JP5778568B2 - Chemical amplification type positive photoresist composition for thick film, thick film photoresist laminate, method for producing thick film photoresist pattern, and method for producing connection terminal - Google Patents

Description

  The present invention relates to a chemically amplified positive photoresist composition for thick film, a thick film photoresist laminate, a method for producing a thick film photoresist pattern, and a method for producing a connection terminal.

  Currently, photofabrication is the mainstream of precision micromachining technology. Photofabrication is the application of a photoresist composition to the workpiece surface to form a photoresist layer, patterning the photoresist layer by photolithography technology, chemical etching and electrolysis using the patterned photoresist layer (photoresist pattern) as a mask. A generic term for technologies for manufacturing various precision parts such as semiconductor packages by performing etching or electroforming mainly composed of electroplating.

  In recent years, with the downsizing of electronic devices, high-density packaging technology for semiconductor packages has progressed, and the use of multi-pin thin film packaging for packages, miniaturization of package size, two-dimensional packaging technology by flip chip method, and three-dimensional packaging technology. Based on this, the mounting density is improved. In such a high-density mounting technology, as connection terminals, for example, protruding electrodes (mounting terminals) such as bumps protruding on the package, or metal posts that connect the rewirings extending from the peripheral terminals on the wafer and the mounting terminals. Etc. are arranged on the substrate with high accuracy.

  A photoresist composition is used for the above photofabrication. As such a photoresist composition, a chemically amplified photoresist composition containing an acid generator is known (Patent Documents 1, 2, etc.). See). The chemically amplified photoresist composition generates an acid from the acid generator by irradiation (exposure), and the acid diffusion is promoted by the heat treatment to cause an acid catalytic reaction to the base resin or the like in the composition. The alkali solubility changes.

  Moreover, as a photoresist composition used for the above photofabrication, there exists a chemically amplified positive photoresist composition for thick films (refer patent document 3 etc.). The chemically amplified positive photoresist composition for thick film is used, for example, for forming bumps and metal posts by a plating process. For example, a thick photoresist layer having a thickness of about 20 μm is formed on a support, exposed through a predetermined mask pattern, and developed to selectively remove (peel) the portions for forming bumps and metal posts. A photoresist pattern is formed. A bump or metal post can be formed by embedding a conductor such as copper in the removed portion (non-resist portion) by plating and then removing the surrounding photoresist pattern.

JP 9-176112 A JP 11-52562 A JP 2010-185986 A

  However, even in the case of a chemically amplified positive photoresist composition for thick film as described in Patent Document 3, when the film thickness is 30 μm or more, a foam bite (bubbles are formed on the surface of the photoresist layer at the time of application or after baking after application). It has been found that there is a problem that Therefore, a chemically amplified positive photoresist composition for thick film that can suppress foaming in a wide range of film thickness has been demanded.

  The present invention has been made in view of the above-mentioned problems, and a chemically amplified positive photoresist composition for thick film capable of forming a good thick film photoresist pattern with suppressed bubble formation, and using such a composition. It is an object of the present invention to provide a thick film photoresist laminate, a method for producing a thick film photoresist pattern, and a method for producing a connection terminal.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above problem can be solved by using a specific organic solvent in the chemically amplified positive photoresist composition for thick film, The present invention has been completed. Specifically, the present invention provides the following.

  A first aspect of the present invention is a thick film chemically amplified positive photoresist composition used for forming a thick film photoresist layer on a support, which generates an acid upon irradiation with actinic rays or radiation. It contains an acid generator (A), a resin (B) whose solubility in alkali is increased by the action of an acid, and an organic solvent (S). The organic solvent (S) comprises propylene glycol monomethyl ether acetate and 3 -A chemically amplified positive photoresist composition for thick film, which is a mixed solvent obtained by mixing methoxybutyl acetate with a mass ratio of 60:40 to 20:80.

  According to a second aspect of the present invention, there is provided a thick film photoresist laminate comprising a support and a thick film photoresist layer comprising a thick film chemically amplified positive photoresist composition according to the present invention. It is.

  According to a third aspect of the present invention, there is provided a laminating step of laminating a thick film photoresist layer made of a chemically amplified positive photoresist composition for thick film according to the present invention on a support, and an active layer on the thick film photoresist layer. A method for producing a thick film photoresist pattern, comprising: an exposure step of irradiating with light or radiation; and a development step of developing the thick photoresist layer after exposure to obtain a thick film photoresist pattern.

  According to a fourth aspect of the present invention, there is provided a method of manufacturing a connection terminal comprising a step of forming a connection terminal made of a conductor in a non-resist portion of the thick film photoresist pattern obtained by the third aspect.

  According to the present invention, a chemically amplified positive photoresist composition for thick film capable of forming a good thick film photoresist pattern with reduced bubble formation, a thick film photoresist laminate using such a composition, A method for manufacturing a film photoresist pattern and a method for manufacturing a connection terminal can be provided.

≪Chemically amplified positive photoresist composition for thick film≫
The chemically amplified positive photoresist composition for thick film according to the present invention (hereinafter simply referred to as “photoresist composition”) comprises an acid generator (A) that generates an acid upon irradiation with actinic rays or radiation, an acid generator It contains at least the resin (B) whose solubility in alkali is increased by the action and the organic solvent (S). This photoresist composition is suitably used for the formation of connection terminals such as bumps and metal posts, wiring patterns, and the like in the manufacture of electronic components such as circuit boards and CSPs (chip size packages) mounted on the circuit boards. Hereinafter, each component contained in the photoresist composition according to the present invention will be described in detail.

