acrylic acid 1- (adamantan-1-yl) -1- Examples include units in which a polymerizable unsaturated bond such as methylethyl is cleaved.

  Furthermore, the (B3) acrylic resin comprises a copolymer containing structural units derived from a polymerizable compound having an ether bond with respect to the structural units represented by the general formulas (b5) to (b10). A resin is preferred.

  Such a structural unit is a structural unit derived from a polymerizable compound having an ether bond. Examples of polymerizable compounds having an ether bond include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol ( Exemplified radical polymerizable compounds such as (meth) acrylic acid derivatives having ether bonds and ester bonds such as (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate Preferably, it is 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylateAny of these compounds may be used alone or in combination of two or more.

  Furthermore, (B3) acrylic resin can contain other polymerizable compounds as constituent units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anionic polymerizable compounds. For example, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl Methacrylic acid derivatives having a carboxyl group and an ester bond such as phthalic acid and 2-methacryloyloxyethylhexahydrophthalic acid; (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate Alkyl esters; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) ) (Meth) acrylic acid aryl esters such as acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methyl Vinyl group-containing aromatic compounds such as hydroxystyrene and α-ethylhydroxystyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugated diolefins such as butadiene and isoprene; Nitrile groups such as acrylonitrile and methacrylonitrile Polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

  Among the components (B), it is preferable to use an acrylic resin (B3).

  Among the acrylic resins (B3), structural units represented by the general formulas (b5) to (b10), a structural unit derived from a polymerizable compound having an ether bond, a (meth) acrylic acid unit, It is preferable that it is a copolymer which has a structural unit which consists of (meth) acrylic acid alkylesters.

  The proportion of the structural units represented by the general formulas (b5) to (b10) in the copolymer is preferably 20 to 70% by mass.

  Moreover, the polystyrene conversion mass average molecular weight of a component (B) becomes like this. Preferably it is 10,000-600,000, More preferably, it is 50,000-600,000, More preferably, it is 230,000-550,000 is there. By setting it as such a mass average molecular weight, the resin physical property of a resist becomes excellent.

  Furthermore, the component (B) is preferably a resin having a dispersity of 1.05 or more. Here, the “dispersion degree” is a value obtained by dividing the mass average molecular weight by the number average molecular weight. By setting such a degree of dispersion, resist plating resistance and resin physical properties are excellent.

  The content of the component (B) is preferably 5 to 60% by mass in the solid content of the chemically amplified positive photoresist composition.

<Alkali-soluble resin (C)>
In order to improve the resin physical properties of the resist, the chemically amplified positive photoresist composition of the present invention preferably further contains an alkali-soluble resin (referred to herein as “component (C)”). . Component (C) is preferably at least one selected from the group consisting of novolak resin (C1), polyhydroxystyrene resin (C2), acrylic resin (C3), and polyvinyl resin (C4).

[Novolac resin (C1)]
As the novolak resin (C1), those having a mass average molecular weight of 1,000 to 50,000 are preferable.

  The novolak resin (C1) can be obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and an aldehyde in the presence of an acid catalyst. Examples of phenols used at this time include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p. -Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3, 4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglicinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol, etc. It is.

  Examples of aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. The catalyst for the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used as the acid catalyst.

  It is possible to further improve the flexibility of the resin by using o-cresol, substituting the hydrogen atom of the hydroxyl group in the resin with another substituent, or using bulky aldehydes. is there.

[Polyhydroxystyrene resin (C2)]
The polyhydroxystyrene resin (C2) preferably has a mass average molecular weight of 1,000 to 50,000.

  Examples of the hydroxystyrene compound constituting the polyhydroxystyrene resin (C2) include p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene, and the like. Further, the polyhydroxystyrene resin (C2) is preferably a copolymer with a styrene resin. Examples of the styrene compound constituting such a styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, Examples include α-methylstyrene.

[Acrylic resin (C3)]
As the acrylic resin (C3), those having a mass average molecular weight of 50,000 to 800,000 are preferable.

  Such an acrylic resin (C3) is preferably one comprising a monomer unit derived from a polymerizable compound having an ether bond and a monomer unit derived from a polymerizable compound having a carboxyl group.

  Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxypolyethylene glycol ( Examples include (meth) acrylic acid derivatives having an ether bond and an ester bond such as (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and preferably 2-methoxyethyl acrylate. And methoxytriethylene glycol acrylate. Any one of these compounds may be used alone, or two or more thereof may be used in combination.

