TW201812445A - Chemically-amplified type positive photo sensitive resin composition, method for manufacturing substrate with casting mold, and method for manufacturing plating molded article - Google Patents

Abstract

A chemically-amplified type positive photosensitive resin composition with excellent sensitivity and rectangularity, a method for manufacturing substrate with casting mold, and a method for manufacturing plating molded article are provided. The chemically-amplified type positive photosensitive resin composition includes a resin (A) with acid-dissociated protecting group and obtained by polymerizing a mixture, a photoacid generator (C), a solvent(D), a thiol compound (E), and a anthracene compound (F). The thiol compound (E) includes the structure represented by formula (E-1).

Description

Chemically amplified positive photosensitive resin composition, method for producing substrate with mold, and method for producing electroplated molded body

The present invention relates to a chemically amplified positive photosensitive resin composition, a method for producing a substrate with a mold, and a method for producing a plated molded article, and more particularly to a chemical capable of improving the problem of poor sensitivity and rectangularity. An enlarged positive photosensitive resin composition, a method for producing a mold-attached substrate obtained from the chemically amplified positive photosensitive resin composition, and a plated molded article obtained from the substrate with the mold attached thereto Production method.

Nowadays, optoelectronic processing has become the mainstream of precision micro-machining technology. The term "photoelectric processing" refers to the application of a photoresist composition on the surface of a workpiece to form a photoresist layer, and the photoresist layer is patterned by photolithography to form a patterned photoresist layer (light). The resist pattern is a general term for a technique of manufacturing various precision parts such as a semiconductor package by chemical etching, electrolytic etching, or electroforming mainly using plating.

In addition, in recent years, with the miniaturization of electronic devices, high-density assembly technology of semiconductor packages has progressed rapidly, and assembly of multi-pin films of packages has been achieved, and the size of packages has been reduced, and two-dimensional assembly of flip-chip methods has been carried out. Increased assembly density of technology and 3D assembly technology. In such a high-density assembly technique, as a connection terminal, for example, a bump electrode (assembly terminal) for connecting a bump or the like protruding toward the package, a rewiring and an assembly terminal extending from a peripheral terminal on the wafer The metal pillars and the like are arranged on the substrate with high precision.

As the above-mentioned photovoltaic processing system, a photoresist composition is used, and as such a photoresist composition, a chemically amplified photoresist composition containing an acid generator is known (see Patent Documents 1, 2, etc.). The chemically amplified photoresist composition generates an acid from an acid generator by radiation irradiation (exposure), promotes diffusion of acid by heat treatment, and reacts with a matrix resin in the composition to cause an acid catalyst to change its alkali dissolution. Sex.

Such a chemically amplified positive-type photoresist composition is used, for example, in the formation of an electroplated molded body such as a bump or a metal post in a plating step. Specifically, a chemically amplified photoresist composition is used, and a photoresist layer having a desired film thickness is formed on a support such as a metal substrate, and exposed and developed through a predetermined mask pattern to form a template. A photoresist pattern in which a portion where bumps or metal pillars are to be formed is selectively removed (peeled). Thereafter, by embedding a conductor such as copper in the removed portion (non-photosensitive portion), the photoresist pattern around the photoresist pattern is removed, whereby a bump or a metal pillar can be formed.

However, the aforementioned chemically amplified positive-type photoresist composition has the disadvantages of poor sensitivity and poor rectangularity of the formed photoresist pattern, and cannot be accepted by the industry. Therefore, how to provide a chemically amplified positive-type photoresist composition capable of forming a photoresist pattern with good sensitivity and rectangularity is a problem that those skilled in the art are currently trying to solve. [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 9-176112 (Patent Document 2)

In view of the above, the present invention provides a chemically amplified positive photosensitive resin composition, which can improve the problem of poor sensitivity and rectangularity by using the chemically amplified positive photosensitive resin composition.

The present invention provides a chemically amplified positive photosensitive resin composition comprising: a resin (A), a photoacid generator (C), and a solvent (D) obtained by copolymerization of a monomer mixture and containing an acid dissociable protecting group. ), a thiol compound (E), and a quinone compound (F). Wherein the thiol compound (E) has a structure represented by the following formula (E-1): In the formula (E-1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ represents a single bond or a carbon number of 1 to 10. An alkyl group, R ⁴ represents a u-valent organic group; and u represents an integer of 2 to 6.

In an embodiment of the invention, the above monomer mixture comprises a monomer (a1) having a structure represented by the following formula (A-1): In the formula (A-1), L ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a carbon number of 1 to 6. a linear or branched fluorinated alkyl group; L ² , L ³ , and L ⁴ each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms or a carbon number of 1 to 6; A linear or branched fluoroalkyl group, or L ³ and L ⁴ are bonded to each other to form a hydrocarbon ring having 5 to 20 carbon atoms.

In an embodiment of the invention, the monomer mixture comprises a monomer (a2), and the monomer (a2) comprises a polyoxyalkylene chain.

In an embodiment of the invention, the chemically amplified positive photosensitive resin composition further includes a novolak resin (B).

In an embodiment of the invention, the total amount of the resin (A) used is 100 parts by weight, the photoacid generator (C) is contained in an amount of from 0.5 part by weight to 4.5 parts by weight, and the solvent (D) is contained in an amount of 60 parts by weight. The content of the thiol compound (E) is from 0.3 part by weight to 3 parts by weight, and the content of the quinone compound (F) is from 0.2 part by weight to 1.5 parts by weight to 600 parts by weight.

In an embodiment of the invention, the monomer (a1) is used in an amount of from 20 parts by weight to 80 parts by weight based on 100 parts by total of the total of the monomer mixture.

In an embodiment of the invention, the monomer (a2) is used in an amount of 10 parts by weight to 60 parts by weight based on 100 parts by weight of the total of the monomer mixture.

In an embodiment of the invention, the total amount of the resin (A) used is 100 parts by weight, and the content of the novolak resin (B) is from 20 parts by weight to 180 parts by weight.

The present invention also provides a method for producing a substrate with a mold, comprising: a laminating step of laminating a photosensitive resin composed of the above chemically amplified positive photosensitive resin composition on a metal surface of a substrate having a metal surface In the layer and the exposure step, the photosensitive resin layer is irradiated with actinic rays or radiation, and a developing step, and the exposed photosensitive resin layer is developed to form a mold for forming a plated molded body.

The present invention further provides a method for producing a plated molded body, comprising the step of forming a plated molded body in a mold by performing electroplating on a mold-attached substrate manufactured by the method for manufacturing a substrate with a mold as described above.

In the chemically amplified positive-type photosensitive resin composition of the present invention, since the thiol compound (E) and the quinone compound (F) are contained, the problem of poor sensitivity and rectangularity can be improved.

The above described features and advantages of the invention will be apparent from the following description.

< Chemical Amplifying Positive Photosensitive Resin Composition > The present invention provides a chemically amplified positive photosensitive resin composition comprising: a resin (A) obtained by copolymerizing a monomer mixture and containing An acid dissociable protecting group, a photoacid generator (C), a solvent (D), a thiol compound (E), and an anthraquinone compound (F). Further, the chemically amplified positive photosensitive resin composition of the present invention may further contain a novolak resin (B) and an additive (G).

The respective components used in the chemically amplified positive photosensitive resin composition of the present invention will be described in detail below.

Here, the following description means that acrylic acid and/or methacrylic acid is represented by (meth)acrylic acid, and acrylate and/or methacrylate is represented by (meth)acrylate; similarly, (meth) The acryl fluorenyl group means an acryl fluorenyl group and/or a methacryl fluorenyl group. Resin ( A )

The resin (A) is obtained by copolymerization of a monomer mixture and contains an acid dissociable protecting group. Specifically, the monomer mixture may include a monomer (a1) having a structure represented by the formula (A-1), a polyoxyalkylene group-containing monomer (a2), having the formula (A-2) or A monomer (a3) having a structure represented by the formula (A-3) and another monomer (a4). Monomer having a structure represented by formula (A-1) ( a1 )

The monomer (a1) having the structure represented by the formula (A-1) is as follows: In the formula (A-1), L ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a carbon number of 1 to 6. a linear or branched fluorinated alkyl group; L ² , L ³ , and L ⁴ each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms or a carbon number of 1 to 6; A linear or branched fluorinated alkyl group, or L ³ and L ⁴ are bonded to each other to form a hydrocarbon ring having 5 to 20 carbon atoms.