<Acid generator (A)>
The acid generator (A) used in the present invention is a compound that generates an acid by irradiation with actinic rays or radiation, and is not particularly limited as long as it is a compound that generates an acid directly or indirectly by light.

  As a 1st aspect in an acid generator (A), the compound represented by the following general formula (a1) is mentioned.

In the general formula (a1), X ^1a represents a sulfur atom or an iodine atom having a valence g, and g is 1 or 2. h represents the number of repeating units in the structure in parentheses. R ^1a is an organic group bonded to X ^1a and is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or an alkyl group having 2 to 30 carbon atoms. Represents an alkenyl group or an alkynyl group having 2 to 30 carbon atoms, and R ^1a represents alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl , Heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and at least one selected from the group consisting of halogen may be substituted. The number of R ^1a is g + h (g−1) +1, and R ^1a may be the same as or different from each other. Also, directly with each other two or more ^{R 1a,} or _{-O -, - S -, -} SO -, - SO 2 -, - NH -, - NR 2a -, - CO -, - COO -, - CONH- May be bonded via an alkylene group having 1 to 3 carbon atoms or a phenylene group to form a ring structure containing X ^1a . R ^2a is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

X ^2a is a structure represented by the following general formula (a2).

In the general formula (a2), X ^4a represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent group of a heterocyclic compound having 8 to 20 carbon atoms, and X ^4a represents It may be substituted with at least one selected from the group consisting of alkyl having 1 to 8 carbons, alkoxy having 1 to 8 carbons, aryl having 6 to 10 carbons, hydroxy, cyano, nitro, and halogen. Good. X ^5a is _{-O -, - S -, -} SO -, - SO 2 -, - NH -, - NR 2a -, - CO -, - COO -, - CONH-, alkylene group having 1 to 3 carbon atoms, Or represents a phenylene group. h represents the number of repeating units in the structure in parentheses. The h + 1 X ^4a and the h X ^5a may be the same or different. R ^2a is the same as defined above.

X ^3a- is an onium counter ion, and examples thereof include a fluorinated alkyl fluorophosphate anion represented by the following general formula (a17) or a borate anion represented by the following general formula (a18).

In the general formula (a17), R ^3a represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. j shows the number and is an integer of 1-5. j R ^3a may be the same or different.

In the general formula (a18), R ^{4a to} R ^7a each independently represents a fluorine atom or a phenyl group, and part or all of the hydrogen atoms of the phenyl group are selected from the group consisting of a fluorine atom and a trifluoromethyl group. It may be substituted with at least one selected.

  Examples of the onium ion in the compound represented by the general formula (a1) include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide. Bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2 -Chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo- 10-thia-9,10-dihydroanthra N-2-yldiphenylsulfonium, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- (4-benzoylphenylthio) phenyl Diphenylsulfonium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 4-biphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 3-biphenylsulfonium, [4- (4-acetophenylthio) phenyl] diphenylsulfonium, oct Decylmethylphenacylsulfonium, diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) Examples thereof include phenyliodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, and 4-isobutylphenyl (p-tolyl) iodonium.

  Among the onium ions in the compound represented by the general formula (a1), a preferable onium ion includes a sulfonium ion represented by the following general formula (a19).

In the general formula (a19), R ^8a is independently a hydrogen atom, alkyl, hydroxy, alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, halogen atom, aryl optionally having substituent, arylcarbonyl, Represents a group selected from the group consisting of X ^2a represents the same meaning as X ^2a in the general formula (a1).

  Specific examples of the sulfonium ion represented by the general formula (a19) include 4- (phenylthio) phenyldiphenylsulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4 -(4-benzoylphenylthio) phenyldiphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 4-biphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 3-biphenylsulfonium, [4- (4-acetophenylthio) phenyl] diphenylsulfonium.

In the fluorinated alkyl fluorophosphate anion represented by the general formula (a17), R ^3a represents an alkyl group substituted with a fluorine atom, preferably having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. is there. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and cyclopropyl, cyclobutyl and cyclopentyl. And the ratio of the hydrogen atom of the alkyl group substituted by a fluorine atom is usually 80% or more, preferably 90% or more, and more preferably 100%. When the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium fluorinated alkyl fluorophosphate represented by the general formula (a1) is lowered.

Particularly preferred R ^3a is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%. Specific examples include 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, (CF ₃ ) ₃ C may be mentioned. . The number j of R ^3a is an integer of 1 to 5, preferably 2 to 4, particularly preferably 2 or 3.

Specific examples of preferred fluorinated alkyl fluorophosphate anions include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [((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 ) ₃ PF ₃ ] ⁻ , and among 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 Particularly preferred.

Preferred specific examples of the borate anion represented by the general formula (a18) include tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ), tetrakis [(trifluoromethyl) phenyl] borate. ([B (C ₆ H ₄ CF ₃ ) ₄ ] ⁻ ), difluorobis (pentafluorophenyl) borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ⁻ ), trifluoro (pentafluorophenyl) borate ([( C ₆ F ₅ ) BF ₃ ] ⁻ ), tetrakis (difluorophenyl) borate ([B (C ₆ H ₃ F ₂ ) ₄ ] ⁻ ) and the like. Among these, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferable.