  Examples of the polymerizable compound having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, 2-methacryloyloxyethyl succinic acid, and 2-methacryloyloxy. Examples thereof include compounds having a carboxyl group and an ester bond such as ethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid, and acrylic acid and methacrylic acid are preferable. Any one of these compounds may be used alone, or two or more thereof may be used in combination.

[Polyvinyl resin (C4)]
The polyvinyl resin (C4) preferably has a mass average molecular weight of 10,000 to 200,000, more preferably 50,000 to 100,000.

  The polyvinyl resin (C4) is poly (vinyl lower alkyl ether), and can be obtained by polymerizing any one of vinyl lower alkyl ethers represented by the following general formula (c1) or a mixture of two or more ( Co) polymer.

In the general formula (c1), R ^1c represents a linear or branched alkyl group having 1 to 6 carbon atoms.

  The polyvinyl resin (C4) is a polymer obtained from a vinyl compound. Specifically, polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, Examples thereof include polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol, and copolymers thereof. Of these, polyvinyl methyl ether is preferred in view of the low glass transition point.

  The content of the component (C) is preferably 5 to 95 parts by mass, more preferably 10 to 90 parts by mass with respect to 100 parts by mass of the component (B). When the amount is 5 parts by mass or more, the resin physical properties of the resist can be improved, and when the amount is 95 parts by mass or less, there is a tendency that film loss during development can be prevented.

<Acid diffusion control agent (D)>
The chemical amplification type positive photoresist composition for thick film of the present invention further comprises an acid diffusion control agent (D) (in this specification, “component (D ) ")). As the component (D), a nitrogen-containing compound (D1) is preferable, and an organic carboxylic acid (D2), an oxo acid of phosphorus, or a derivative thereof can be further contained as necessary.

[Nitrogen-containing compound (D1)]
Examples of the nitrogen-containing compound (D1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tribenzylamine, diethanolamine, triethanolamine, n-hexylamine, n-heptylamine, n -Octylamine, n-nonylamine, ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4, 4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propi Amide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazole, benz Imidazole, 4-methylimidazole, 8-oxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri (2-pyridyl) -S-triazine, morpholine, 4-methylmorpholine, piperazine, 1,4- Examples thereof include dimethylpiperazine and 1,4-diazabicyclo [2.2.2] octane. Of these, alkanolamines such as triethanolamine are particularly preferred. Any of these may be used alone or in combination of two or more.

  The nitrogen-containing compound (D1) is usually used in a range of 0 to 5 parts by mass, particularly in a range of 0 to 3 parts by mass, with respect to 100 parts by mass of the total mass of the component (B) and the component (C). It is preferable to be used.

[Organic carboxylic acid (D2) or phosphorus oxo acid or derivative thereof]
Among organic carboxylic acids (D2) or phosphorous oxo acids or derivatives thereof, as the organic carboxylic acids, specifically, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable. In particular, salicylic acid is preferred.

  Examples of phosphorus oxo acids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and other phosphoric acid or derivatives such as esters thereof, phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid Phosphonic acids such as acid-di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and derivatives thereof, phosphinic acids such as phosphinic acid, phenylphosphinic acid and esters thereof Among them, phosphonic acid is particularly preferable. These may be used alone or in combination of two or more.

  Such (D2) organic carboxylic acid, or phosphorus oxo acid or derivative thereof is usually used in the range of 0 to 5 parts by mass with respect to 100 parts by mass as the total mass of component (B) and component (C). In particular, it is preferably used in the range of 0 to 3 parts by mass.

  In order to form a salt and stabilize it, the organic carboxylic acid (D2) or phosphorus oxo acid or its derivative is preferably used in an amount equivalent to the nitrogen-containing compound (D1).

  The chemically amplified positive photoresist composition of the present invention may further contain an adhesion assistant in order to improve the adhesion to the substrate. As the adhesion aid used, a functional silane coupling agent is preferable. Specific functional silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, and epoxy groups. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. The content of the adhesion assistant is preferably 20 parts by mass or less with respect to 100 parts by mass of the total mass of the component (B) and the component (C).