Further, examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, and an isopentyl group. New amyl and so on. Further, the fluorinated alkyl group means a part or all of the hydrogen atom of the above alkyl group is substituted with a fluorine atom.

When L ³ and L ^{4 are} not bonded to each other to form a hydrocarbon ring, L ² , L ³ and L ^{4 are} preferably a linear or branched alkyl group having 2 to 4 carbon atoms.

The above L ³ and L ⁴ may form an aliphatic cyclic group having 5 to 20 carbon atoms together with the carbon atom to which the two are bonded. Specific examples of such an aliphatic cyclic group include a group in which one or more hydrogen atoms are removed by a polycycloalkane such as a monocycloalkane, a dicycloalkane, a tricycloalkane or a tetracycloalkane. Specific examples thereof include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or adamantane, norbornane, isobornene, tricyclodecane, and tetracyclododecane. The polycycloalkane removes a group of one or more hydrogen atoms. In particular, a group in which one or more hydrogen atoms are removed by cyclohexane or adamantane (which may further have a substituent) is preferred.

In addition, when the aliphatic cyclic group formed by the above L ³ and L ⁴ has a substituent on the ring skeleton, examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom ( =O) an equipolar group or a linear or branched alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (=O) is preferred.

Specific examples of the monomer (a1) having a structure represented by the formula (A-1) include the following compounds represented by the formula (A-1-1) to the formula (A-1-33): Formula (A-1-1) Formula (A-1-2) Formula (A-1-3) Formula (A-1-4) Formula (A-1-5) Formula (A-1-6) Formula (A-1-7) Formula (A-1-8) Formula (A-1-9) Formula (A-1-10) Formula (A-1-11) Formula (A-1-12) Formula (A-1-13) Formula (A-1-14) Formula (A-1-15) Formula (A-1-16) Formula (A-1-17) Formula (A-1-18) Formula (A-1-19) Formula (A-1-20) Formula (A-1-21) Formula (A-1-22) Formula (A-1-23) Formula (A-1-24) Formula (A-1-25) Formula (A-1-26) Formula (A-1-27) Formula (A-1-28) Formula (A-1-29) Formula (A-1-30) Formula (A-1-31) Formula (A-1-32) In the formula (A-1-1-1) to the formula (A-1-33), L ¹¹ represents a hydrogen atom or a methyl group.

The monomer (a1) is used in an amount of from 20 parts by weight to 80 parts by weight, based on the total amount of the monomer mixture, preferably from 25 parts by weight to 75 parts by weight, more preferably from 30 parts by weight to 70 parts by weight. .

When the monomer mixture (a1) having a structure represented by the formula (A-1) is included in the monomer mixture, the squareness of the chemically amplified positive photosensitive resin composition can be further improved. Monomer containing polyoxyalkylene chain ( a2 )

The polyoxyalkylene-containing monomer (a2) may be exemplified by the following specific examples, but is not limited to these specific examples: ethylene oxide (hereinafter referred to as EO) modified benzyl cresol ( Product name: ARONIX TO-901), EO modified dodecyl acrylate (trade name: ARONIX TO-950), EO modified tridecyl acrylate (trade name: ARONIX TO-951), acrylic acid (2 -ethylhexyl-polyethylene glycol) ester (trade name: ARONIX TO-946~TO-949), the above is manufactured by East Asia Synthetic Co., Ltd.; acrylic acid (ethyl-diethylene glycol) ester (trade name: Light Acrylate EC-A), acrylic acid (methoxy-triethylene glycol) ester (trade name: Light Acrylate MTG-A), acrylic acid (methoxy-polyethylene glycol) ester (trade name: Light Acrylate 130A) Acrylic (phenoxy-polyethylene glycol) ester (trade name: Light Acrylate P-200A), acrylic acid (nonylphenyl-polyoxyethyl chain addenda) ester (trade name: Light Acrylate NP-4EA, NP-8EA), the above is manufactured by Kyoeisha Chemical Co., Ltd.; polyethylene glycol acrylate (trade name: BLEMMER AE-350), polyethylene glycol methacrylate (trade name: BL) EMMER PE-90, PE-200, PE-350), acrylic acid (methoxy-polyethylene glycol) ester (trade name: BLEMMER AME-400), methacrylic acid (methoxy-polyethylene glycol) ester (trade name: BLEMMER PME-100, PME-200, PME-400), polypropylene glycol methacrylate (trade name: BLEMMER PP-500, PP-800), methacrylic acid (polyethylene glycol-polypropylene glycol) Ester (trade name: BLEMMER 70PEP-370B), methacrylic acid (polyethylene glycol-polybutylene glycol) ester (trade name: BLEMMER 50PET-800), methacrylic acid (octyloxy-polyethylene glycol-poly Propylene glycol) ester (trade name: BLEMMER 50POEP-800B, 50AOEP-800B), the above is manufactured by Nippon Oil & Fat Co., Ltd.; methacrylic acid (methoxy-diethylene glycol) ester (trade name: NK Ester M-20G , M-40G, M-90G), and acrylic acid (phenoxy-diethylene glycol) ester (trade name: NK Ester AMP-20G), the above is manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

The monomer (a2) is used in an amount of 10 parts by weight to 60 parts by weight, based on 100 parts by weight based on the total amount of the monomer mixture, preferably 15 parts by weight to 55 parts by weight, more preferably 20 parts by weight to 50 parts by weight. .

When the monomer mixture contains the polyoxyalkylene group-containing monomer (a2), the sensitivity of the chemically amplified positive photosensitive resin composition can be further improved. a monomer having a structure represented by formula (A-2) or formula (A-3) ( a3 )

The monomer (a3) having a structure represented by the formula (A-2) or the formula (A-3) is as follows: Formula (A-2) In the formula (A-2) and the formula (A-3), L ⁵ to L ¹⁰ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms; Y represents a alicyclic group or alkyl group which may have a substituent, p represents an integer of 0 to 4, and q represents 0 or 1.

Further, in the formula (A-2) and the formula (A-3), a linear or branched alkyl group of L ⁵ to L ¹⁰ and a linear or branched fluorinated alkyl group are defined as described above. The linear or branched alkyl group defined by L ¹ in the formula (A-1) and the linear or branched fluorinated alkyl group are the same, and will not be described herein.

When Y is an alicyclic group or an alkyl group, a group in which one or more hydrogen atoms are removed by a polycycloalkane such as a monocycloalkane, a dicycloalkane, a tricycloalkane or a tetracycloalkane may be mentioned. Specific examples thereof include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or adamantane, norbornane, isobornene, tricyclodecane, and tetracyclododecane. The polycycloalkane removes a group of one or more hydrogen atoms. In particular, a group in which one or more hydrogen atoms are removed from adamantane (which may further have a substituent) is preferred.

In addition, when the alicyclic group represented by Y has a substituent on the ring skeleton, examples of the substituent include a polar group such as a hydroxyl group, a carboxyl group, a cyano group, or an oxygen atom (=O), or A linear or branched alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (=O) is preferred.

Further, when Y is an alkyl group, a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 6 to 15 carbon atoms is preferred. Such an alkyl group is particularly preferably an alkoxyalkyl group, and examples of such an alkoxyalkyl group include 1-methoxyethyl, 1-ethoxyethyl and 1-n-propoxy B. , 1-isopropoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-tert-butoxyethyl, 1-methoxypropyl, 1-B Oxypropyl, 1-methoxy-1-methyl-ethyl, 1-ethoxy-1-methylethyl, and the like.

Specific examples of the monomer (a3) having a structure represented by the formula (A-2) or the formula (A-3) include the following formula (A-2-1) to formula (A-2-24). a compound represented by the formula (A-3-1) to the formula (A-3-15): Formula (A-2-1) Formula (A-2-2) Formula (A-2-3) Formula (A-2-4) Formula (A-2-5) Formula (A-2-6) Formula (A-2-7) Formula (A-2-8) Formula (A-2-9) Formula (A-2-10) Formula (A-2-11) Formula (A-2-12) Formula (A-2-13) Formula (A-2-14) Formula (A-2-15) Formula (A-2-16) Formula (A-2-17) Formula (A-2-18) Formula (A-2-19) Formula (A-2-20) Formula (A-2-21) Formula (A-2-22) Formula (A-2-23) Formula (A-2-24) Formula (A-3-1) Formula (A-3-2) Formula (A-3-3) Formula (A-3-4) Formula (A-3-5) Formula (A-3-6) Formula (A-3-7) Formula (A-3-8) Formula (A-3-9) Formula (A-3-10) Formula (A-3-11) Formula (A-3-12) Formula (A-3-13) Formula (A-3-14) Formula (A-3-15) Formula (A-2-1)~Formula (A-2-24), Formula (A-3-1)~Formula (A-3-15), L ¹¹ represents a hydrogen atom Or methyl. Other monomer ( a4 )

In the monomer mixture, as long as the effects of the present invention are not impaired, other monomers (a4) which do not belong to the above monomer (a1) to monomer (a3) may be further included. The other monomer (a4) is, for example, a known radical polymerizable compound or an anionic polymerizable compound.