  As a second aspect of the acid generator (A), 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2 -(2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (5-ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ethenyl ] -S-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2 -(3,5-diethoxyf Nyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl)- 6- [2- (3-Methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) ethenyl]- s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- (3 , 4-methylenedioxyphenyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis- Lichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4- Bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- [2- (5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3 , 5- Dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, tris (1,3-dibromopropyl) -1 , 3,5-triazine, halogen-containing triazine compounds such as tris (2,3-dibromopropyl) -1,3,5-triazine, and the following general formulas such as tris (2,3-dibromopropyl) isocyanurate ( and halogen-containing triazine compounds represented by a3).

In the general formula (a3), R ^9a , R ^10a and R ^11a each independently represent a halogenated alkyl group.

  In addition, as a third aspect in the acid generator (A), α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzene Sulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, and oxime sulfonate The compound represented by the following general formula (a4) containing a group is mentioned.

In the general formula (a4), R ^12a represents a monovalent, divalent, or trivalent organic group, and R ^13a represents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic group. N represents the number of repeating units having a structure in parentheses.

In the above general formula (a4), the aromatic compound group refers to a group of a compound exhibiting physical and chemical properties peculiar to an aromatic compound. For example, an aryl group such as a phenyl group or a naphthyl group, And heteroaryl groups such as a thienyl group and the like. These may have one or more suitable substituents such as a halogen atom, an alkyl group, an alkoxy group, and a nitro group on the ring. R ^13a is particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. In particular, a compound in which R ^12a is an aromatic compound group and R ^13a is an alkyl group having 1 to 4 carbon atoms is preferable.

As the acid generator represented by the general formula (a4), when n = 1, R ^12a is any one of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and R ^13a is a methyl group, Specifically, α- (methylsulfonyloxyimino) -1-phenylacetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- (p -Methoxyphenyl) acetonitrile, [2- (propylsulfonyloxyimino) -2,3-dihydroxythiophene-3-ylidene] (o-tolyl) acetonitrile, and the like. When n = 2, the acid generator represented by the general formula (a4) specifically includes an acid generator represented by the following formula.

  Moreover, as a 4th aspect in an acid generator (A), the onium salt which has a naphthalene ring in a cation part is mentioned. This “having a naphthalene ring” means having a structure derived from naphthalene, and means that at least two ring structures and their aromaticity are maintained. The naphthalene ring may have a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. The structure derived from the naphthalene ring may be a monovalent group (one free valence) or a divalent group (two free valences) or more, but may be a monovalent group. Desirable (however, at this time, the free valence is counted excluding the portion bonded to the substituent). The number of naphthalene rings is preferably 1 to 3.

  As the cation portion of the onium salt having a naphthalene ring in such a cation portion, a structure represented by the following general formula (a5) is preferable.

In the general formula (a5), at least one of R ^14a , R ^15a and R ^16a represents a group represented by the following general formula (a6), and the rest is a linear or branched group having 1 to 6 carbon atoms. An alkyl group, a phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of R ^14a , R ^15a and R ^16a is a group represented by the following general formula (a6), and the remaining two are each independently a linear or branched group having 1 to 6 carbon atoms. It is an alkylene group, and these terminals may be bonded to form a ring.

In the general formula (a6), R ^17a and R ^18a are each independently a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched group having 1 to 6 carbon atoms. Represents an alkyl group, and R ^19a represents a straight-chain or branched alkylene group having 1 to 6 carbon atoms which may have a single bond or a substituent. l and m each independently represent an integer of 0 to 2, and l + m is 3 or less. However, when a plurality of R ^17a are present, they may be the same as or different from each other. When a plurality of R ^18a are present, they may be the same as or different from each other.

Of the R ^14a , R ^15a and R ^16a , the number of groups represented by the general formula (a6) is preferably one from the viewpoint of the stability of the compound, and the rest is a straight chain having 1 to 6 carbon atoms. Or branched alkylene groups, and these ends may be bonded to form a ring. In this case, the two alkylene groups constitute a 3- to 9-membered ring including a sulfur atom. The number of atoms (including sulfur atoms) constituting the ring is preferably 5-6.

  Examples of the substituent that the alkylene group may have include an oxygen atom (in this case, a carbonyl group is formed together with a carbon atom constituting the alkylene group), a hydroxyl group, and the like.

  Examples of the substituent that the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched alkyl group having 1 to 6 carbon atoms. Is mentioned.

  Suitable examples of these cation moieties include those represented by the following formulas (a7) and (a8), and the structure represented by the following formula (a8) is particularly preferred.

  Such a cation moiety may be an iodonium salt or a sulfonium salt, but a sulfonium salt is desirable from the viewpoint of acid generation efficiency and the like.

  Therefore, an anion capable of forming a sulfonium salt is desirable as a suitable anion part for an onium salt having a naphthalene ring in the cation part.

  The anion portion of such an acid generator is a fluoroalkyl sulfonate ion or an aryl sulfonate ion in which a part or all of hydrogen atoms are fluorinated.

  The alkyl group in the fluoroalkylsulfonic acid ion may be linear, branched or cyclic having 1 to 20 carbon atoms, and preferably has 1 to 10 carbon atoms from the bulk of the acid generated and its diffusion distance. In particular, a branched or annular shape is preferable because of its short diffusion distance. Moreover, since it can synthesize | combine cheaply, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group etc. can be mentioned as a preferable thing.