  The chemically amplified positive photoresist composition of the present invention may further contain a surfactant in order to improve coating properties, antifoaming properties, leveling properties and the like. Examples of surfactants include BM-1000, BM-1100 (both trade names; manufactured by BM Chemie), MegaFuck F142D, MegaFuck F172, MegaFuck F173, MegaFuck F183 (both trade names; Dainippon) Ink Chemical Industry Co., Ltd.), Fluorard FC-135, Fluorard FC-170C, Fluorard FC-430, Fluorard FC-431 (all trade names; manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S -131, Surflon S-141, Surflon S-145 (all trade names; manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all trade names; Toray Silicone) Commercially available fluorosurfactants such as Not determined.

  The chemically amplified positive photoresist composition of the present invention may further contain an acid, an acid anhydride, or a high boiling point solvent in order to finely adjust the solubility in an alkali developer. Examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3 -Hydroxy monocarboxylic acids such as hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid Oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid , Butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid Polyvalent carboxylic acids such as butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride, hexa hexahydrate Hydrophthalic acid, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride And acid anhydrides such as acid, anhydrous benzophenone tetracarboxylic acid, ethylene glycol bistrimellitic anhydride, and glycerin tris anhydrous trimellitate. Examples of high-boiling solvents include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl Ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, Examples thereof include propylene carbonate and phenyl cellosolve acetate. The amount of the compound used for finely adjusting the solubility in the alkali developer as described above can be adjusted according to the application and application method, and is particularly limited as long as the composition can be mixed uniformly. Although not a thing, it is 60 mass% or less with respect to the total mass of the composition obtained, Preferably it is 40 mass% or less.

  In addition, the chemically amplified positive photoresist composition of the present invention basically does not require a sensitizer, but can contain a sensitizer as necessary to supplement sensitivity. As such a sensitizer, conventionally known ones can be used. Specifically, anthracene {anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxy Anthracene, 2-tert-butyl-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-dimethoxyanthracene, 9-methoxy-10-methylanthracene, 9,10-diethoxyanthracene, 2-ethyl-9 , 10-diethoxyanthracene, 2-tert-butyl-9,10-diethoxyanthracene, 2,3-dimethyl-9,10-diethoxyanthracene, 9-ethoxy-10-methylanthracene, 9,10-dipropoxy Anthracene, 9,10-diisopropoxyanthracene, 9,10-dietoxy Anthracene, 2-ethyl-9,10-dipropoxyanthracene, 2-tert-butyl-9,10-dipropoxyanthracene, 2,3-dimethyl-9,10-dipropoxyanthracene, 9-isopropoxy-10-methyl Anthracene, 9,10-dibenzyloxyanthracene, 2-ethyl-9,10-dibenzyloxyanthracene, 2-tert-9,10-dibenzyloxyanthracene, 2,3-dimethyl-9,10-dibenzyloxy Anthracene, 9-benzyloxy-10-methylanthracene, 9,10-di-α-methylbenzyloxyanthracene, 2-ethyl-9,10-di-α-methylbenzyloxyanthracene, 2-tert-9,10- Di-α-methylbenzyloxyanthracene, 2,3-dimethyl-9,10-di- α-methylbenzyloxyanthracene, 9- (α-methylbenzyloxy) -10-methylanthracene, 9,10-diphenylanthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9-methylanthracene, 9-bromoanthracene, 9 -Methylthioanthracene and 9-ethylthioanthracene etc.}; pyrene; 1,2-benzanthracene; perylene; tetracene; coronene; thioxanthone {thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone And 2,4-diethylthioxanthone}; phenothiazine; xanthone; naphthalene {1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4 -Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,7-dimethoxynaphthalene, 1,1'-thiobis (2-naphthol), 1,1'-bi -(2-naphthol) and 4-methoxy-1-naphthol and the like}; ketone {dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2- Hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloro Acetophenone, p-tert-butyltrichloroacetophenone, p Azidobenzalacetophenone, 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxyethoxy) phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone and 4-benzoyl-4 ' -Methyldiphenyl sulfide, etc.}; carbazole {N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, N-glycidylcarbazole, etc.}; chrysene { 1,4-dimethoxychrysene, 1,4-diethoxychrysene, 1,4-dipropoxychrysene, 1,4-dibenzyloxychrysene, 1,4-di-α-methylbenzyloxychrysene, etc.}; phenanthrene {9 -Hydroxyphenanthrene, 9-methoxyphenanthrene, 9-ethoxyphenanthrene, 9-benzyloxyphenanthrene, 9,10-dimethoxyphenanthrene, 9,10-diethoxyphenanthrene, 9,10-dipropoxyphenanthrene, 9,10-dibenzyloxy Phenanthrene, 9,10-di-α-methylbenzyloxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, 9-hydroxy-10-ethoxyphenanthrene, etc.}. Any one of these may be used alone, or two or more thereof may be mixed and used.