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; and 2-methylpropenyloxyethyl amber. a carboxyl group and an ester bond such as 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxyethylphthalic acid or 2-methylpropenyloxyethylhexahydrophthalic acid a methacrylic acid derivative; (meth)acrylic acid alkyl ester, methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate (hydroxy) (meth) acrylate such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; glycidyl (meth)acrylate, (methyl) 2-methylglycidyl acrylate, 3,4-epoxybutyl (meth)acrylate, -6,7-epoxyheptyl (meth)acrylate, (meth)acrylic acid-3,4 - epoxycyclohexyl esters such as epoxycyclohexyl ester or (meth)acrylic acid-3,4-epoxycyclohexylmethyl ester; phenyl (meth)acrylate, benzyl (meth)acrylate, etc. Acrylate aryl esters; diethyl maleate, fuma Dicarboxylic acid diesters such as dibutyl ester; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, α-B Vinyl-containing aromatic compounds such as hydroxy styrene; vinyl-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; acrylonitrile, methacrylonitrile, etc. A polymerizable compound containing a nitrile group; a chlorine-containing polymerizable compound such as vinyl chloride or vinylidene chloride; a polymerizable compound containing a guanamine bond such as acrylamide or methacrylamide.

In addition, examples of the polymerizable compound include aliphatic polycyclic group-containing (meth) acrylates having a non-dissociable acid group, and vinyl group-containing aromatic compounds. The aliphatic polycyclic group which is non-dissociable acid is preferably a tricyclic fluorenyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, a norbornyl group, etc., and is preferably industrially easy to obtain. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

Specific examples of the (meth) acrylate having an aliphatic polycyclic group having an acid non-dissociable property include the following formulas (A-4-1) to (A-4-5). Compound: Formula (A-4-1) Formula (A-4-2) Formula (A-4-3) Formula (A-4-4) Formula (A-4-5) In the formula (A-4-1) to the formula (A-4-5), L ¹¹ represents a hydrogen atom or a methyl group.

The other monomer (a4) is used in an amount of 5 parts by weight to 40 parts by weight, based on the total amount of the monomer mixture, preferably 8 parts by weight to 35 parts by weight, more preferably 10 parts by weight to 30 parts by weight. Share.

The solvent used in the preparation of the resin (A) includes, but is not limited to, (1) an alcohol compound: methanol, ethanol, benzyl alcohol, 2-phenylethanol, or 3-phenyl-1-propanol, etc.; (2) an ether compound : tetrahydrofuran, etc.; (3) glycol ether compound: ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.; (4) ethylene glycol alkyl ether acetate: ethylene glycol Ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether acetate, etc.; (5) diethylene glycol compounds: diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol single Dibutyl glycol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, etc.; (6) dipropylene glycol compound: dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ether, etc.; (7) propylene glycol monoalkyl ether compound: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.; 8) Propylene glycol alkyl ether acetate compound: Propylene glycol monomethyl ether aceta Te), propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc.; (9) propylene glycol alkyl ether propionate compound: propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol propyl ether Propionate, propylene glycol butyl ether propionate, etc.; (10) aromatic hydrocarbon compounds: toluene, xylene, etc.; (11) ketone compounds: methyl ethyl ketone, cyclohexanone, diacetone alcohol, etc.; (12) ester compounds : methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate , methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropionic acid Ester, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate Ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, C Butyl acetate, methyl butoxyacetate, ethyl butoxylate, propyl butoxyacetate, butyl butoxyacetate, 3-methoxybutyl acetate, 2-methoxypropyl Methyl ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropane Ethyl acetate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropane Propyl acrylate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropane Butyl acrylate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-propoxypropane Methyl ester, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butoxypropane Ethyl acetate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, etc., which may be used singly or in combination.

The polymerization initiator used in the preparation of the resin (A) includes, but is not limited to, an azo compound or a peroxide, and may be used singly or in combination.

Azo compounds such as, but not limited to, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) [2,2'-Azobis (2,4) -dimethylvaleronitrile)], 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-2-methylbutyronitrile [2,2 '-azobis-2-methyl butyronitrile, 4,4'-azobis(4-cyanovaleric acid), dimethyl 2,2'-azobis(2-methylpropionate), 2, 2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile) and the like.

Peroxides such as, but not limited to, benzamidine peroxide, dodecyl peroxide, t-butyl peroxyvalerate, 1,1-bis(tert-butylperoxy)cyclohexane, hydrogen peroxide Wait.

The reaction temperature at the time of preparing the resin (A) is 40 to 120 degrees, and the polymerization time is 3 to 12 hours.

The resin (A) has a weight average molecular weight of 5,000 to 50,000; preferably 6,000 to 45,000; more preferably 7,000 to 40,000. Novolak resin ( B )

The novolak resin (B) is obtained by a polycondensation reaction of an aldehyde compound and an aromatic hydroxy compound in the presence of an acidic catalyst.

Specific examples of the aldehyde compound, such as: formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde (crotonaldehyde), cyclohexanealdehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropanal, β Phenylpropanal, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, and the like. The above aldehyde compounds may be used singly or in combination of plural kinds. Preferably, the aldehyde compound can be formaldehyde or benzaldehyde.

Specific examples of the aromatic hydroxy compound include phenol such as phenol, m-cresol, p-cresol, and o-cresol (cresol). a compound; a xylenol compound such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol or 3,4-xylenol; m-ethylphenol , p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol , an alkyl group such as 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol or 6-t-butyl-3-methylphenol An alkylphenol compound; an alkane such as p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol or m-propoxyphenol. Alkoxy phenol compound; isopropenyl phenol, p-isopropenyl phenol, 2-methyl-4-isopropenyl phenol, 2-ethyl-4-isopropenyl phenol, etc. Isopropenyl phenol compound; aryl phenol compound of phenyl phenol; 4 , 4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, and other polyhydroxyphenols Class of compounds. The aromatic hydroxy compound may be used singly or in combination of plural kinds.

Preferably, the aromatic hydroxy compound may be 3,5-xylenol, 3,4-xylenol, 2,5-xylenol, o-cresol, m-cresol or p-cresol.

Specific examples of the acidic catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid or p-toluenesulfonic acid.

The novolak resin (B) may be used singly or in combination of plural kinds. The total amount of the resin (A) used is 100 parts by weight, and the content of the novolac resin (B) is from 20 parts by weight to 180 parts by weight, preferably from 25 parts by weight to 160 parts by weight, more preferably from 30 parts by weight to 140 parts by weight. Parts by weight.

The novolak resin (B) has a weight average molecular weight of 5,000 to 50,000; preferably 6,000 to 45,000; more preferably 7,000 to 40,000.

When the novolac resin (B) is contained in the chemically amplified positive photosensitive resin composition, the squareness can be further improved. Photoacid generator ( C )

The photoacid generator (C) is a compound which generates an acid by irradiation with actinic rays or radiation, and is not particularly limited as long as it is a compound which can directly or indirectly generate an acid by light. The photoacid generator (C) is preferably an acid generator of the first to fifth aspects described below. Hereinafter, among the photoacid generators (C) which are suitably used in the photosensitive resin composition, the first to fifth aspects will be described.