  The aryl group in the aryl sulfonate ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include an alkyl group, a phenyl group which may or may not be substituted with a halogen atom, and a naphthyl group. In particular, an aryl group having 6 to 10 carbon atoms is preferable because it can be synthesized at low cost. Specific examples of preferable ones include a phenyl group, a toluenesulfonyl group, an ethylphenyl group, a naphthyl group, and a methylnaphthyl group.

  In the fluoroalkyl sulfonate ion or aryl sulfonate ion, the fluorination rate when part or all of the hydrogen atoms are fluorinated is preferably 10 to 100%, more preferably 50 to 100%, In particular, those in which all hydrogen atoms are substituted with fluorine atoms are preferred because the strength of the acid is increased. Specific examples thereof include trifluoromethane sulfonate, perfluorobutane sulfonate, perfluorooctane sulfonate, and perfluorobenzene sulfonate.

  Among these, preferable anion moieties include those represented by the following general formula (a9).

In the general formula (a9), R ^20a is a group represented by the following general formulas (a10) and (a11) or a group represented by the following formula (a12).

In the general formula (a10), x represents an integer of 1 to 4. In the general formula (a11), R ^21a represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Represents a group, and y represents an integer of 1 to 3. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferable from the viewpoint of safety.

  Moreover, as an anion part, what contains the nitrogen represented by the following general formula (a13) and (a14) can also be used.

Above general formula (a13), in (a14), X ^a represents a linear or branched alkylene group having at least one hydrogen atom is substituted with a fluorine atom, the carbon number of the alkylene group having 2 to 6 Preferably 3 to 5 and most preferably 3 carbon atoms. Y ^a and Z ^a each independently represents a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, Is 1-7, more preferably 1-3.

The smaller the carbon number of the alkylene group of X ^a or the carbon number of the alkyl group of Y ^a and Z ^a , the better the solubility in an organic solvent, which is preferable.

Further, in the alkylene group of X ^a or the alkyl group of Y ^a and Z ^a , the larger the number of hydrogen atoms substituted with fluorine atoms, the more preferable the strength of the acid. The proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all hydrogen atoms are substituted with fluorine atoms. A perfluoroalkylene group or a perfluoroalkyl group.

  Preferable examples of the onium salt having a naphthalene ring in such a cation moiety include compounds represented by the following formulas (a15) and (a16).

  The fifth aspect of the acid generator (A) includes bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4- Bissulfonyldiazomethanes such as dimethylphenylsulfonyl) diazomethane; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, Nitrobenzyl derivatives such as nitrobenzyl carbonate and dinitrobenzyl carbonate; pyrogallol trimesylate, pyrogallol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccine Sulfonic acid esters such as amide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide and N-methylsulfonyloxyphthalimide; trifluoromethanesulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; Iodonium hexafluorophosphate, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium Trifluoromethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluoro Onium salts such as Tan sulfonate; benzoin tosylate, benzoin tosylate such as α- methyl benzoin tosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzyl carbonate and the like.

  This acid generator (A) may be used alone or in combination of two or more. The content of the acid generator (A) is preferably 0.1 to 10% by mass, and preferably 0.5 to 3% by mass with respect to the total mass of the photoresist composition according to the present invention. More preferred. By setting it as the above range, sufficient sensitivity can be obtained, solubility in an organic solvent is good, a uniform solution is obtained, and storage stability is improved.

<Resin (B)>
The resin (B) whose solubility in an alkali is increased by the action of an acid is not particularly limited, and any resin whose solubility in an alkali is increased by the action of an acid can be used. Among these, it is preferable to contain at least one resin selected from the group consisting of novolac resin (B1), polyhydroxystyrene resin (B2), and acrylic resin (B3).

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

In the general formula (b1), R ^1b represents an acid dissociable, dissolution inhibiting group, and R ^2b and R ^3b each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the acid dissociable, dissolution inhibiting group represented by R ^1b include groups represented by the following general formulas (b2) and (b3), linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms. , A vinyloxyethyl 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 a carbon number. Represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, R ^7b represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and o represents 0 or 1 Represent.

  Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. . Examples of the cyclic alkyl group include a cyclopentyl group and a 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 and the like. 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 a trimethylsilyl group and a tri-tert-butyldimethylsilyl group.

[Polyhydroxystyrene resin (B2)]
As polyhydroxystyrene resin (B2), resin containing the structural unit 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, and R ^9b represents an acid dissociable, dissolution inhibiting group.

  The said C1-C6 alkyl group is a C1-C6 linear, branched, or cyclic alkyl group, for example. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

As the acid dissociable, dissolution inhibiting group represented by R ^9b , the same acid dissociable, dissolution inhibiting groups as exemplified in the general formulas (b2) and (b3) can be used.

  Furthermore, the polyhydroxystyrene resin (B2) 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. Examples of such a polymerizable compound 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, 2- Methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid and other methacrylic acid derivatives having a carboxyl group and an ester bond; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (Meth) acrylic acid alkyl esters such as (meth) acrylate; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meta (Meth) acrylic acid aryl esters such as acrylate and benzyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxy Vinyl group-containing aromatic compounds such as styrene, α-methylhydroxystyrene and α-ethylhydroxystyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugated diolefins such as butadiene and isoprene; Acrylonitrile, methacrylonitrile Nitrile group-containing polymerizable compounds such as; 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 acrylic resin (B3), resin containing the structural unit represented by the following general formula (b5)-(b7) can be used.