  The amount of these sensitizers used is 5 to 500 parts by mass, preferably 10 to 300 parts by mass, with respect to 100 parts by mass of the sulfonium salt represented by the general formula (A-1).

  The chemically amplified positive photoresist composition of the present invention can be appropriately mixed with an organic solvent for viscosity adjustment. Specific examples of organic solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, diester Polyhydric alcohols such as propylene glycol and dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; ethyl formate; Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate , Ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 2-hydroxy-3- Mention may be made of esters such as methyl methylbutanoate, 3-methoxybutyl acetate and 3-methyl-3-methoxybutyl acetate; and aromatic hydrocarbons such as toluene and xylene. Any one of these may be used alone, or two or more thereof may be mixed and used.

  The amount of these organic solvents used is such that the concentration of the solid content is 5 μm or more so that the thickness of the photoresist layer obtained by using the chemically amplified positive photoresist composition of the present invention (for example, spin coating method) is 5 μm or more. Is preferably in the range of 30% by mass or more.

  The chemical amplification type positive photoresist composition for thick film of the present invention can be prepared, for example, by mixing and stirring the above components by a usual method. If necessary, a disperser such as a dissolver, a homogenizer, or a three roll mill is used. You may disperse and mix using a machine. Further, after mixing, it may be filtered using a mesh, a membrane filter or the like.

  The chemically amplified positive photoresist composition of the present invention is suitable for forming a photoresist layer having a thickness of usually 5 to 150 μm, more preferably 10 to 120 μm, and further preferably 10 to 100 μm on a support. ing. This photoresist laminate is obtained by laminating a photoresist layer made of the chemically amplified positive photoresist composition of the present invention on a support.

  The support is not particularly limited, and a conventionally known one can be used. For example, a substrate for electronic parts or a substrate on which a predetermined wiring pattern is formed can be exemplified. Examples of the substrate include a metal substrate such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, and aluminum, and a glass substrate. In particular, the chemically amplified positive photoresist composition of the present invention can form a resist pattern satisfactorily even on a copper substrate. As a material for the wiring pattern, for example, copper, solder, chromium, aluminum, nickel, gold, or the like is used.

  The photoresist laminate can be produced, for example, as follows. That is, a desired coating film is formed by applying a solution of the chemically amplified positive photoresist composition prepared as described above onto a support and removing the solvent by heating. As a coating method on the support, methods such as a spin coating method, a slit coating method, a roll coating method, a screen printing method, and an applicator method can be employed. The pre-baking conditions of the coating film of the composition of the present invention vary depending on the type of each component in the composition, the blending ratio, the coating film thickness, etc., but usually 70 to 150 ° C., preferably 80 to 140 ° C. What is necessary is just about 60 minutes.

  The film thickness of the photoresist layer is usually 5 to 150 μm, preferably 10 to 120 μm, more preferably 10 to 100 μm.

  In order to form a resist pattern using the thus obtained photoresist laminate, light or radiation, for example, having a wavelength of 300 to 500 nm is passed through the obtained photoresist layer through a mask having a predetermined pattern. Irradiation (exposure) with ultraviolet rays or visible rays may be performed selectively.

Here, “light” may be light that activates the acid generator to generate acid, and includes ultraviolet rays, visible rays, and far ultraviolet rays, and “radiation” means X-rays, electron beams, It means an ion beam. As a light or radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, an LED lamp, or the like can be used. Further, the radiation irradiation amount varies depending on the kind of each component in the composition, the blending amount, the film thickness of the coating film, etc., but is, for example, 50 to 10,000 mJ / cm ² in the case of using an ultrahigh pressure mercury lamp.

  Then, after the exposure, the diffusion of the acid is promoted by heating using a known method to change the alkali solubility of the photoresist layer in the exposed portion. Next, for example, using a predetermined alkaline aqueous solution as a developer, unnecessary portions are dissolved and removed to obtain a predetermined resist pattern.

  Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethyl. Ethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0 An aqueous solution of an alkali such as -5-nonane can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, isopropanol or a surfactant to the alkaline aqueous solution can also be used as a developer.