The first form of the photoacid generator (C) is a compound represented by the following formula (C-1): In the formula (C-1), X ¹ represents a g-valent sulfur atom or an iodine atom, and g is 1 or 2. h represents the number of repeating units of the structure in parentheses. W ¹ is an organic group bonded to X ¹ and represents 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, and a carbon number. An alkenyl group of 2 to 30 or an alkynyl group having 2 to 30 carbon atoms, and W ¹ may be via an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group or an arylthiocarbonyl group. , methoxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkanesulfonyl, arylsulfonyl, alkoxy, At least one substitution selected from the group consisting of an amine group, a cyano group, a nitro group, and a halogen. The number of W ¹ is g+h(g-1)+1, and W ¹ may be identical or different from each other. Further, two or more W ¹ may be directly bonded to each other or via -O-, -S-, -SO-, -SO ₂ -, -NH-, -NW ² -, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenyl group bonded to form a ring structure containing X ¹ . W ² is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

X ² is a structure represented by the following formula (C-1a): In the formula (C-1a), X ⁴ represents an alkylene group having 1 to 8 carbon atoms, an extended aryl group having 6 to 20 carbon atoms, or a carbon number of 8 to 20 a divalent hetero group, X ⁴ may be via an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxyl group, a cyano group, or a nitro group. And at least one substitution selected from the group consisting of halogens. X ⁵ represents -O-, -S-, -SO-, -SO ₂ -, -NH-, -NW ² -, -CO-, -COO-, -CONH-, and a carbon number of 1 to 3 Alkyl, or phenyl. h represents the number of repeating units of the structure in parentheses. h+1 X ⁴ and h X ⁵ may be the same or different, respectively. The W ² system is the same as defined above.

(X ³ ) ^- is a counter ion, and a fluoroalkyl fluorophosphate anion represented by the following formula (C-1b) or a borate anion represented by the following formula (C-1c) [(W ³ ) _j PF _6-j ] ^- Formula (C-1b) In the formula (C-1b), W ³ represents an alkyl group in which 80% or more of hydrogen atoms are substituted with a fluorine atom. j represents the number thereof, and is an integer of 1 to 5. j W ³ may be the same or different. In the formula (C-1c), W ⁴ to W ⁷ each independently represent a fluorine atom or a phenyl group, and a part or all of the hydrogen atoms in the phenyl group may be formed via a fluorine atom and a trifluoromethyl group. At least one substitution selected from the group.

Examples of the phosphonium ion in the compound represented by the formula (C-1) include triphenylsulfonium, tri-p-tolylhydrazine, 4-(phenylthio)phenyldiphenylphosphonium, and bis[4-( Diphenylmercapto)phenyl]thioether, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]indolyl}phenyl] sulfide, double {4-[double (4- Fluorophenyl)indenyl]phenyl}thioether, 4-(4-benzylidene-2-chlorophenylthio)phenylbis(4-fluorophenyl)anthracene, 7-isopropyl-9- Oxy-10-thia-9,10-dihydroindol-2-yldi-p-tolylhydrazine, 7-isopropyl-9-oxy-10-thia-9,10-dihydroanthracene- 2-yldiphenylanthracene, 2-[(diphenyl)indenyl]thiazinone, 4-[4-(4-tri-butylbenzylidene)phenylthio]phenyldi-pair Tolylhydrazine, 4-(4-benzylidenephenylthio)phenyldiphenylphosphonium, diphenylphenethylhydrazine, 4-hydroxyphenylmethylbenzylhydrazine, 2-naphthylmethyl (1-ethoxycarbonyl)ethyl hydrazine, 4-hydroxyphenylmethyl phenethyl hydrazine, phenyl [4-(4-biphenylthio)phenyl] 4-biphenyl hydrazine, phenyl [ 4-(4-biphenylthio)phenyl]3-biphenyl fluorene, [4-(4-ethylphenylthio)phenyl]diphenyl fluorene, octadecylmethyl phenyl hydrazino, Diphenyl hydrazine, di-p-tolyl fluorene, bis(4-dodecylphenyl) fluorene, (4-methoxyphenyl)anthracene, (4-octyloxyphenyl)phenylhydrazine, bis(4-dodecyloxy)phenylhydrazine, 4-(2-hydroxytetradecyloxy)phenyl Phenylhydrazine, 4-isopropylphenyl (p-tolyl) anthracene, or 4-isobutylphenyl (p-tolyl) anthracene or the like.

Among the cerium ions in the compound represented by the above formula (C-1), preferred cerium ions include cerium ions represented by the following formula (C-1d): In the formula (C-1d), W ⁸ independently represents a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, a halogen atom, or a substituent. A group selected from the group consisting of an aryl group and an arylcarbonyl group. X ² represents the same meaning as X ² in the above formula (C-1).

Specific examples of the phosphonium ion represented by the above formula (C-1d) include 4-(phenylthio)phenyldiphenylphosphonium and 4-(4-benzoguanidino-2-chlorophenylthio). Phenyl bis(4-fluorophenyl)anthracene, 4-(4-benzylidenephenylthio)phenyldiphenylanthracene, phenyl[4-(4-biphenylthio)phenyl]4 -biphenyl fluorene, phenyl [4-(4-biphenylthio)phenyl]3-biphenyl fluorene, [4-(4-ethylphenylthio)phenyl]diphenyl fluorene, diphenyl [4-(p-triphenylthio)phenyl]diphenylphosphonium.

In the fluoroalkylfluorophosphate anion represented by the above formula (C-1b), W ³ represents an alkyl group substituted by a fluorine atom, preferably a carbon number of 1 to 8, more preferably 1 to 4 carbon atoms. Specific examples of the alkyl group include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or an octyl group; an isopropyl group, an isobutyl group, a secondary butyl group, and a tertiary butyl group; Or a branched alkyl group; even a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group; and the ratio of the hydrogen atom of the alkyl group to the fluorine atom is usually 80% or more, preferably 90% or more. More preferably 100%. When the substitution ratio of a fluorine atom is less than 80%, the acid strength of the fluorinated fluoroalkyl fluorophosphate represented by the above formula (C-1) is lowered.

Particularly preferred W ³ is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution ratio of 100%, and specific examples thereof include CF ₃ and 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. The number j of W ^{3 is} an integer of 1 to 5, preferably 2 to 4, and particularly preferably 2 or 3.

Specific examples of the preferred fluoroalkyl fluorophosphate anion 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 ] ^- , among these, particularly preferably [(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 ] ^- .

Preferred examples of the borate anion represented by the above formula (C-1c) include quinone (pentafluorophenyl) borate ([B(C ₆ F ₅ ) ₄ ] ^- ), 肆 [(three) Fluoromethyl)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 ] ^- ), 肆(difluorophenyl)borate ([B(C ₆ H ₃ F ₂ ) ₄ ] ^- ), etc. . Among them, particularly preferred is quinone (pentafluorophenyl) borate ([B(C ₆ F ₅ ) ₄ ] ^- ).

As the second form of the acid generator (A), 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine and 2,4-bis(trichloromethane) are mentioned. -6-[2-(2-furyl)vinyl]symmetric triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)ethene Symmetrical triazine, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)vinyl]symmetric triazine, 2,4-bis(trichloromethane) -6-[2-(5-propyl-2-furanyl)vinyl]symmetric triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethyl Oxyphenyl)vinyl]symmetric triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)vinyl]symmetric triazine, 2, 4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)vinyl]symmetric triazine, 2,4-bis(trichloromethyl)-6-[2 -(3-methoxy-5-ethoxyphenyl)vinyl]symmetric triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-propane Oxyphenyl)vinyl]symmetric triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)vinyl]symmetric triazine, 2 ,4-bis(trichloromethyl)-6-(3,4-methylenedioxyphenyl) symmetric triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4- Methoxy)phenyl symmetric triazine, 2,4-bis-trichloro Methyl-6-(2-bromo-4-methoxy)phenyl symmetric triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylbenzene Symmetrical triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl symmetrical 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)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl) 2-furyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,5-dimethoxyphenyl)vinyl ]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis ( Trichloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three Halogen-containing triazine compounds such as azine, 1,3-(dibromopropyl)-1,3,5-triazine, ginseng (2,3-dibromopropyl)-1,3,5-triazine And a halogen-containing triazine compound represented by the following formula (C-2) such as (2,3-dibromopropyl)trimeric isocyanate. In the formula (C-2), W ⁹ to W ¹¹ are each independently represented by a haloalkyl group.

Further, examples of the third form of the photoacid generator (C) include α-(p-toluenesulfonyloxyimino)-phenylacetonitrile and α-(phenylsulfonyloxyimino)-2. ,4-dichlorophenylacetonitrile, α-(phenylsulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorophenylsulfonyloxyimino)-4- Methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-chloropentenylacetonitrile, and a compound represented by the following formula (C-3) containing a sulfonic acid sulfhydryl group. In the formula (C-3), W ¹² represents a monovalent, divalent or trivalent organic group, and W ¹³ represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic compound. Base, n represents the number of repeating units of the structure within the brackets.

In the above formula (C-3), the aromatic compound group represents a group of a compound which exhibits physical and chemical properties peculiar to the aromatic compound, and examples thereof include an aryl group such as a phenyl group or a naphthyl group, or a furyl group or a thienyl group. Isoheteroaryl. These may also have one or more suitable substituents on the ring, such as a halogen atom, an alkyl group, an alkoxy group, a nitro group or the like. Further, W ^{13 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 W ¹² is an aromatic compound group and W ¹³ is an alkyl group having 1 to 4 carbon atoms is preferable.

As the acid generator represented by the above formula (C-3), when n=1, a compound in which W ¹² is a phenyl group, a methylphenyl group or a methoxyphenyl group, and W ¹³ is a methyl group is exemplified. Specific examples thereof include α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, --(Methanesulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile, [2-(propanesulfonyloxyimino)-2,3-dihydroxythiophene-3- Subunit] (o-tolyl) acetonitrile and the like. When n=2, the acid generator represented by the above formula (C-3) specifically includes an acid represented by the following formula (C-3-1) to formula (C-3-8). Producer: Formula (C-3-1) Formula (C-3-2) Formula (C-3-3) Formula (C-3-4) Formula (C-3-5) Formula (C-3-6) Formula (C-3-7) Formula (C-3-8)

Further, as a fourth aspect of the photoacid generator (C), a phosphonium salt having a naphthalene ring in a cationic portion can be given. The term "having a naphthalene ring" means a structure derived from naphthalene, meaning a structure of at least two rings, and can maintain the aromaticity thereof. The naphthalene ring may have 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 (free valence of 1), or a divalent group (free valence of 2) or more, and more preferably a monovalent group (only, at this time, the deduction is as described above) The part of the substituent bond is combined to calculate the free atomic valence). The number of naphthalene rings is preferably from 1 to 3.

The cationic moiety of the phosphonium salt having a naphthalene ring as such a cationic moiety is preferably a structure represented by the following formula (C-4): In the formula (C-4), at least one of W ¹⁴ to W ¹⁶ represents a group represented by the following formula (C-4a), and the remainder represents a linear chain having 1 to 6 carbon atoms. Or a branched 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 W ¹⁴ to W ¹⁶ is a group represented by the following formula (C-4a), and the other two are independently a linear or branched alkyl group having a carbon number of W ¹⁴ to W ¹⁶ . These ends can be bonded and ring-shaped. In the formula (C-4a), W ¹⁷ and W ¹⁸ each independently represent a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a carbon atom number. A straight or branched alkyl group of 1 to 6, and W ¹⁸ represents a single bond or a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent. l and m respectively represent an integer of 0~2, and l+m is 3 or less. When there are a plurality of W ¹⁷ , they may be the same or different from each other. When there are a plurality of W ^18s , they may be identical or different from each other.

The number of the groups represented by the above formula (C-4a) in the above W ¹⁴ to W ^{16 is} preferably one based on the stability of the compound, and the remainder is a linear or branched form having 1 to 6 carbon atoms. An alkyl group, the ends of which may be bonded to form a ring. In this case, the above two alkylene groups may contain a sulfur atom to form a 3 to 9 membered ring. The number of atoms (sulfur atoms) constituting the ring is preferably from 5 to 6.

In addition, examples of the substituent which the above-mentioned alkylene group may have include an oxygen atom (in this case, a carbon atom together with a carbon atom constituting a stretch alkyl group), a hydroxyl group, and the like.

In addition, examples of the substituent which 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 carbon number of 1 to 6. Alkyl and the like.

In the case of the above-mentioned formula (C-4b) or (C-4c), it is preferable to use a structure represented by the following formula (C-4c). Formula (C-4b) Formula (C-4c)

As such a cationic moiety, it may be a phosphonium salt or a phosphonium salt; and an anthracene salt is preferable from the viewpoint of acid production efficiency and the like.

Therefore, an anion moiety suitable for a phosphonium salt having a naphthalene ring as a cationic moiety is preferably an anion capable of forming a phosphonium salt.

As an anion portion of such an acid generator, a part or all of a hydrogen atom is a fluorinated fluoroalkylsulfonate ion or an arylsulfonate ion.

The alkyl group in the fluoroalkylsulfonate ion may be a linear, branched or cyclic group having 1 to 20 carbon atoms, and preferably has a carbon number of 1 based on the volume of the acid produced and the diffusion distance thereof. To 10. Particularly branched or ring-shaped is preferred because of the short diffusion distance. Further, examples of the synthesis at a low cost include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group and the like.

The aryl group in the arylsulfonic acid ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group which may be substituted by an alkyl group or a halogen atom. In particular, from the viewpoint of inexpensive synthesis, an aryl group having 6 to 10 carbon atoms is preferred. Specific examples of the preferred ones include a phenyl group, a tolsulfonyl group, an ethylphenyl group, a naphthyl group, a methylnaphthyl group and the like.

In the above fluoroalkylsulfonate ion or arylsulfonate ion, the fluorination rate when a part or all of the hydrogen atom is fluorinated is preferably from 10 to 100%, more preferably from 50 to 100%, and particularly substituted by a fluorine atom. All of the hydrogen atoms are preferred because of the enhanced strength of the acid. Specific examples thereof include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, and perfluorobenzenesulfonate.

Among these, the preferred anion moiety is represented by the following formula (C-4d): W ²⁰ SO ₃ ^- Formula (C-4d) In the formula (C-4d), W ²⁰ is a formula The groups shown by (C-4e), (C-4f), and (C-4g). -C _x F _2x+1 (C-4e) Formula (C-4f) Formula (C-4g) In the formula (C-4e), x represents an integer of 1 to 4. In the formula (C-4f), W ²¹ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched carbon group having 1 to 6 carbon atoms. Alkoxy, y represents an integer from 1 to 3. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.

Further, as the anion portion, a nitrogen-containing one represented by the following formula (C-4h) or formula (C-4i) can also be used. Formula (C-4h) In the formula (C-4h), in the formula (C-4i), X ^a represents a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group The number of carbon atoms is 2 to 6, preferably 3 to 5, and most preferably the number of carbon atoms is 3. Further, Y ^a and Z ^a each independently represent 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, preferably 1 to 7 carbon atoms. Good for 1~3.

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

Further, in the alkyl group of X ^a or the alkyl group of Y ^a or Z ^a , the more the number of hydrogen atoms substituted by a fluorine atom, the stronger the strength of the acid, which is preferable. The proportion of the fluorine atom in the alkyl group or the alkyl group, that is, the fluorination rate is preferably from 70 to 100%, more preferably from 90 to 100%, most preferably a perfluoroalkylene group in which all hydrogen atoms are replaced by a fluorine atom. Base or perfluoroalkyl.

Examples of the sulfonium salt having a naphthalene ring as such a cation moiety include compounds represented by the following formula (C-4j) and formula (C-4k): Formula (C-4j) Formula (C-4k)

Further, as a fifth form of the photoacid generator (C), bis(p-toluenesulfonyl)diazomethane or bis(1,1-dimethylethylsulfonyl)diazomethane may be mentioned. Bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, etc.; dinitrosulfonyldiazomethane; p-toluenesulfonic acid 2-nitrobyl Ester, 2,6-dinitrobenzyl methyl p-toluenesulfonate, nitrobenzyl methyl tosylate, dinitrophenyl methyl toluenesulfonate, nitrophenyl methyl sulfonate, nitrobenzyl methyl carbonate , nitrobenzyl derivative such as dinitrophenyl carbonate; pyrogallol triflate, pyrogallol trimethyl sulfonate, benzyl tosylate, benzyl sulfonate , N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, N-methylsulfonyloxyortho a sulfonate such as benzoquinone; a triflate such as N-hydroxyphthalimide or N-hydroxynaphthyl imine; diphenylphosphonium hexafluorophosphate, (4) -Methoxyphenyl)phenylindole trifluoromethanesulfonate, bis(p-terphenyl)phosphonium triflate, three Anthracene salts such as hexafluorophosphate, (4-methoxyphenyl)diphenylphosphonium trifluoromethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate Benzoin tosylate such as benzoin tosylate or α-methylbenzoin tosylate; other diphenylphosphonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzyl carbonate, etc. .

The photoacid generator (C) may be used singly or in combination of two or more. Further, the total amount of the resin (A) used is 100 parts by weight, and the photoacid generator (C) is contained in an amount of from 0.5 part by weight to 4.5 parts by weight, preferably from 0.6 part by weight to 4 parts by weight, more preferably 0.7% by weight. Parts to 3.5 parts by weight. When the amount of the photoacid generator (C) is in the above range, it is easy to prepare a photosensitive resin composition having a good sensitivity, a uniform solution, and excellent storage stability. Solvent ( D )

The type of the solvent (D) is not particularly limited as long as it does not impair the object of the present invention, and can be suitably selected from the organic solvents conventionally used in the positive photosensitive resin composition.

Specific examples of the solvent (D) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol and ethylene glycol monoacetate. , diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl Polyols such as ethers and derivatives thereof; cyclic ethers such as dioxane; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, acetoacetic acid Methyl ester, ethyl acetate ethyl acetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, 2-hydroxypropionic acid Ethyl ester, ethyl 2-hydroxy-2-methylpropanoate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxy An ester such as butyl acetate; an aromatic hydrocarbon such as toluene or xylene; These may be used singly or in combination of two or more.

The solvent (D) is used in an amount of from 60 parts by weight to 600 parts by weight, based on the total amount of the resin (A), preferably from 70 parts by weight to 500 parts by weight, more preferably from 80 parts by weight to 400 parts by weight. . Thiol compound ( E )

The thiol compound (E) has a structure represented by the following formula (E-1): In the formula (E-1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ represents a single bond or a carbon number of 1 to 10. An alkyl group, R ⁴ represents a u-valent organic group; and u represents an integer of 2 to 6.

When R ¹ and R ² are an alkyl group, the alkyl group may be linear or branched, and is preferably linear. When R ¹ and R ² are an alkyl group, the number of carbon atoms of the alkyl group is preferably from 1 to 4, particularly preferably 1 or 2, most preferably 1. As a combination of R ¹ and R ² , one is preferably a hydrogen atom and the other is an alkyl group, and particularly preferably one is a hydrogen atom and the other is a methyl group.

When R ³ is an alkylene group, the alkylene group may be linear or branched, preferably linear. When R ³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably from 1 to 10, more preferably from 1 to 5, particularly preferably from 1 or 2, most preferably 1.

The u-valent organic group defined by R ⁴ is specifically a 2 to 6-valent aliphatic group which may contain an atom other than carbon. Examples of the atom other than carbon which R ⁴ may contain include a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The structure of the aliphatic group to which R ⁴ belongs may be a linear chain, a branched chain or a ring shape, or a structure in which such a structure is combined.

Among the thiol compound (E) represented by the formula (E-1), a compound represented by the following formula (E-2) is more preferred: In the formula (E-2), R ⁴ and u have the same meanings as in the formula (E-1), and R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Specific examples of the thiol compound (E) include specific examples of the following formulas (E-3) to (E-16), but are not limited to these specific examples: Formula (E-3) Formula (E-4) Formula (E-5) Formula (E-6) Formula (E-7) Formula (E-8) Formula (E-9) Formula (E-10) Formula (E-11) Formula (E-12) Formula (E-13) Formula (E-14) Formula (E-15) Formula (E-16)

The total amount of the resin (A) used is 100 parts by weight, and the content of the thiol compound (E) is from 0.3 part by weight to 3 parts by weight, preferably from 0.4 part by weight to 2.8 part by weight, more preferably from 0.5 part by weight to 2.5 parts by weight. Parts by weight.

When the chemically amplified positive photosensitive resin composition does not contain the thiol compound (E) represented by the formula (E-1), the photoresist pattern formed thereof has poor squareness. Terpenoids ( F )

The following specific examples of the quinone compound (F) can be exemplified, but are not limited to these specific examples: anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 2-ethyl -9,10-dimethoxyanthracene, 2-tert-butyl-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-dimethoxyanthracene, 9-methoxy Base-10-methylindole, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-tert-butyl-9,10-diethoxyanthracene, 2,3-Dimethyl-9,10-diethoxyanthracene, 9-ethoxy-10-methylindole, 9,10-dipropoxyindole, 9,10-diisopropoxyanthracene , 2-ethyl-9,10-dipropoxyfluorene, 2-tert-butyl-9,10-dipropoxyfluorene, 2,3-dimethyl-9,10-dipropoxyfluorene , 9-isopropoxy-10-methylindole, 9,10-xyleneoxyanthracene, 2-ethyl-9,10-xyleneoxyanthracene, 2-tert-butyl-9,10- Methyl xylene oxide, 2,3-dimethyl-9,10-xyleneoxyanthracene, 9-tolyloxy-10-methylindole, 9,10-di-α-methyltolyloxyindole , 2-ethyl-9,10-di-α-methyltolyloxypurine, 2-tert-butyl-9,10-di-α-methyltolyloxypurine, 2,3-dimethyl -9,10-di-α-methyltolyloxypurine, 9-(α-methyltoluene Base)-10-methylindole, 9,10-diphenylanthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9-methyloxime, 9-bromoindole, 9-methylthioguanidine, a compound such as 9-ethylthioguanidine.

The total amount of the resin (A) used is 100 parts by weight, and the content of the quinone compound (F) is from 0.2 part by weight to 1.5 parts by weight, preferably from 0.25 part by weight to 1.3 parts by weight, more preferably from 0.3 part by weight to 1.1 parts by weight. Parts by weight.

When the oxime compound (F) is not contained in the chemically amplified positive photosensitive resin composition, the sensitivity of the chemically amplified positive photosensitive resin composition is poor. Additive ( G )

The chemically amplified positive-type photosensitive resin composition may further contain an additive (G) as long as it does not impair the effects of the present invention, and the additive (G) may be used singly or in combination of two or more, depending on actual needs. The specific content of the additive (G) will be described below.

The chemically amplified positive photosensitive resin composition may further contain a polyethylene resin as an additive (G) in order to improve plasticity. Specific examples of the polyethylene resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinylbenzoic acid, polyvinyl methyl ether, polyethylene diethyl ether, polyvinyl alcohol, and polyvinylpyrrole. A ketone, a polyvinyl phenol, a copolymer of these, and the like. The polyethylene resin is preferably polyvinyl methyl ether based on a lower glass transition point.

Further, in the chemically amplified positive-type photosensitive resin composition, in order to improve the adhesion between the template formed using the photosensitive resin composition and the metal substrate, a further auxiliary agent may be further contained as the additive (G).

Further, the chemically amplified positive photosensitive resin composition may further contain a surfactant as an additive (G) in order to improve coatability, defoaming property, leveling property, and the like. Specific examples of the surfactant include BM-1000, BM-1100 (both manufactured by BM Chmie Co., Ltd.), MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F183 (all manufactured by DIC Corporation), and FLUORAD FC-135. , FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (both Sumitomo 3M), SURFLON S-112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLON S-145 (both Commercially available fluorine-based surfactants, such as SH-30PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicone Co., Ltd.), are not limited thereto.

Further, the chemically amplified positive photosensitive resin composition may further contain an acid, an acid anhydride, or a high-boiling solvent as an additive (G) in order to finely adjust the solubility in the developing solution.

Specific examples of the acid and the 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, Hydroxyl groups 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, syringic acid Monocarboxylic 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, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, Polycarboxylic acids such as 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecene succinic anhydride, propane tricarboxylic anhydride, maleic anhydride, hexahydrophthalic anhydride , methyltetrahydrophthalic anhydride, humic anhydride, 1,2,3,4-butane tetracarboxylic anhydride, cyclopentane tetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, partial benzene Triacetic anhydride, diphenyl Benzophenone tetracarboxylic acid anhydride, ethylene glycol bis trimellitic anhydride, glycerol, trimellitic anhydride reference anhydride; and the like.

Further, specific examples of the high-boiling solvent include N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, and N. N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ether, dihexyl ether, acetonitrile, isophorone, hexanoic acid, octanoic acid, 1-octanol , 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl racerus Acetate and the like.

Further, in the chemically amplified positive photosensitive resin composition, a sensitizer may be further contained as an additive (G) in order to enhance sensitivity. < Method for Producing Chemical Amplified Positive Photosensitive Resin Composition >

The method for producing the chemically amplified positive photosensitive resin composition is not particularly limited, and the above components can be obtained by mixing and stirring the usual components by a usual method. Examples of the apparatus which can be used when mixing and stirring the above components include a dissolving machine, a homogenizer, a three-roll mill, and the like. After uniformly mixing the above components, the resulting mixture may be further filtered using a sieve, a membrane filter or the like. < Method of Manufacturing Substrate with Mold >

The method of forming the photoresist pattern as a mold for forming a plated molded body on the metal surface of the substrate having the metal surface is not particularly limited, using the above chemically amplified positive photosensitive resin composition.

A preferred method includes a step of laminating, and stacking a photosensitive resin layer composed of the above-described chemically amplified positive photosensitive resin composition on a metal surface of a substrate having a metal surface; and an exposure step; The photosensitive resin layer is irradiated with actinic rays or radiation; and the developing step is to develop a photosensitive resin layer after exposure to form a method of manufacturing a substrate with a mold for forming a mold for plating a molded body.

The substrate to which the photosensitive resin layer is to be deposited is not particularly limited, and a conventionally known one can be used, and examples thereof include a substrate for an electronic component or a predetermined wiring pattern formed thereon. As the substrate, a metal surface is used; as the metal species constituting the metal surface, copper, gold, aluminum, and more preferably copper.

The photosensitive resin layer is laminated on the substrate, for example, in the following manner. That is, a liquid chemically amplified positive photosensitive resin composition is applied onto a substrate, and the solvent is removed by heating to form a photosensitive resin layer having a desired film thickness. The thickness of the photosensitive resin layer is not particularly limited as long as it can form a resist pattern as a template in a desired film thickness. The film thickness of the photosensitive resin layer is not particularly limited, but is preferably 10 μm or more, more preferably 10 to 150 μm, particularly preferably 20 to 120 μm, and most preferably 20 to 100 μm.

As a method of applying the photosensitive resin composition on the substrate, a method such as a spin coating method, a slit coating method, a roll coating method, a screen printing method, or a scattering method can be employed. It is preferred to pre-baking the photosensitive resin layer. The prebaking conditions vary depending on the type, blending ratio, coating film thickness, and the like of the respective components in the photosensitive resin composition, but are usually 70 to 150 ° C, preferably 80 to 140 ° C and 2 to 60 minutes. about.

The photosensitive resin layer formed as described above is selectively irradiated (exposed) with actinic rays or radiation, for example, ultraviolet rays or visible rays having a wavelength of 300 to 500 nm, through a mask of a predetermined pattern.

As a line source of radiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, an argon laser or the like can be used. Further, the radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, gamma rays, electron beams, proton beams, neutron beams, ion beams, and the like. The amount of radiation exposure varies depending on the composition of the photosensitive resin composition or the thickness of the photosensitive resin layer, and is, for example, 100 to 10000 mJ/cm ² when an ultrahigh pressure mercury lamp is used. Further, the radiation contains light that activates the photoacid generator (C) to generate an acid.

After the exposure, the photosensitive resin layer is heated by a known method to promote the diffusion of the acid, and the alkali solubility of the photosensitive resin layer is changed in the exposed portion of the photosensitive resin film.

Next, the photosensitive resin layer after the exposure is developed in accordance with a conventional method, and the soluble portion is dissolved and removed to form a predetermined photoresist pattern. At this time, an alkaline aqueous solution was used as the developing solution.

As the developing solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl Diethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene An aqueous solution of a base such as 1,5-diazabicyclo[4,3,0]-5-nonane. 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 aqueous solution of the above-mentioned alkali may be used as the developing solution.

The development time varies depending on the composition of the photosensitive resin composition or the thickness of the photosensitive resin layer, and is usually 1 to 30 minutes. The development method may be any one of a liquid coating method, a dipping method, a paddle method, and a jet developing method.

After the development, the water is washed for 30 to 90 seconds, and dried by an air spray gun or an oven. Thus, a mold-attached substrate having a photoresist pattern as a mold on a metal surface of a substrate having a metal surface can be manufactured. < Method for Producing Electroplated Molded Body >

For example, by attaching a conductor such as a metal to a non-resistance portion (a portion removed by a developing liquid) in a mold having a mold-formed substrate formed by the above method, a connection such as a bump or a metal post can be formed. Electroplated molded body such as a terminal. Further, the plating treatment method is not particularly limited, and various methods known per se can be employed. As the plating solution, it is particularly preferable to use a plating solder, a copper plating, a gold plating, or a nickel plating solution. The residual mold is finally removed by a usual method using a stripper or the like.

According to the above method, a photoresist pattern capable of suppressing undercut and simultaneously serving as a mold is formed. By using the substrate having the mold capable of suppressing the undercut thus obtained, it is possible to produce a plated molded body excellent in adhesion to the substrate.

The invention will be described in detail below by way of examples, but the invention is not limited by the examples. < Examples > Synthesis Example of Resin ( A )

The synthesis examples A-1 to A-10 of the resin (A) are explained below:

Synthesis Example A-1 A nitrogen inlet port, a stirrer, a heater, a condenser, and a thermometer were placed on a four-necked conical flask having a volume of 1000 ml. Then, 50 parts by weight of diethylene glycol dimethyl ether was added, and the temperature of the oil bath was raised to 70 °C. Next, 20 parts by weight of a compound represented by the formula (A-1-26) (abbreviated as (a11)) and 20 parts by weight of a compound represented by the formula (A-2-2) (abbreviated as (a31) )), 20 parts by weight of a compound represented by the formula (A-3-1) (abbreviated as (a33)), 10 parts by weight of methacrylic acid (abbreviated as (a41)), and 30 parts by weight of methacrylic acid 2-hydroxyethyl ester (abbreviated as (a43)) and 3.5 parts by weight of 2,2'-azobis-2-methylbutyronitrile (abbreviated as AMBN) were added to a four-necked flask and the mixture was slowly stirred. Solution. The reaction temperature of the entire polymerization process was maintained at 70 ° C, and the polymerization time was continued for 6 hours. After the completion of the polymerization, the polymerization product was taken out from the four-necked flask, and the solvent was removed to obtain a resin (A-1).

Synthesis Examples A-2 to A-10 Synthesis Examples A-2 to A-10 were prepared in the same manner as in Synthesis Example A-1 to prepare resins (A-2) to (A-10), except that: The reaction temperature, reaction time, type of components, and amount of use are shown in Table 1.

Further, the compounds corresponding to the abbreviations in the following Synthesis Examples A-1 to A-10 are as follows.

[Table 1] Synthesis example of novolak resin ( B )

Hereinafter, Synthesis Examples B-1 to B-6 of the novolak resin (B) will be described:

Synthesis Example B-1 A nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer were placed on a four-necked flask having a volume of 1000 ml, and 0.40 mol of m-cresol (abbreviated as (b12)) was added after introducing nitrogen gas. 0.50 mol of p-cresol (abbreviated as (b13)), 0.10 mol of 3,5-xylenol (abbreviated as (b14)), 0.65 mol of formaldehyde (abbreviated as (b21)) and 0.02 Moly oxalic acid. The reaction solution was warmed to 100 ° C with gentle stirring, and polycondensed at this temperature for 6 hours. Then, the reaction solution was heated to 180 ° C, and dried under reduced pressure at a pressure of 10 mmHg, and the solvent was devolatilized to obtain a novolak resin (B-1).

Synthesis Examples B-2 to B-6 Synthesis Examples B-2 to B-6 were prepared in the same manner as in Synthesis Example B-1 to prepare novolak resins (B-2) to (B-6), except that : Change the reaction temperature, reaction time, type of components and amount of use, and are detailed in Table 2.

Further, the compounds corresponding to the abbreviations in the following Synthesis Examples B-1 to B-6 are as follows.

[Table 2] Example of chemically amplified positive photosensitive resin composition

Hereinafter, Examples 1 to 14 and Comparative Examples 1 to 6 of the chemically amplified positive photosensitive resin composition will be described:

Example 1 100 parts by weight of the resin (A-1) obtained in the above Synthesis Example, 0.5 part by weight of the photoacid generator C-1 (hereinafter abbreviated as C-1), and 3.0 parts by weight of the formula (E-6) The compound shown (hereinafter referred to as E-1) and 0.2 parts by weight of 9,10-dibutoxyanthracene (hereinafter abbreviated as F-1) were added to 60 parts by weight of propylene glycol methyl ether acetate (hereinafter referred to as D-1). Thereafter, the chemically amplified positive photosensitive resin composition is prepared by dissolving and mixing in a rocking stirrer, and the chemically amplified positive photosensitive resin composition is evaluated by the following measurement evaluation methods. The results obtained are shown in Table 3.

Example 2 to Example 14 Examples 2 to 14 were the same operation methods as those of the chemically amplified positive photosensitive resin composition of Example 1, except that Examples 2 to 14 were used. The types and amounts of raw materials in the chemically amplified positive photosensitive resin composition were changed, and the formulations and the following evaluation results are shown in Tables 3 and 4.

Comparative Example 1 to Comparative Example 6 Comparative Examples 1 to 6 used the same operation method as the method for producing the chemically amplified positive photosensitive resin composition of Example 1, except that Comparative Example 1 to Comparative Example 6 were used. The type and amount of the raw materials in the chemically amplified positive photosensitive resin composition were changed, and the formulation and the following evaluation results are shown in Table 4.

The compounds corresponding to the labels in Tables 3 and 4 are as follows.

[table 3]

[Table 4] Evaluation method

a. Sensitivity The chemically amplified positive photosensitive resin composition of the examples and the comparative examples was applied onto a 6-inch copper substrate by a spin coater to form a photosensitive resin layer having a film thickness of 50 μm. Thereafter, the photosensitive resin layer was prebaked at 110 ° C for 6 minutes. After the prebaking, a mask having a hole pattern of 60 μm in diameter and an exposure apparatus Titan 2 (manufactured by Ultratech Co., Ltd.) were used to perform pattern exposure with g lines, h lines, and i lines, and the exposure amount was changed stepwise. Next, the substrate was placed on a hot plate, and post-exposure heating (PEB) was performed at 100 ° C for 3 minutes. Thereafter, a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) was dropped on the photosensitive resin layer, and left at 23 ° C for 60 seconds, and the development was repeated four times. Thereafter, washing with running water was carried out, and nitrogen gas was further blown to obtain a thick film resist pattern having a contact hole pattern of 50 μm diameter. Then, the exposure amount in which the pattern residue was not observed, that is, the minimum exposure amount required for forming the thick film photoresist pattern, was obtained as an index of sensitivity. The evaluation criteria are as follows: ◎: exposure amount <100 mJ/cm ² ○: 100 mJ/cm ² ≦ exposure amount <150 mJ/cm ² Δ: 150 mJ/cm ² ≦ exposure amount <200 mJ/cm ² ╳: exposure amount ≧200 mJ/cm ²

b. Rectangularity Please refer to FIG. 1. FIG. 1 is a schematic diagram showing the rectangularity of the photoresist pattern. After the exposure and development steps of the photosensitive resin layer applied to the substrate 100, the photoresist pattern 120 having the photoresist portion 122 and the non-photoresist portion 124 is formed. The cross-sectional shape of the photoresist pattern having the optimum exposure amount was observed, and the values of the bottom width L _b and the top width L _t were measured, and the L _t /L _b value was calculated as an index of the rectangularity. The evaluation criteria are as follows: ◎: 0.9 < L _t / L _b < 1.1 ○: 0.85 < L _t / L _b ≦ 0.9; 1.1 ≦ L _t / L _b < 1.15 △: 0.75 < L _t / L _b ≦ 0.85; 1.15 ≦ L _t /L _b <1.25 ╳: L _t /L _b <0.75; L _t /L _b >1.25 evaluation result

It is understood from Tables 3 and 4 that the chemistry of the thiol compound (E) is not contained as compared with the chemically amplified positive photosensitive resin composition containing the thiol compound (E) (Examples 1 to 14). The amplified positive photosensitive resin compositions (Comparative Examples 1, 3, 4, and 6) have poor squareness; and the chemically amplified positive photosensitive resin composition containing the fluorene-based compound (F) (Example 1 to In the case of Example 14), the chemically amplified positive photosensitive resin compositions (Comparative Examples 2, 3, 5, and 6) which did not contain the quinone compound (F) had poor sensitivity.

Meanwhile, when the monomer mixture (a1) having the structure represented by the formula (A-1) (Examples 1-5, 9, 11, 14) is contained in the monomer mixture for copolymerization of the resin (A) , its rectangular performance is better. Further, when the monomer mixture (a2) containing the polyoxyalkylene chain (Examples 2-6, 10, 11) is further included in the monomer mixture, the sensitivity is better.

Further, when the novolac resin (B) (Examples 3-5, 13, and 14) is contained in the chemically amplified positive photosensitive resin composition, the rectangularity is also better.

As described above, since the chemically amplified positive photosensitive resin composition of the present invention contains the thiol compound (E) and the quinone compound (F), the problem of poor sensitivity and rectangularity can be improved.

On the other hand, if the resin (A) in the chemically amplified positive photosensitive resin composition of the present invention is copolymerized from a monomer mixture containing the specific monomer (a1), or the chemically amplified positive type of the present invention When the photosensitive resin composition further contains the novolak resin (B), the resulting resist pattern can further obtain better rectangularity.

Further, when the resin (A) in the chemically amplified positive photosensitive resin composition of the present invention is obtained by copolymerization of a monomer mixture containing a specific monomer (a2), the obtained resist pattern can further Get better sensitivity.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

100‧‧‧Substrate

120‧‧‧resist pattern

122‧‧‧Resistance Department

124‧‧‧ Non-resistive parts

L _b ‧‧‧ bottom width

L _t ‧‧‧ top width

FIG. 1 is a schematic view showing the squareness of a photoresist pattern.

Claims (10)

A chemically amplified positive photosensitive resin composition comprising: a resin (A) obtained by copolymerization of a monomer mixture and containing an acid dissociable protecting group; a photoacid generator (C) a solvent (D); a thiol compound (E); and a quinone compound (F); wherein the thiol compound (E) has a structure represented by the following formula (E-1): In the formula (E-1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ represents a single bond or a carbon number of 1 to 10. An alkyl group, R ⁴ represents a u-valent organic group; and u represents an integer of 2 to 6. The chemically amplified positive photosensitive resin composition according to claim 1, wherein the monomer mixture comprises a monomer (a1) having the following formula (A-1) ) the structure shown: In the formula (A-1), L ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a carbon number of 1 to 6. a linear or branched fluorinated alkyl group; L ² , L ³ , and L ⁴ each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms or a carbon number of 1 to 6; A linear or branched fluoroalkyl group, or L ³ and L ⁴ are bonded to each other to form a hydrocarbon ring having 5 to 20 carbon atoms. The chemically amplified positive photosensitive resin composition according to claim 1, wherein the monomer mixture comprises a monomer (a2) containing a polyoxyalkylene chain. The chemically amplified positive photosensitive resin composition according to claim 1, which further comprises a novolak resin (B). The chemically amplified positive photosensitive resin composition according to claim 1, wherein the photoacid generator (C) is contained in an amount of 100 parts by weight based on the total amount of the resin (A) used. 0.5 parts by weight to 4.5 parts by weight, the solvent (D) is contained in an amount of 60 parts by weight to 600 parts by weight, and the thiol compound (E) is contained in an amount of 0.3 parts by weight to 3 parts by weight, the hydrazine compound ( The content of F) is from 0.2 part by weight to 1.5 parts by weight. The chemically amplified positive photosensitive resin composition according to claim 2, wherein the monomer (a1) is used in an amount of 20 parts by weight based on 100 parts by weight of the total of the monomer mixture. Up to 80 parts by weight. The chemically amplified positive photosensitive resin composition according to claim 3, wherein the monomer (a2) is used in an amount of 10 parts by weight based on 100 parts by weight of the total of the monomer mixture. Up to 60 parts by weight. The chemically amplified positive photosensitive resin composition according to claim 4, wherein the content of the novolak resin (B) is 20 based on 100 parts by weight of the total amount of the resin (A). Parts by weight to 180 parts by weight. A method of manufacturing a substrate with a mold, comprising: a laminating step of depositing a chemical increase as described in any one of claims 1 to 8 on the metal surface of a substrate having a metal surface a photosensitive resin layer composed of a positive photosensitive resin composition; an exposure step of irradiating the photosensitive resin layer with actinic rays or radiation; and a developing step of developing the exposed photosensitive resin layer, A mold for forming an electroplated formed body is formed. A method for producing an electroplated formed body, comprising: electroplating a mold-attached substrate manufactured by the method for manufacturing a mold-attached substrate according to claim 9 of the invention, and forming a plating in the mold The step of forming the body.