In the above general formulas (b5) to (b7), R ^{10b to} R ^17b each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or 1 to 6 carbon atoms. Represents a linear or branched fluorinated alkyl group (wherein R ^11b is not a hydrogen atom), and X ^b is a hydrocarbon having 5 to 20 carbon atoms together with the carbon atom to which it is bonded. forms a ring, Y ^b is substituted represents those aliphatic cyclic group or an alkyl group, p represents an integer of 0 to 4, q represents 0 or 1.

  Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, and the like. Can be mentioned. 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.

^Xb 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 an aliphatic cyclic group 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 alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (═O) is particularly preferable.

Y ^b is an aliphatic cyclic group or an alkyl group, and examples thereof 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 and the like. In particular, a group in which one or more hydrogen atoms are removed from adamantane (which may further have a substituent) is preferable.

Furthermore, the alicyclic group of the abovementioned Y ^b is, if they have a substituent on the ring skeleton, examples of the substituent, a hydroxyl group, a carboxyl group, a cyano group, an oxygen atom (= O) polar groups such as And a linear or branched alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (═O) is particularly preferable.

Also, if Y ^b is an alkyl group, having 1 to 20 carbon atoms, it is preferred that preferably a linear or branched alkyl group having 6 to 15. Such an alkyl group is particularly preferably an alkoxyalkyl group. Examples of the 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.

  Preferable specific examples of the structural unit represented by the general formula (b5) include those represented by the following formulas (b5-1) to (b5-33).

In the above formulas (b5-1) to (b5-33), R ^18b represents a hydrogen atom or a methyl group.

  Preferable specific examples of the structural unit represented by the general formula (b6) include those represented by the following formulas (b6-1) to (b6-24).

In the above formulas (b6-1) to (b6-24), R ^18b represents a hydrogen atom or a methyl group.

  Preferable specific examples of the structural unit represented by the general formula (b7) include those represented by the following formulas (b7-1) to (b7-15).

In the above formulas (b7-1) to (b7-15), R ^18b represents a hydrogen atom or a methyl group.

  Further, the acrylic resin (B3) is made of 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 (b7). A resin is preferred.

  Examples of the polymerizable compound having an ether bond include radical polymerizable compounds such as a (meth) acrylic acid derivative having an ether bond and an ester bond, and specific examples include 2-methoxyethyl (meth) acrylate. 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) Examples thereof include acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. The polymerizable compound having an ether bond is preferably 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, or methoxytriethylene glycol (meth) acrylate. These polymerizable compounds may be used alone or in combination of two or more.

  Furthermore, other polymerizable compounds can be included in the acrylic resin (B3) 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.

  Examples of such polymerizable compounds 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. Methacrylic acid derivatives having a carboxyl group and an ester bond such as ethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth ) (Meth) acrylic acid alkyl esters such as acrylate and cyclohexyl (meth) acrylate; (meth) acrylic acid hydroxyal such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate (Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloro Vinyl group-containing aromatic compounds such as methylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene Nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide; Kill.

  Examples of the polymerizable compound include (meth) acrylic acid esters having a non-acid dissociable aliphatic polycyclic group, and vinyl group-containing aromatic compounds. As the non-acid-dissociable aliphatic polycyclic group, a tricyclodecanyl group, an adamantyl group, a tetracyclododecanyl group, an isobornyl group, a norbornyl group, and the like are particularly preferable in terms of industrial availability. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

  Specific examples of (meth) acrylic acid esters having an acid non-dissociable aliphatic polycyclic group include those having the structures of the following formulas (b8-1) to (b8-5). it can.

In the above formulas (b8-1) to (b8-5), R ^19b represents a hydrogen atom or a methyl group.

  Among the resins (B), it is preferable to use an acrylic resin (B3). Among such acrylic resins (B3), those derived from the structural unit represented by the general formula (b5), structural units derived from (meth) acrylic acid, and (meth) acrylic acid alkyl esters. A copolymer having a structural unit and a structural unit derived from (meth) acrylic acid aryl esters is preferable.

  Such a copolymer is preferably a copolymer represented by the following general formula (b9).

In the general formula (b9), R ^20b represents a hydrogen atom or a methyl group, R ^21b represents a linear or branched alkyl group having 2 to 4 carbon atoms, and X ^b has the same meaning as described above. , R ^22b represents a linear or branched alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 1 to 6 carbon atoms, and R ^23b represents an aryl group having 6 to 12 carbon atoms.

  Furthermore, in the copolymer represented by the general formula (b9), s, t, u, v represent the molar ratio of each structural unit, s is 8-45 mol%, and t is 10-65. Mol%, u is 3 to 25 mol%, and v is 6 to 25 mol%.

  The polystyrene equivalent mass average molecular weight of the resin (B) is preferably 10,000 to 600,000, more preferably 20,000 to 400,000, and still more preferably 30,000 to 300,000. By adopting such a mass average molecular weight, sufficient strength of the thick photoresist layer can be maintained without lowering the peelability from the support, and furthermore, preventing the occurrence of profile swelling and cracking during plating. Can do.

  The resin (B) is preferably a resin having a dispersity of 1.05 or more. Here, the degree of dispersion is a value obtained by dividing the mass average molecular weight by the number average molecular weight. By setting it as such a dispersion degree, the problem that the stress tolerance with respect to desired plating and the metal layer obtained by a plating process become easy to swell can be avoided.

  The content of the resin (B) is preferably 5 to 60% by mass with respect to the total mass of the photoresist composition according to the present invention.

<Alkali-soluble resin (C)>
The photoresist composition according to the present invention preferably further contains an alkali-soluble resin (C) in order to improve crack resistance. Here, the alkali-soluble resin is a resin film having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), and a 1 μm-thick resin film is formed on the substrate to form a 2.38% by mass TMAH aqueous solution. When immersed for 1 minute, it means one that dissolves by 0.01 μm or more. The alkali-soluble resin (C) is preferably at least one resin selected from the group consisting of a novolak resin (C1), a polyhydroxystyrene resin (C2), and an acrylic resin (C3).

[Novolac resin (C1)]
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 the phenols 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- Examples include trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglicinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol and the like.
Examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like.
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.

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

  The novolak resin (C1) preferably has a mass average molecular weight of 1,000 to 50,000.

[Polyhydroxystyrene resin (C2)]
Examples of the hydroxystyrene compound constituting the polyhydroxystyrene resin (C2) include p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene, and the like.
Furthermore, 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, α-methylstyrene, and the like.

  The polyhydroxystyrene resin (C2) preferably has a mass average molecular weight of 1000 to 50000.

[Acrylic resin (C3)]
The acrylic resin (C3) preferably includes a structural unit derived from a polymerizable compound having an ether bond and a structural 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, and tetrahydrofurfuryl (meth) acrylate. The polymerizable compound having an ether bond is preferably 2-methoxyethyl acrylate or methoxytriethylene glycol acrylate. These polymerizable compounds may be used alone or in combination of two or more.

  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, and 2-methacryloyloxyethylhexahydrophthalic acid. The polymerizable compound having a carboxyl group is preferably acrylic acid or methacrylic acid. These polymerizable compounds may be used alone or in combination of two or more.

  The acrylic resin (C3) preferably has a mass average molecular weight of 50,000 to 800,000.

  The content of the alkali-soluble resin (C) is preferably 0 to 80 parts by mass, more preferably 0 to 60 parts by mass when the total of the resin (B) and the resin (C) is 100 parts by mass. is there. By making content of alkali-soluble resin (C) into said range, there exists a tendency which can improve crack tolerance and can prevent the film loss at the time of image development.

<Acid diffusion control agent (D)>
The photoresist composition according to the present invention preferably further contains an acid diffusion control agent (D) for the purpose of improving the photoresist pattern shape, the stability of holding and the like. As the acid diffusion controller (D), a nitrogen-containing compound (D1) is preferable, and an organic carboxylic acid, or an oxo acid of phosphorus or a derivative thereof (D2) 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, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, and 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-di Tylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea Imidazole, benzimidazole, 4-methylimidazole, 8-oxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri (2-pyridyl) -S-triazine, morpholine, 4-methylmorpholine, piperazine, Examples include 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, pyridine and the like. These may be used alone or in combination of two or more.

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

[Organic carboxylic acid or phosphorus oxo acid or derivative (D2)]
Among organic carboxylic acids or phosphorus oxo acids or derivatives thereof (D2), specifically, as malonic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are preferable. 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 the like phosphoric acid and derivatives thereof such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid- Phosphonic acids such as di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and derivatives thereof; phosphinic acids such as phosphinic acid and phenylphosphinic acid and their esters Derivatives thereof, and the like. Among these, phosphonic acid is particularly preferable. These may be used alone or in combination of two or more.

  The organic carboxylic acid or phosphorus oxo acid or derivative thereof (D2) is usually used in the range of 0 to 5 parts by mass with respect to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (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 is preferable to use an organic carboxylic acid, or an oxo acid of phosphorus or a derivative thereof (D2) in an amount equivalent to the nitrogen-containing compound (D1).

<Organic solvent (S)>
The photoresist composition according to the present invention uses a mixed solvent in which propylene glycol monomethyl ether and 3-methoxybutyl acetate are mixed at a mass ratio of 60:40 to 20:80 as the organic solvent (S). By mixing 3-methoxybutyl acetate with propylene glycol monomethyl ether acetate in a ratio within the above range, bubble biting is less likely to occur during prebaking after coating, and a good thick film photoresist pattern can be formed.

  Content of an organic solvent (S) is not specifically limited, For example, it can be made to contain in the range from which the solid content concentration of the photoresist composition which concerns on this invention will be 30-65 mass%.

<Other ingredients>
The photoresist composition according to the present invention may further contain a polyvinyl resin in order to improve plasticity. Specific examples of the polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol, and copolymers thereof. Is mentioned. The polyvinyl resin is preferably polyvinyl methyl ether because of its low glass transition point.

  Further, the photoresist composition according to the present invention may further contain an adhesion assistant in order to improve the adhesion to the support.

  In addition, the photoresist composition according to the present invention may further contain a surfactant in order to improve coating properties, antifoaming properties, leveling properties and the like. Specific examples of the surfactant include BM-1000, BM-1100 (all manufactured by BM Chemie), MegaFuck F142D, MegaFuck F172, MegaFuck F173, MegaFak F183 (all manufactured by Dainippon Ink & Chemicals, Inc.) ), Fluorard FC-135, Fluorard FC-170C, Fluorard FC-430, Fluorard FC-431 (all manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Commercially available fluorosurfactants such as Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone Co., Ltd.) However, it is not limited to these.

  Further, the photoresist composition according to 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 a developer.

  Specific examples of the acid and acid anhydride include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid and cinnamic acid; lactic acid, 2-hydroxybutyric acid, Hydroxy monocarboxylic acids such as 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid and syringic acid Acids: 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 Acid, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarbo Polycarboxylic acids such as acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride, Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, anhydrous And acid anhydrides such as trimellitic acid, benzophenone anhydride tetracarboxylic acid, ethylene glycol bistrimellitic anhydride, and glycerin tris anhydrous trimellitate.

  Specific examples of the high boiling point solvent include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl Ethyl 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 , Propylene carbonate, phenyl cellosolve acetate and the like.

  Moreover, the photoresist composition according to the present invention may further contain a sensitizer in order to improve sensitivity.

<Preparation of photoresist composition>
The photoresist composition according to the present invention may be prepared by simply mixing and stirring the above components by a usual method. Also good. Moreover, after mixing, you may filter using a mesh, a membrane filter, etc. further.

≪Thick film photoresist laminate≫
The thick film photoresist laminate of the present invention is obtained by laminating a thick film photoresist layer made of the above chemically amplified positive photoresist composition for thick film on a support. The support is not particularly limited, and a conventionally known one can be used, and examples thereof include a substrate for electronic components and a substrate on which a predetermined wiring pattern is formed. Examples of the substrate include a metal substrate such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, and aluminum, a glass substrate, and the like. As a material for the wiring pattern, for example, copper, solder, chromium, aluminum, nickel, gold or the like is used.

  The thick film photoresist laminate as described above can be manufactured, for example, as follows. That is, a thick film chemically amplified positive photoresist composition solution prepared as described above is applied onto a support, and the solvent is removed by heating to form a desired coating film. As a coating method on a to-be-processed support body, methods, such as a spin coat method, a slit coat method, a roll coat method, a screen printing method, an applicator method, are employable. The pre-baking conditions for 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 are usually 70 to 150 ° C., preferably 80 to 140 ° C. ~ About 60 minutes.

  The thickness of the thick photoresist layer of the present invention is desirably 10 to 150 μm, preferably 20 to 120 μm, and more preferably 20 to 80 μm.

≪Method for manufacturing thick film photoresist pattern≫
The method for producing a thick film photoresist pattern according to the present invention comprises a laminating step of laminating a thick film photoresist layer comprising the photoresist composition according to the present invention on a support, and irradiating the thick film photoresist layer with actinic rays or radiation. And a developing step of developing the thick film photoresist layer after exposure to obtain a thick film photoresist pattern.

  In order to form a photoresist pattern using the thick film photoresist laminate obtained as described above, an actinic ray or radiation, for example, a wavelength is applied to the obtained thick film photoresist layer through a mask having a predetermined pattern. Irradiation (exposure) with ultraviolet rays or visible rays of 300 to 500 nm is selectively performed.

As a radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like can be used. The radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, γ rays, electron beams, proton beams, neutron beams, ion beams, and the like. The amount of radiation irradiation varies depending on the composition of the photoresist composition according to the present invention and the thickness of the thick photoresist layer, but is, for example, 100 to 10,000 mJ / cm ² when using an ultrahigh pressure mercury lamp. The radiation includes light that activates the acid generator (A) in order to generate an acid.

  After the exposure, the diffusion of the acid is promoted by heating using a known method to change the alkali solubility of the thick film photoresist layer in the exposed portion.

  Next, in the development step, for example, a predetermined alkaline aqueous solution is used as a developer, and unnecessary portions are dissolved and removed to obtain a predetermined thick film photoresist 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, Dimethylethanolamine, 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 or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.

  The development time varies depending on the composition of the photoresist composition according to the present invention and the film thickness of the thick photoresist layer, but is usually 1 to 30 minutes. The developing method may be any of a liquid piling method, a dipping method, a paddle method, a spray developing method, and the like.

  After the development, washing with running water is performed for 30 to 90 seconds, and dried using an air gun, an oven, or the like. In this way, a thick film photoresist pattern can be manufactured.

≪Connection terminal manufacturing method≫
A connection terminal such as a bump or a metal post is formed by embedding a conductor such as metal in the non-resist portion (portion removed by the developer) of the thick-film photoresist pattern obtained as described above by plating or the like. be able to. 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 thick film photoresist pattern is finally removed using a stripping solution or the like according to a conventional method.

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

<Examples 1-12, Comparative Examples 1-8>
Each component shown in Table 1 was uniformly dissolved in an organic solvent, filtered through a membrane filter having a pore size of 1 μm, and a photoresist composition was prepared so that the solid content concentration was 48 mass%. Numerical values in parentheses in Table 1 represent parts by mass of each component. The viscosity of the prepared photoresist composition was 4000 cP.

  ZA-1: a compound represented by the following formula

  ZA-2: Compound represented by the following formula

  ZA-3: Compound represented by the following formula

  ZB-1: Acrylic resin represented by the following formula (mass average molecular weight 40000, dispersity 1.8)

ZB-2: Acrylic resin (acrylic acid unit: phenyl acrylate unit: methyl adamantyl acrylate unit = 10: 30: 60 (molar ratio), molecular weight 200,000)
ZB-3: Acrylic resin (acrylic acid unit: methoxypolyethylene glycol acrylate unit: methyladamantyl acrylate unit = 10: 30: 60 (molar ratio), molecular weight 50,000)
ZB-4: novolak resin (m / p-cresol = 6/4 and 10% of the hydroxyl group of novolak resin obtained by addition condensation in the presence of formaldehyde and acid catalyst, protected with ethyl vinyl ether, molecular weight 20,000)
ZB-5: acrylic resin (acrylic acid unit: methyl acrylate unit: methoxytriethylene glycol acrylate unit: cyclohexyl acrylate unit: ethyl cyclohexyl acrylate = 10: 10: 10: 30: 40 (molar ratio), molecular weight 200,000)
ZC-1: novolak resin (obtained by addition condensation with m / p-cresol = 6/4 in the presence of formaldehyde and an acid catalyst, molecular weight 8000)
ZC-2: Polyhydroxystyrene resin (VP-2500: Nippon Soda Co., Ltd., molecular weight 3000)
PGMEA: Propylene glycol monomethyl ether acetate MA: 3-methoxybutyl acetate HP: 2-heptanone PGME: Propylene glycol monomethyl ether EL: Ethyl lactate CH: Cyclohexanone BA: Butyl acetate TPA: Tri-n-pentylamine

<Evaluation>
[Bubble evaluation]
The photoresist compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 8 were applied onto an 8-inch silicon substrate (scrubbed in a lattice pattern at a spacing of 2 cm, depth of 80 μm) using a spin coater. A thick photoresist layer having a thickness of 50 μm was obtained. The thick photoresist layer was prebaked at 140 ° C. for 5 minutes. After pre-baking, the number of bubbles having a diameter of 100 μm or more generated on the entire surface of the photoresist film was visually counted. The results are shown in Table 2.

  As can be seen from Table 2, in Examples 1 to 12 using a mixed solvent in which PGMEA and MA were mixed at a mass ratio of 60:40 to 20:80 as the organic solvent, the generation of bubbles was small. In addition, in Comparative Example 3 (MA alone) and Comparative Example 4 (HP alone), the generation of bubbles was small. However, in other comparative examples using PGMEA, PGME, EL, CH, and BA alone as the organic solvent, bubbles were easily generated.

[Photoresist pattern shape]
The photoresist compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were applied on an 8-inch copper substrate using a spin coater to obtain a thick photoresist layer having a thickness of 50 μm. The thick photoresist layer was prebaked at 140 ° C. for 5 minutes. After pre-baking, pattern exposure was performed with a ghi line using a mask having a predetermined hole pattern and an exposure apparatus Prism GHI (manufactured by Ultratech). Next, the substrate was placed on a hot plate and post-exposure heating (PEB) was performed at 80 ° C. for 3 minutes. Thereafter, an aqueous 2.38% tetramethylammonium hydroxide (TMAH) solution was dropped onto the thick photoresist layer and allowed to stand at 23 ° C. for 60 seconds, and this was repeated three times for development. Thereafter, it was washed with running water and blown with nitrogen to obtain a thick film resist pattern having a 40 μm contact hole pattern. The cross-sectional shape of this contact hole pattern was confirmed with a scanning electron microscope. The evaluation result was that the cross-sectional shape was rectangular, ◎, tapered shape, but the shape that can be used is ◯, and the taper shape was ×. The results are shown in Table 3.

  As can be seen from Table 3, good photoresist patterns were obtained in Examples 1 to 3 using mixed solvents in which PGMEA and MA were mixed at a mass ratio of 60:40 to 20:80 as organic solvents. It can be seen that these photoresist compositions are compositions in which the generation of bubbles is small and a favorable photoresist pattern can be formed. On the other hand, it was found that when the photoresist compositions of Comparative Examples 3 and 4 in which the generation of bubbles was small were used, the cross-sectional shape of the photoresist pattern was a taper shape, which was not suitable for use. The photoresist compositions of Comparative Examples 1 and 2 form a good photoresist pattern, but many bubbles are generated as shown in Table 2 and are not suitable for use.

Claims (7)

A thick film chemically amplified positive photoresist composition used for forming a thick photoresist layer on a support,
An acid generator (A) that generates an acid upon irradiation with actinic rays or radiation, a resin (B) whose solubility in an alkali is increased by the action of an acid, and an organic solvent (S),
A chemically amplified positive photoresist composition for thick film, wherein the organic solvent (S) is a mixed solvent in which propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are mixed at a mass ratio of 60:40 to 20:80.   The chemically amplified positive photoresist composition for thick film according to claim 1, further comprising an alkali-soluble resin (C).   The thick film according to claim 2, wherein the alkali-soluble resin (C) includes at least one resin selected from the group consisting of a novolac resin (C1), a polyhydroxystyrene resin (C2), and an acrylic resin (C3). Chemically amplified positive photoresist composition.   The chemically amplified positive photoresist composition for thick film according to any one of claims 1 to 3, further comprising an acid diffusion control agent (D).   A thick film photoresist laminate comprising a support and a thick film photoresist layer made of the chemically amplified positive photoresist composition for thick film according to any one of claims 1 to 4. . A laminating step of laminating a thick film photoresist layer comprising a chemically amplified positive photoresist composition for thick film according to any one of claims 1 to 4 on a support;
An exposure step of irradiating the thick photoresist layer with actinic rays or radiation; and
Developing the thick photoresist layer after exposure to obtain a thick photoresist pattern; and
For producing a thick film photoresist pattern comprising:   A method for producing a connection terminal, comprising a step of forming a connection terminal made of a conductor in a non-resist portion of a thick film photoresist pattern obtained by the method for producing a thick film photoresist pattern according to claim 6.