  The development time varies depending on the type of each component of the composition, the blending ratio, and the dry film thickness of the composition, but it is usually 1 to 30 minutes, and the development method is the liquid piling method, dipping method, paddle method, spray development method. Any of these may be used. After the development, washing with running water is performed for 30 to 90 seconds and dried using an air gun, oven, or the like.

  Forming connection terminals such as metal posts and bumps by embedding a conductor such as metal in the non-resist portion (the portion removed with the alkaline developer) of the resist pattern thus obtained by, for example, plating. Can do. The plating method is not particularly limited, and various conventionally known methods can be employed. As the plating solution, solder plating, copper plating, gold plating, or nickel plating solution is particularly preferably used. The remaining resist pattern is finally removed using a stripping solution or the like according to a conventional method.

  The chemically amplified positive photoresist composition of the present invention can also be used as a dry film. This dry film has a protective film formed on both sides of a layer made of the chemically amplified positive photoresist composition of the present invention. The thickness of the layer made of the chemically amplified positive photoresist composition is usually in the range of 10 to 150 μm, preferably 20 to 120 μm, more preferably 20 to 80 μm. Moreover, a protective film is not specifically limited, The resin film conventionally used for the dry film can be used. As an example, one may be a polyethylene terephthalate film and the other may be one selected from the group consisting of a polyethylene terephthalate film, a polypropylene film, and a polyethylene film.

  The chemical amplification type positive dry film as described above can be manufactured, for example, as follows. That is, a solution of a chemically amplified positive photoresist composition prepared as described above is applied on one protective film, and the solvent is removed by heating to form a desired coating film. The drying conditions vary depending on the type of each component in the composition, the blending ratio, the coating film thickness, etc., but are usually 60 to 100 ° C. and about 5 to 20 minutes.

  In order to form a resist pattern using the thus obtained chemically amplified dry film, one protective film of the chemically amplified positive dry film is peeled off and the exposed surface is directed to the support side described above. Then, after laminating on the support to obtain a photoresist layer, after prebaking to dry the resist, the other protective film may be peeled off.

  In the photoresist layer thus obtained on the support, a resist pattern can be formed in the same manner as described above with respect to the photoresist layer formed by coating directly on the support. .

  Examples of the present invention will be described below, but it is not intended that the scope of the present invention be limited to these examples.

<Examples 1-6>
1 part by mass of each compound represented by the following chemical formulas (PAG-1) to (PAG-6) as component (A), 40 parts by mass of resin represented by the following chemical formula (Resin-1) as component (B), As a component (C), 60 parts by mass of a novolak resin obtained by addition condensation of m-cresol and p-cresol in the presence of formaldehyde and an acid catalyst were uniformly dissolved in propylene glycol monomethyl ether acetate, and the pore size was 1 μm. Filtration through a membrane filter gave a chemically amplified positive photoresist composition having a solid content of 40% by mass.

<Comparative Examples 1-3>
As in Example 1, except that 1 part by mass of each of the compounds represented by the following chemical formulas (PAG-7), (PAG-8) and (PAG-9) was used as the component (A), Mold photoresist composition was obtained.

<Evaluation>
Using the chemically amplified positive resist compositions prepared in Examples 1-6 and Comparative Examples 1-3, photosensitivity (sensitivity) was evaluated as follows immediately after preparation and after storage at 40 ° C. for 1 month. The storage stability was judged according to the following criteria.
○: Sensitivity change after storage at 40 ° C. × 1 month is less than 5% of sensitivity immediately after preparation ×: Sensitivity change after storage at 40 ° C. × 1 month is 5% or more of sensitivity immediately after preparation

  Each composition was spin-coated on a silicon wafer substrate and then dried to obtain a photoresist layer having a thickness of about 20 μm. This resist layer was pre-baked at 130 ° C. for 6 minutes using a hot plate. After pre-baking, pattern exposure (i-line) was performed using TME-150RSC (manufactured by Topcon Corporation), and post-exposure heating (PEB) was performed at 75 ° C. for 5 minutes using a hot plate. Thereafter, the film was developed for 5 minutes by an immersion method using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, washed with running water, and blown with nitrogen to obtain a 10 μm line and space pattern. Further, below that, the minimum exposure amount at which no residue of this pattern was observed, that is, the minimum essential exposure amount (corresponding to the sensitivity) necessary for forming the resist pattern was measured. The results are shown in Table 1.

  As shown in Table 1, the chemically amplified positive photoresist compositions of Examples 1 to 6 were more sensitive than those using conventional onium salt acid generators as in Comparative Examples 1 to 3. It was. Moreover, the composition of an Example did not have a bad storage stability like the comparative example 3.

  The chemically amplified positive photoresist composition of the present invention has a good storage stability and is highly sensitive to actinic rays or radiation, particularly i-line, as a circuit board, CSP, MEMS device, This is useful for forming connection terminals such as bumps and metal posts, wiring patterns, etc. in the manufacture of electronic components.

Claims (9)

A chemically amplified positive photoresist composition comprising:
A component (A) that is a compound that generates an acid upon irradiation with light or radiation, and a component (B) that is a resin whose solubility in alkali is increased by the action of an acid,
The component (A) is represented by the following general formula (A-1):

[In the formula (A-1), R ^{1 to} R ⁶ are each an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, or an acyloxy group. Group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, substituted an amino group, a cyano group, a nitro group or a halogen atom, m ¹ ~m ^6, represents the number of R ¹ to R ⁶ each, m ^1, m ⁴ and m ⁶ is an integer of 0 to 5, m ² , M ³ and m ⁵ are integers from 0 to 4, and X ⁻ represents a monovalent polyatomic anion. A chemically amplified positive photoresist composition comprising a sulfonium salt represented by the following formula: 2. The chemically amplified positive photoresist composition according to claim 1, wherein R ^{1 to} R ⁶ are independently selected from a methyl group, a methoxy group, and an acetyl group. R ¹ , R ³ , R ⁴ and R ⁶ are independently of each other a methyl group or a methoxy group, m ¹ , m ³ , m ⁴ and m ⁶ are all 1, and m ² and m ⁵ are both The chemically amplified positive photoresist composition according to claim 1, wherein the composition is a sulfonium salt that is 0. 4. 4. The chemically amplified positive photoresist composition according to claim 1, wherein m ^{1 to} m ⁶ are all 0. 5. Wherein X ^{_{-, MY a -, (Rf)}} b PF 6-b -, R 7 c BY 4-c -, R 7 c GaY 4-c -, R 8 SO 3 -, (R 8 SO 2) 3 C ^- or _{^{(R 8 SO 2) 2 N}} - anion (here represented by, M is a phosphorus atom, a boron atom, an arsenic atom or an antimony atom, Y is a halogen atom, Rf is fluorine least 80 mol% of hydrogen atoms An alkyl group substituted with an atom, P is a phosphorus atom, F is a fluorine atom, R ⁷ is a phenyl group in which at least one hydrogen atom is substituted with a halogen atom, a trifluoromethyl group, a nitro group or a cyano group, B Is a boron atom, Ga is a gallium atom, R ⁸ is an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, a is an integer of 4 to 6, b Is an integer from 1 to 5, and c is an integer from 1 to 4. 1 to chemically amplified positive photoresist composition according to any one of 4. X ⁻ is SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B _{^{-, (C 6 F 5)}} 4 Ga -, ((CF 3) 2 C 6 H 3) 4 Ga -, trifluoromethanesulfonic acid anion, nonafluorobutanesulfonic acid anion, benzenesulfonic acid anion, p- toluenesulfonic acid 6. The method according to claim 1, comprising at least one selected from the group consisting of an anion, (CF ₃ SO ₂ ) ₃ C ⁻ , and (CF ₃ SO ₂ ) ₂ N ^−. Chemically amplified positive photoresist composition.   The component (B) contains at least one resin selected from the group consisting of a novolak resin (B1), a polyhydroxystyrene resin (B2), and an acrylic resin (B3). 7. The chemically amplified positive photoresist composition according to any one of items 6 to 6.   The chemically amplified positive photoresist composition according to any one of claims 1 to 7, further comprising an alkali-soluble resin (C) and an acid diffusion controller (D). A laminating step of laminating a 10 to 150 μm-thick photoresist layer made of the chemically amplified positive photoresist composition according to claim 1 on a support to obtain a photoresist laminate;
An exposure step of selectively irradiating light or radiation to the photoresist laminate;
A development step of developing the photoresist laminate after the exposure step to obtain a resist pattern;
A method for producing a resist pattern, comprising: