TW201823861A - 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 novolac resin (B), a photoacid generator (C), and a solvent(D). The novolac resin (B) includes a high-ortho novolac resin (B-1), which 18%~25% of methylene group in the resin is bonded in ortho-ortho arrangement.

Description

Chemically amplified positive-type 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 manufacturing a substrate with a mold, and a method for manufacturing an electroplated molded body, and more particularly, it relates to a chemical capable of improving the sensitivity and the problem of poor rectangularity. Amplified positive photosensitive resin composition, manufacturing method of substrate with mold made of said chemically amplified positive photosensitive resin composition, and plated molded body made of said substrate with mold Production method.

Today, optoelectronic processing has become the mainstream of precision micromachining technology. The so-called "photoelectric processing" refers to coating a photoresist composition on the surface of a processed object to form a photoresist layer, patterning the photoresist layer using photolithography technology, and then patterning the photoresist layer (light (Resistance pattern) is a general term for a technology for manufacturing various precision parts such as semiconductor packages by chemical etching, electrolytic etching, or electroforming using electroplating as a main body.

In recent years, with the miniaturization of electronic devices, the high-density assembly technology of semiconductor packages has progressed rapidly, and multi-pin film assembly of packages, miniaturization of package sizes, and two-dimensional assembly using flip-chip methods have been sought. Technology, 3D assembly technology to increase the assembly density. In such high-density assembly technologies, as the connection terminals, for example, bump electrodes (assembly terminals) for connecting bumps protruding toward the package body, rewiring and assembly terminals extending from peripheral terminals on the wafer are used. Metal pillars and the like are arranged on the substrate with high precision.

As described above, a photoresist composition is used in the photoelectric processing system. As such a photoresist composition, a chemically amplified photoresist composition containing an acid generator is known (refer to Patent Documents 1, 2 and the like). The chemically amplified photoresist composition generates an acid from an acid generator through radiation (exposure), promotes the diffusion of the acid through heat treatment, and causes an acid catalyst reaction with the matrix resin in the composition to change its alkali dissolution. Sex.

Such a chemically amplified positive photoresist composition is used, for example, to form a plated molded body such as a bump or a metal pillar in a plating step. Specifically, a chemically amplified photoresist composition is used to form a photoresist layer of a desired thickness on a support such as a metal substrate, and exposed and developed through a predetermined mask pattern to form light used as a template. A resist pattern in which portions intended to form bumps or metal pillars are selectively removed (peeled). Thereafter, after removing the removed portion (non-photoresistive portion) by burying a conductor such as copper by plating, and then removing the surrounding photoresist pattern, a bump or a metal pillar can be formed.

However, the aforementioned chemically amplified positive photoresist composition has the disadvantages of poor sensitivity and poor rectangularity of the formed photoresist pattern, which cannot be accepted by the industry. Therefore, how to provide a chemically amplified positive photoresist composition that can form a photoresist pattern with excellent sensitivity and rectangularity is a problem that is currently urgently sought by those skilled in the art. [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 9-176112 [Patent Document 2] Japanese Patent Application Laid-Open No. 11-52562

In view of this, the present invention provides a chemically amplified positive photosensitive resin composition. The use of the chemically amplified positive photosensitive resin composition can improve the problems of poor sensitivity and poor rectangularity.

The present invention provides a chemically amplified positive photosensitive resin composition, including: resin (A), obtained by copolymerizing a monomer mixture, and containing an acid dissociative protective group, a novolac resin (B), and a photoacid generator (C) and solvent (D). The above-mentioned novolak resin (B) includes a high ortho novolac resin (B-1), and the high ortho novolac resin (B-1) has an elongation of 18% to 25%. The methyl group is bonded to the ortho-ortho position.

In one embodiment of the present invention, the monomer mixture includes a monomer (a1) and has a structure represented by the following formula (A-1): Formula (A-1) In 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 group having 1 to 6 carbon atoms. Linear or branched fluorinated alkyl; L ² , L ³ , and L ⁴ each independently represent a linear or branched alkyl having 1 to 6 carbon atoms, or a carbon having 1 to 6 carbon atoms 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 present invention, the monomer mixture includes a monomer (a2), and the monomer (a2) contains a cyclic ether group.

In an embodiment of the present invention, the chemically amplified positive photosensitive resin composition further includes a thiol compound (E), and has a structure represented by the following formula (E-1): Formula (E-1) In 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 atom having 1 to 10 carbon atoms. Alkyl, R ⁴ represents a u-valent organic group; u represents an integer of 2 to 6.

According to an embodiment of the present invention, the chemically amplified positive photosensitive resin composition further includes an anthracene-based compound (F).

In one embodiment of the present invention, the content of the novolac resin (B) is 20 to 150 parts by weight based on the total amount of the resin (A) used, and the content of the photoacid generator (C) is 0.5 to 5 parts by weight, and the content of the solvent (D) is 30 to 360 parts by weight.

In one embodiment of the present invention, based on the total amount of the resin (A) used, 100 parts by weight, and the content of the high ortho novolac resin (B-1) is 20 to 120 parts by weight.

In one embodiment of the present invention, based on the total amount of the monomer mixture being 100 parts by weight, the content of the monomer (a1) is 10 to 60 parts by weight.

In one embodiment of the present invention, based on the total amount of the monomer mixture being 100 parts by weight, the content of the monomer (a2) is 5 to 30 parts by weight.

In an embodiment of the present invention, the content of the thiol compound (E) is 0.3 to 3 parts by weight based on the total amount of the resin (A) used.

In one embodiment of the present invention, the content of the anthracene compound (F) is 0.2 to 1.5 parts by weight based on the total amount of the resin (A) used.

The present invention also provides a method for manufacturing a substrate with a mold, which includes a lamination step of laminating a photosensitivity composed of the chemically amplified positive photosensitive resin composition as described above on a metal surface of a substrate having a metal surface. A resin layer, an exposure step, irradiating the photosensitive resin layer with active light or radiation, and a development step to develop the exposed photosensitive resin layer to form a mold for forming a plated molded body.

The present invention further provides a method for manufacturing a plated molded body, which includes the steps of forming a plated molded body in a mold by performing electroplating on a substrate with a mold manufactured by the method for manufacturing a substrate with a mold as described above.

Based on the above, the chemically amplified positive photosensitive resin composition of the present invention contains a high ortho novolac resin (B-1) having an ortho-ortho position with an methyl extension bond of 18% to 25%, Therefore, the problem of poor sensitivity and rectangularity can be improved.

In order to make the above features and advantages of the present invention more comprehensible, embodiments are hereinafter described in detail with reference to the accompanying drawings.

< Chemically amplified positive photosensitive resin composition > The present invention provides a chemically amplified positive photosensitive resin composition, including: resin (A), obtained by copolymerizing a monomer mixture, and containing an acid dissociative protective group Novolac resin (B), photoacid generator (C), and solvent (D). The above-mentioned novolac resin (B) includes high ortho novolac resin (B-1), and high ortho novolac resin (B-1) B-1) 18% to 25% of methylene bonds are ortho-ortho. In addition, the chemically amplified positive photosensitive resin composition of the present invention may further include a thiol compound (E), an anthracene compound (F), and an additive (G).

Hereinafter, each component of the chemically amplified positive photosensitive resin composition used in the present invention will be described in detail.

Here, it is explained that acrylic acid and / or methacrylic acid are represented by (meth) acrylic acid, and acrylate and / or methacrylic acid ester are represented by (meth) acrylate; similarly, (meth) Acrylofluorenyl refers to acrylfluorenyl and / or methacrylfluorenyl. Resin ( A )

The resin (A) is obtained by copolymerizing a monomer mixture and contains an acid-dissociable protective group. Specifically, the monomer mixture may include a monomer (a1) having a structure represented by formula (A-1), a monomer (a2) containing a cyclic ether group, or a monomer having a structure represented by formula (A-2) or formula ( A-3) monomer (a3) and other monomers (a4). Monomer ( a1 ) having a structure represented by formula (A-1 )

The monomer (a1) having a structure represented by the formula (A-1) is as follows: Formula (A-1) In 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 group having 1 to 6 carbon atoms. Linear or branched fluorinated alkyl; L ² , L ³ , and L ⁴ each independently represent a linear or branched alkyl having 1 to 6 carbon atoms, or a carbon having 1 to 6 carbon atoms 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.

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 third butyl group, a pentyl group, an isopentyl group, Neopentyl, etc. In addition, a fluorinated alkyl group means that a part or all of the hydrogen atoms of the alkyl group are 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 atoms to which they are bonded. Specific examples of such an aliphatic cyclic group include a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as a monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. Specific examples include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or adamantane, norbornane, isobornene, tricyclodecane, and tetracyclododecane. Isopolycycloalkane groups to remove more than one hydrogen atom. Particularly, a group (which may further have a substituent) for removing one or more hydrogen atoms from cyclohexane or adamantane is preferred.

In addition, when the aliphatic cyclic group formed by the above-mentioned L ³ and L ⁴ has a substituent on its ring skeleton, examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom ( = O) and other polar groups, or linear or branched alkyl groups having 1 to 4 carbon atoms. As the polar group, an oxygen atom (= O) is particularly 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) Formula (A-1-33) In formulas (A-1-1) to (A-1-33), L ¹¹ represents a hydrogen atom or a methyl group.

The used amount of the monomer (a1) is 10 to 60 parts by weight, preferably 12 to 55 parts by weight, and more preferably 15 to 50 parts by weight based on the total amount of the monomer mixture. .

When the monomer mixture includes a monomer (a1) having a structure represented by the formula (A-1), the rectangularity of the chemically amplified positive photosensitive resin composition can be further improved. Cyclic ether group containing monomer (a2)

Examples of the cyclic ether group-containing monomer (a2) include propylene oxide (meth) acrylate, 2-methyl propylene oxide (meth) acrylate, and 3,4-epoxy (meth) acrylate Butyl, -6,7-epoxyheptyl (meth) acrylate, -3,4-epoxycyclohexyl (meth) acrylate or -3,4-epoxycyclohexyl methyl (meth) acrylate Three-membered ring class; 3-((meth) acryloyloxymethyl] oxetane), 3- (meth) acryloyloxymethyl-3-ethyl ring Oxypropane, 3- (meth) acrylic acid oxymethyl-2-methylpropylene oxide, 3- (meth) acrylic acid oxymethyl-2-trifluoromethyl propylene oxide, 3- (methyl ) Acrylic acid oxymethyl-2-pentafluoroethyl propylene oxide, 3- (meth) acrylic acid oxymethyl-2-phenyloxypropylene, 3- (meth) acrylic acid oxymethyl-2 2,2-difluoropropylene oxide, 3- (meth) acryloxymethyl-2,2,4-trifluoropropylene oxide, 3- (meth) acryloxymethyl-2,2,4 4,4-tetrafluoropropylene oxide, 3- (meth) acryloxyethyloxypropylene oxide, 3- (meth) acryloxyethyl-3-ethylpropylene oxide, 2-ethyl-3 -(Meth) acrylic acid oxyethyl propylene oxide, 3- (meth) acrylic acid oxyethyl-2-trifluoro Propylene oxide, 3- (meth) acryloxyethyl-2-pentafluoroethyl propylene oxide, 3- (meth) acryloxyethyl-2-phenylpropylene oxide, 2,2 -Difluoro-3- (meth) acrylic acid oxyethyl propylene oxide, 3- (meth) acrylic acid oxyethyl-2,2,4-trifluoropropylene oxide, 3- (meth) propylene Ethoxyethyl-2,2,4,4-tetrafluoropropylene oxide, 2- (meth) propylene ethoxymethyl propylene oxide, 2-methyl-2- (meth) propylene ethoxymethyl Propylene oxide, 3-methyl-2- (meth) propylene oxymethyl propylene oxide, 4-methyl-2- (meth) propylene oxymethyl propylene oxide, 2- (methyl) Acrylic acid oxymethyl-2-trifluoromethyl propylene oxide, 2- (meth) acrylic acid oxymethyl-3-trifluoromethyl propylene oxide, 2- (meth) acrylic acid oxymethyl- 4-trifluoromethyl propylene oxide, 2- (meth) acryloxymethyl-2-pentafluoroethyl propylene oxide, 2- (meth) acryloxymethyl-3-pentafluoroethyl Propylene oxide, 2- (meth) acryloxymethyl-4-pentafluoroethyl propylene oxide, 2- (meth) acryloxymethyl-2-phenylpropylene oxide, 2- (formyl) Acryl) propenyloxymethyl-3-phenylpropylene oxide, 2- (meth) propenyloxymethyl-4-phenylpropylene oxide, 2,3-difluoro-2- (meth) acryloxymethyl propylene oxide, 2,4-difluoro-2- (meth) acryloxymethyl propylene oxide, 3,3-difluoro -2- (meth) acrylic acid oxymethyl propylene oxide, 2,4-difluoro-2- (meth) acrylic acid oxymethyl propylene oxide, 3,4-difluoro-2- (methyl ) Acrylic acid oxymethyl propylene oxide, 4,4-difluoro-2- (meth) acrylic acid oxymethyl propylene oxide, 2- (meth) acrylic acid oxymethyl-3,3,4- Trifluoropropylene oxide, 2- (meth) acryloxymethyl-3,4,4-trifluoropropylene oxide, 2- (meth) acryloxymethyl-3,3,4,4- Tetrafluoropropylene oxide, 2- (meth) acryloxyethyl propylene oxide, 2- (meth) acryloxyethyl-2-methylpropylene oxide, 2- (meth) acryloxy Ethyl-4-methylpropylene oxide, 2- (meth) acryloxyethyl-2-trifluoromethylpropylene oxide, 2- (meth) acryloxyethyl-3-trifluoromethyl Propylene oxide, 2- (meth) acryloxyethyl-4-trifluoromethyl propylene oxide, 2- (meth) acryloxyethyl-2-pentafluoroethyl propylene oxide, 2 -(Meth) acryloxyethyl-3-pentafluoroethyl propylene oxide, 2- (meth) acryloxyethyl-4-pentafluoroethyl propylene oxide, 2- (methyl) Allyloxyethyl-2-phenylpropylene oxide, 2- (meth) acryloxyethyl-3-phenylpropylene oxide, 2- (meth) acryloxyethyl-4-phenyl Propylene oxide, 2,3-difluoro-2- (meth) acryloxyethyl propylene oxide, 2,4-difluoro-2- (meth) acryloxyethyl propylene oxide, 3, 3-difluoro-2- (meth) acryloxyethyl propylene oxide, 3,4-difluoro-2- (meth) acryloxyethyl propylene oxide, 4,4-difluoro-2 -(Meth) acrylic acid oxyethyl propylene oxide, 2- (meth) acrylic acid oxyethyl-3,3,4-trifluoropropylene oxide, 2- (meth) acrylic acid oxyethyl- Four-membered rings such as 3,4,4-trifluoropropylene oxide, 2- (meth) acryloxyethyl-3,3,4,4-tetrafluoropropylene oxide; etc .; tetrahydrofuran (meth) acrylate Esters, tetrahydrofuran (meth) acrylate modified with caprolactone, (2-methyl-2-isobutyl-1,3-dioxocyclo-4-yl) methyl (meth) acrylate ((2-methyl-2-isobutyl-1,3-dioxolan-4-yl) methyl (meth) acrylate), (2-methyl-2-ethyl-1,3-dioxycyclopent-4-yl ) ((2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl (meth) acrylate), (1,4-dioxo [4,5] Dec-2-yl) methyl ( (1,4-dioxaspiro [4,5] dec-2-yl) methyl (meth) acrylate), (2,2-dimethyl-1,3-dioxocyclo-4-yl ) Five-membered rings such as ((2,2-dimethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate); (meth) acrylic morpholine (( meth) acryloyl morpholine), tetrahydropyranyl (meth) acrylate, and 2-methyltetrahydropyranyl (meth) acrylate. Among them, a cyclic ether-based acrylate monomer having a four-membered ring or more is preferred, and a cyclic ether-based acrylate monomer having a five-membered ring or more is more preferred.

The cyclic ether group-containing monomer (a2) can be used singly or in combination.

The used amount of the monomer (a2) is 5 to 30 parts by weight, preferably 8 to 28 parts by weight, and more preferably 10 to 25 parts by weight based on the total amount of the monomer mixture. .

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

The monomer (a3) having a structure represented by formula (A-2) or formula (A-3) is as follows: Formula (A-2) In formula (A-3) In formula (A-2) and 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 an alicyclic group or alkyl group which may have a substituent, p represents an integer of 0 to 4, and q represents 0 or 1.

In the formulas (A-2) and (A-3), the definitions of the linear or branched alkyl groups and the linear or branched fluorinated alkyl groups of L ⁵ to L ¹⁰ are the same as those described above. The linear or branched alkyl group as defined by L ¹ in formula (A-1) and the linear or branched fluorinated alkyl group are the same, and are not repeated here.

When Y is an alicyclic group or an alkyl group, examples thereof include a group in which one or more hydrogen atoms are removed from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane, and a tetracycloalkane. Specific examples include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or adamantane, norbornane, isobornene, tricyclodecane, and tetracyclododecane. Isopolycycloalkane groups to remove more than one hydrogen atom. Particularly preferred is a group (which may further have a substituent) for removing one or more hydrogen atoms from adamantane.

When the alicyclic group represented by Y has a substituent on its ring skeleton, examples of the substituent include polar groups such as a hydroxyl group, a carboxyl group, a cyano group, and 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 particularly preferred.

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

Specific examples of the monomer (a3) having a structure represented by formula (A-2) or formula (A-3) include the following formulae (A-2-1) to (A-2-24) Compounds represented by formulae (A-3-1) to (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) In formula (A-3-15), (A-2-1) to (A-2-24), (A-3-1) to (A-3-15), L ¹¹ represents a hydrogen atom Or methyl. Other monomers ( a4 )

The monomer mixture may further include other monomers (a4) that do not belong to the monomers (a1) to (a3) as long as the effects of the present invention are not affected. The other monomer (a4) is, for example, a well-known radical polymerizable compound or an anionic polymerizable compound.

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; and 2-methacrylic acid oxyethyl amber Acid, 2-methacrylic acid oxyethyl maleic acid, 2-methacrylic acid oxyethyl phthalic acid, 2-methacrylic acid oxyethyl hexahydrophthalic acid, etc. have carboxyl and ester bonds Methacrylic acid derivatives; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. ; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate Aryl (meth) acrylates such as esters; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethyl Vinyl-containing aromatic compounds such as styrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene; vinyl groups such as vinyl acetate Aliphatic compounds; conjugated dienes such as butadiene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride ; Acrylamide, methacrylamide and other polymerizable compounds containing amidine bonds.

Examples of the polymerizable compound include (meth) acrylates having an acid non-dissociable aliphatic polycyclic group and vinyl-containing aromatic compounds. As the acid non-dissociable aliphatic polycyclic group, tricyclodecyl, adamantyl, tetracyclododecyl, isobornyl, norbornyl and the like are preferred, and it is preferable from the viewpoint 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 the following formulae (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 Formulas (A-4-1) to (A-4-5), L ¹¹ represents a hydrogen atom or a methyl group.

Based on 100 parts by weight of the total amount of the monomer mixture, the use amount of the other monomer (a4) is 20 to 85 parts by weight, preferably 25 to 80 parts by weight, and more preferably 30 to 75 parts by weight Serving. Method for producing resin ( A )

The solvent used in preparing the resin (A) includes, but is not limited to, (1) alcohol compounds: methanol, ethanol, benzyl alcohol, 2-phenylethanol, or 3-phenyl-1-propanol, etc .; (2) ether compounds : Tetrahydrofuran, etc .; (3) glycol ether compounds: ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc .; (4) ethylene glycol alkyl ether acetate: ethylene glycol butane Ether acetate, ethylene glycol ether acetate, ethylene glycol methyl ether acetate, etc .; (5) diethylene glycol compounds: diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, etc .; (6) Dipropylene glycol compounds: 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 compounds: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc .; 8) Propylene glycol alkyl ether acetate compounds: Propylene glycol monomethyl ether aceta te), propylene glycol ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc .; (9) propylene glycol alkyl ether propionates: propylene glycol methyl ether propionate, propylene glycol 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 glycolate, ethyl glycolate, butyl glycolate, methyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate Esters, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate , Ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, propane Butyl acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, 3-methoxybutyl acetate, 2-methoxypropyl Methyl ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate Ethyl acetate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropionate Propyl ester, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Butyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-propoxypropionate Methyl ester, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butoxypropionate Ethyl acetate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, etc. This solvent can be used alone or in combination.

The polymerization initiator used in preparing the resin (A) includes, but is not limited to, azo compounds or peroxides, and may be used alone 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, benzophenazine peroxide, dodecyl peroxide, third butyl peroxyvalerate, 1,1-bis (third butyl peroxide) cyclohexane, Hydrogen peroxide, etc.

The reaction temperature when preparing the resin (A) is 40 to 120 ° C, 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. Novolac resin ( B )

The novolak resin (B) contains a high ortho novolac resin (B-1), and the high ortho novolac resin (B-1) has an extension methyl group of 18% to 25% in the ortho-ortho position . The novolak resin (B) may optionally include other novolak resin (B-2). High ortho-position novolac resin ( B-1 )

High ortho-position novolak resin (B-1) is generally composed of aromatic hydroxy compounds and aldehydes in the presence of a divalent metal salt catalyst, and condensed after dehydration under reduced pressure under acidic (pH 1 to 5). Got. Secondly, an acid catalyst can be optionally added to perform a dehydration condensation reaction and remove unreacted monomers. The dehydration condensation reaction can be referred to Japanese Patent Laid-Open No. 55-090523, Japanese Patent Laid-Open No. 59-080418, and Japanese Patent Laid-Open The reaction method disclosed in Sho 62-230815 is not repeated here.

Specific examples of the aforementioned aromatic hydroxy compound include phenol (phenol); m-cresol, p-cresol, or o-cresol (cresol) cresol); 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 , 2-Third-butylphenol, 2-Third-butyl-4-methylphenol, 2-Third-butyl-5-methylphenol or 6-Third-butyl-3-methylphenol Alkyl phenols; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol or m-propoxyphenol, etc. Alkoxy phenols; o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol or 2-ethyl-4-isopropenylphenol Isopropenyl phenols; phenyl phenols; aryl phenols; 4,4'-dihydroxybiphenyl, bisphenol A, m- Diphenol (resorcinol), of - dihydroxybenzene (Hydroquinone) or pyrogallol (1% pyrogallol) much like hydroxybenzotriazole (polyhydroxyphenol) and the like. These aromatic hydroxy compounds may be used singly or in combination. Among these, the aromatic hydroxy compound is preferably o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, or 2,3,5-trimethylphenol Wait.

Specific examples of the above-mentioned aldehydes condensed with aromatic hydroxy compounds, such as: formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein ( acrolein, crotonaldehyde, cyclo hexanealdehyde, furfural, furylacrolein, benzaldehyde, terephthal aldehyde, phenylacetaldehyde, α- Phenylpropanal, β-phenylpropanal, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde , O-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde or cinnamaldehyde. These aldehydes can be used alone or in combination. The aldehydes are preferably formaldehyde.

When preparing the high ortho-position novolak resin (B-1) of the present invention, the molar ratio of aromatic hydroxy compounds and aldehydes is usually 1: 0.5 to 0.85, preferably 1: 0.55 to 0.82, and more preferably 1: 0.6 to 0.8.

Specific examples of the above-mentioned divalent metal salt catalyst include zinc acetate, manganese acetate, barium acetate, manganese nitrate, zinc borate, zinc chloride, or zinc oxide. These divalent metal catalysts can be used singly or in combination. Based on 100 parts by weight of the aromatic hydroxy compound, the amount of the divalent metal catalyst used is usually 0.01 to 1.0 parts by weight, preferably 0.03 to 0.8 parts by weight, and more preferably 0.05 to 0.5 parts by weight Serving.

Specific examples of the above-mentioned acid catalysts include dimethyl sulfate, diethyl sulfate or dipropyl sulfate. These acid catalysts may be used singly or in combination. Based on 100 parts by weight of the aromatic hydroxy compound, the usage amount of the acid catalyst is usually 0.005 to 1.0 part by weight, preferably 0.008 to 0.8 part by weight, and more preferably 0.01 to 0.5 part by weight.

The high ortho-position novolak resin (B-1) of the present invention usually has 18% to 25% of methyl groups bonded to the ortho-ortho positions, preferably 19 to 25% of methyl groups. In the ortho-ortho position, and more preferably, 20 to 25% of the methyl groups are bonded to the ortho-ortho position.

The high ortho novolac resin (B-1) has a weight average molecular weight of 4,000 to 36,000; preferably 5,000 to 30,000; more preferably 6,000 to 24,000.

Based on the total amount of the resin (A) being 100 parts by weight, the content of the high ortho novolac resin (B-1) is 20 to 120 parts by weight, preferably 25 to 110 parts by weight, and more preferably 30 parts by weight to 100 parts by weight.

When the chemically amplified positive photosensitive resin composition does not include a high ortho-position novolak resin (B-1), the rectangularity of the chemically amplified positive photosensitive resin composition is not good. Other novolac resins ( B-2 )

Other novolac resins (B-2) are generally made of the aforementioned aromatic hydroxy compounds and aldehydes, and contact with conventional organic acids and / or inorganic acids such as hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, or p-toluenesulfonic acid. It is obtained by carrying out condensation reaction under normal pressure under dehydration and removing unreacted monomer in the presence of a medium. Other novolak resins (B-2) are bonded to methyl groups at ortho-para, para-para, or ortho-ortho positions in a random manner. Photoacid generator ( C )

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

Examples of the first form of the photoacid generator (C) include compounds represented by the following formula (C-1): Formula (C-1) In formula (C-1), X ¹ represents a sulfur atom or an iodine atom having a valence of g, 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 atom. An alkenyl group of 2 to 30, or an alkynyl group of 2 to 30 carbon atoms, W ¹ may pass through an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group , Fluorenyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkanesulfinyl, arylenesulfonyl, alkanesulfonyl, arylsulfonyl, alkyleneoxy, At least one selected from the group consisting of amine, cyano, nitro, and halogen. The number of W ¹ is g + h (g-1) +1, and W ¹ may be the same as or different from each other. In addition, 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 phenylene group is bonded to form a ring structure including 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): Formula (C-1a) In formula (C-1a), X ⁴ represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an alkylene group having 8 to 20 carbon atoms. Divalent hetero group, X ⁴ can pass through 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, and a nitro group And at least one selected from the group consisting of halogens. X ⁵ represents -O-, -S-, -SO-, -SO _2- , -NH-, -NW ^2- , -CO-, -COO-, -CONH-, carbon atoms having a number of 1 to 3 Alkyl, or phenylene. h represents the number of repeating units of the structure in parentheses. The h + 1 X ⁴ and h X ⁵ may be the same or different, respectively. W ² is the same as defined above.

(X ^{3) -} the onium ion (counter ion), may be exemplified by the following formula (C-1b) of FIG fluoroborate fluoroalkyl phosphate anions or the following formula (C-1c) shown in the anion _{^{: [(W 3) j PF}} 6-j] - in formula (C-1b) of formula (C-1b), W ³ represents more than 80% of the hydrogen atoms of the alkyl group substituted with a fluorine atom. j represents the number, and is an integer from 1 to 5. The j W ^3s may be the same or different. In formula (C-1c), in 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 through a fluorine atom and a trifluoromethyl group. At least one substitution selected from the group.

Examples of the onium ion in the compound represented by the formula (C-1) include triphenylphosphonium, tri-p-tolylphosphonium, 4- (phenylthio) phenyldiphenylphosphonium, and bis [4- ( Diphenylfluorenyl) phenyl] sulfide, bis [4- {bis [4- (2-hydroxyethoxy) phenyl] fluorenyl} phenyl] sulfide, bis {4- [bis (4- Fluorophenyl) fluorenyl] phenyl} sulfide, 4- (4-benzylidene-2-chlorophenylthio) phenylbis (4-fluorophenyl) fluorene, 7-isopropyl-9- Oxy-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylfluorene, 7-isopropyl-9-oxy-10-thia-9,10-dihydroanthracene- 2-yldiphenylfluorene, 2-[(diphenyl) fluorenyl] thiaxanthone, 4- [4- (4-tert-butylbenzylfluorenyl) phenylthio] phenyldi-p- Tolylfluorene, 4- (4-benzylidenephenylthio) phenyldiphenylfluorene, diphenylphenethylfluorene, 4-hydroxyphenylmethylbenzylfluorene, 2-naphthylmethyl (1-ethoxycarbonyl) ethylfluorene, 4-hydroxyphenylmethylphenethylfluorene, phenyl [4- (4-biphenylthio) phenyl] 4-biphenylfluorene, phenyl [ 4- (4-biphenylthio) phenyl] 3-biphenylfluorene, [4- (4-ethylfluorenylphenylthio) phenyl] diphenylfluorene, stearylmethylphenethylfluorenylfluorene, Diphenylfluorene, di-p-tolylfluorene, bis (4-dodecylphenyl) fluorene, (4-methoxyphenyl) fluorene, (4-octyloxyphenyl) phenylfluorene, bis (4-dodecyl) phenylfluorene, 4- (2-hydroxytetradecyloxy) phenyl Phenylhydrazone, 4-isopropylphenyl (p-tolyl) fluorene, 4-isobutylphenyl (p-tolyl) fluorene, and the like.

Among the onium ions in the compound represented by the formula (C-1), preferred onium ions include a sulfonium ion represented by the following formula (C-1d): In formula (C-1d), in formula (C-1d), W ⁸ each independently represents a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, and may be substituted. Selected from the group consisting of aryl and arylcarbonyl. X ² has the same meaning as X ² in the formula (C-1).

Specific examples of the europium ion represented by the above formula (C-1d) include 4- (phenylthio) phenyldiphenylsulfonium and 4- (4-benzylfluorenyl-2-chlorophenylthio). ) Phenylbis (4-fluorophenyl) fluorene, 4- (4-benzylidenephenylthio) phenyldiphenylfluorene, phenyl [4- (4-biphenylthio) phenyl] 4 -Biphenylphosphonium, phenyl [4- (4-biphenylthio) phenyl] 3-biphenylphosphonium, [4- (4-ethylphenylphenyl) phenyl] diphenylphosphonium, diphenyl [4- (p-triphenylthio) phenyl] diphenylphosphonium.

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

Particularly preferred W ³ 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. 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 fluoroalkylfluorophosphate 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 preferred is [(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 ] ^- .

As preferable specific examples of the borate anion represented by the above formula (C-1c), there may be mentioned (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ^- ), [[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 ] ^- ), (difluorophenyl) borate ([B (C ₆ H ₃ F ₂ ) ₄ ] ^- ), etc. . Among these, particularly preferred is penta (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ^- ).

Examples of the second form of the acid generator (A) include 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-triazine and 2,4-bis (trichloromethyl) ) -6- [2- (2-furanyl) vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furanyl) ethylene Yl] symmetric triazine, 2,4-bis (trichloromethyl) -6- [2- (5-ethyl-2-furanyl) vinyl] symmetric triazine, 2,4-bis (trichloromethyl) ) -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) phenylsymmetric triazine, 2,4-bis-trichloro Methyl-6- (2-bromo-4-methoxy) phenylsymmetric triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylbenzene Symmetric triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenylsymmetric 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-furanyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-methyl 2-furanyl) 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-tris Halogenated triazine compounds such as hydrazine, ginseng (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 ginseng (2,3-dibromopropyl) trimeric isocyanate. Formula (C-2) In formula (C-2), W ⁹ to W ¹¹ are each independently represented as a haloalkyl group.

Further, as a third embodiment of the photoacid generator (C), α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2 , 4-Dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4- A methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-chloropentenylacetonitrile, and a compound represented by the following formula (C-3) containing a sulfonic acid oxime group. Formula (C-3) In 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 parentheses.

In the formula (C-3), the aromatic compound group represents a group of a compound that makes the aromatic compound exhibit unique physical and chemical properties, and examples thereof include aryl groups such as phenyl and naphthyl, or furanyl and thienyl And so on heteroaryl. These may have one or more appropriate substituents on the ring, such as a halogen atom, an alkyl group, an alkoxy group, a nitro group, and the like. Further, W ^{13 is} particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, propyl, and butyl. 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 particularly preferred.

As the acid generator represented by the formula (C-3), when n = 1, compounds in which W ¹² is any of phenyl, methylphenyl, and methoxyphenyl, and W ¹³ is methyl Specific examples include α- (methanesulfonyloxyimino) -1-phenylacetonitrile, α- (methanesulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methanesulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile, [2- (propanesulfonyloxyimino) -2,3-dihydroxythiophene-3- Subunit] (o-tolyl) acetonitrile and the like. When n = 2, examples of the acid generator represented by the formula (C-3) include acids represented by the following formulae (C-3-1) to (C-3-8) Generating agent: 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)

Moreover, as a 4th aspect of a photoacid generator (C), the onium salt which has a naphthalene ring in a cationic part is mentioned. The "having a naphthalene ring" means having a structure derived from naphthalene, meaning a structure of at least two rings, and maintaining their aromaticity. The naphthalene ring may have substituents such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and the like. . The structure derived from the naphthalene ring can be a monovalent radical (free atomic valence is 1), or a divalent radical (free atomic valence is 2) or more. It is more preferably a monovalent radical (however, in this case, it is deducted from the above) (To calculate the free atomic valence of the bonded part of the substituent). The number of naphthalene rings is preferably 1 to 3.

As the cation part of such an onium salt having a naphthalene ring in the cation part, a structure represented by the following formula (C-4) is preferred: Formula (C-4) In formula (C-4), at least one of W ¹⁴ to W ¹⁶ represents a group represented by the following formula (C-4a), and the rest represents a straight chain having 1 to 6 carbon atoms. Alternatively, it may be 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 each independently a linear or branched alkylene group having carbon number W ¹⁴ to W ¹⁶ , These ends can be bonded to form a ring. Formula (C-4a) In 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 number of A linear or branched alkyl group of 1 to 6, W ¹⁸ represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms which may have a substituent. l and m each independently represent an integer from 0 to 2, and l + m is 3 or less. When there is a plurality of W ¹⁷ , they may be the same or different from each other. When plural W ¹⁸ are present, they may be the same as or different from each other.

The number of the groups represented by the above formula (C-4a) among the above W ¹⁴ to W ^{16 is} preferably one from the viewpoint of the stability of the compound, and the rest are linear or branched having 1 to 6 carbon atoms. Alkyl groups, these ends may be bonded to form a ring. In this case, the two alkylene groups may include a sulfur atom to form a 3- to 9-membered ring. The number of atoms (sulfur-containing atoms) constituting the ring is preferably 5 to 6.

Examples of the substituent which the above-mentioned 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 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 group having 1 to 6 carbon atoms. Alkyl, etc.

Those suitable as such cationic moieties include those represented by the following formulae (C-4b) and (C-4c), and a structure represented by the following formula (C-4c) is particularly preferred. Formula (C-4b) Formula (C-4c)

As such a cationic moiety, a sulfonium salt or a sulfonium salt may be used; a sulfonium salt is preferred from the viewpoint of acid production efficiency and the like.

Therefore, an anion part which is suitable as an anion part of an onium salt which has a naphthalene ring in a cationic part is desirable as an anion which can form a sulfonium salt.

As an anion part of such an acid generator, a part or all of hydrogen atoms are fluorinated fluoroalkylsulfonic acid ions or arylsulfonic acid ions.

The alkyl group in the fluoroalkylsulfonic acid ion may be linear, branched, or cyclic with 1 to 20 carbon atoms. Based on the volume of the generated acid and its diffusion distance, the number of carbon atoms is preferably 1 To 10. It is particularly preferable to have a branched or ring shape because the diffusion distance is short. In addition, from the viewpoint of inexpensive synthesis, methyl, ethyl, propyl, butyl, and octyl are preferred.

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 with an alkyl group or a halogen atom. In particular, an aryl group having 6 to 10 carbon atoms is preferred because it can be synthesized inexpensively. Specific preferred examples include phenyl, tosyl, ethylphenyl, naphthyl, and methylnaphthyl.

Among the above fluoroalkylsulfonic acid ions or arylsulfonic acid ions, the fluorination rate when part or all of the hydrogen atoms are fluorinated is preferably 10 to 100%, more preferably 50 to 100%, and especially substituted with fluorine atoms. All hydrogen atoms are preferred because the strength of the acid is increased. Those belonging to this category include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, and perfluorobenzenesulfonate.

Among these, as a preferable anion part, the following formula (C-4d) can be mentioned: W ²⁰ SO ₃ ^- Formula (C-4d) In formula (C-4d), W ²⁰ is the following formula (C-4e), (C-4f), and (C-4g). -C _x F _{2x + 1} (C-4e) Formula (C-4f) Formula (C-4g) In 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 chain having 1 to 6 carbon atoms. Alkoxy, y represents an integer of 1 to 3. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.

In addition, as the anion part, a nitrogen-containing one represented by the following formula (C-4h) or (C-4i) may be used. Formula (C-4h) Formula (C-4i) In formula (C-4h) and formula (C-4i), X ^a represents a linear or branched alkylene group having at least one hydrogen atom substituted with a fluorine atom. The number of carbon atoms is 2 to 6, preferably 3 to 5, and most preferably 3 carbon atoms. In addition, Y ^a and Z ^a each independently represent a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the number of carbon atoms in the alkyl group is 1 to 10, preferably 1 to 7, and more It is preferably 1 ~ 3.

X ^a number of carbon atoms of the alkylene group, or Y ^a, Z ^a group of the smaller number of carbon atoms is more excellent solubility in an organic solvent, and therefore preferred.

And, X ^a or an alkylene group of Y ^a, Z ^a in the alkyl group, the number of substituted hydrogen atoms in the more fluorine atoms, the stronger acid strength, and therefore preferred. 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 perfluoroalkylene in which all hydrogen atoms are replaced by fluorine atoms. Or perfluoroalkyl.

Those which are suitable as such an onium salt having a naphthalene ring in the cationic moiety include compounds represented by the following formulae (C-4j) and (C-4k): Formula (C-4j) Formula (C-4k)

Furthermore, as a fifth embodiment of the photoacid generator (C), bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, Bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane and other bissulfonyldiazomethanes; p-toluenesulfonic acid 2-nitrobenzyl Esters, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate , Nitrobenzyl derivatives such as dinitrobenzyl carbonate, pyrogallol trifluoromethanesulfonate, pyrogallol tritoluenesulfonate, benzyltoluenesulfonate, benzylsulfonate , N-methanesulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, N-methanesulfonyloxyimine Sulfonates such as xylylenediamine; trifluoromethanesulfonates such as N-hydroxyphthalimide and N-hydroxynaphthalene imine; diphenylsulfonium hexafluorophosphate, (4 -Methoxyphenyl) phenylsulfonium triflate, bis (p-tert-butylphenyl) sulfonium triflate, tris Onium salts such as sulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-tributylphenyl) diphenylsulfonium trifluoromethanesulfonate ; Benzoin tosylate such as benzoin tosylate, α-methyl benzoin tosylate; other diphenylphosphonium salts, triphenylphosphonium salts, phenyldiazonium salts, benzyl carbonate, etc. .

The photoacid generator (C) may be used alone or in combination of two or more kinds. In addition, based on the total amount of the resin (A) being 100 parts by weight, the content of the photoacid generator (C) is 0.5 to 5 parts by weight, preferably 0.6 to 4.5 parts by weight, and more preferably 0.7 weight. Parts to 4 parts by weight. Solvent ( D )

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

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, diethylene glycol dimethyl ether, monopropylene ether of dipropylene glycol monoacetate, monoethyl ether, monopropylene Polyols such as ether, monobutyl ether, monophenyl ether and their derivatives; cyclic ethers such as dioxane; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, Methyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, ethyl pyruvate, ethyl ethoxylate, methyl methoxypropionate, ethyl 3-ethoxypropionate, 2-hydroxyl Methyl propionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, Esters such as 3-methyl-3-methoxybutyl acetate, propylene glycol methyl ether acetate; aromatic hydrocarbons such as toluene and xylene. These can be used alone or in combination of two or more.

Based on 100 parts by weight of the total resin (A), the content of the solvent (D) is 30 to 360 parts by weight, preferably 40 to 300 parts by weight, and more preferably 50 to 240 parts by weight . Thiol compound ( E )

The thiol compound (E) has a structure represented by the following formula (E-1): Formula (E-1) In 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 atom having 1 to 10 carbon atoms. Alkyl, R ⁴ represents a u-valent organic group; u represents an integer of 2 to 6.

When R ¹ and R ² are alkyl groups, the alkyl group may be linear or branched, and is preferably linear. When R ¹ and R ² are alkyl groups, the number of carbon atoms in the alkyl group is preferably 1 to 4, particularly preferably 1 or 2, and most preferably 1. As a combination of R ¹ and R ² , one is preferably a hydrogen atom, 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, and is preferably linear. When R ³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.

The u-valent organic group defined by R ⁴ is specifically a 2- to 6-valent aliphatic group which may contain atoms other than carbon. Examples of the atoms other than carbon that R ⁴ may include 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 linear, branched, or cyclic, or a combination of these structures may be used.

Among the thiol compounds (E) represented by the formula (E-1), the compounds represented by the following formula (E-2) are more preferable: Formula (E-2) In formula (E-2), R ⁴ and u have the same definitions as in 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 the following specific examples of the formula (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) (E-14) Formula (E-15) (E-16)

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

When the thiol compound (E) is included in the chemically amplified positive photosensitive resin composition, the rectangularity of the chemically amplified positive photosensitive resin composition can be further improved. Anthracene ( F )

The anthracene compound (F) can be exemplified by the following specific examples, but is 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 Methyl-10-methylanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-third-butyl-9,10-diethoxyanthracene, 2,3-dimethyl-9,10-diethoxyanthracene, 9-ethoxy-10-methylanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene , 2-ethyl-9,10-dipropoxyanthracene, 2-tert-butyl-9,10-dipropoxyanthracene, 2,3-dimethyl-9,10-dipropoxyanthracene , 9-isopropoxy-10-methylanthracene, 9,10-xyloxyanthracene, 2-ethyl-9,10-xyloxyanthracene, 2-tert-butyl-9,10- Xyloxyanthracene, 2,3-dimethyl-9,10-xyloxyanthracene, 9-toloxy-10-methylanthracene, 9,10-di-α-methyltoloxyanthracene , 2-ethyl-9,10-di-α-methyltolyl anthracene, 2-third butyl-9,10-di-α-methyltolyl anthracene, 2,3-dimethyl -9,10-di-α-methyltoluene anthracene, 9- (α-methyltoluene Group) -10-methylanthracene, 9,10-diphenylanthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9-methylanthracene, 9-bromoanthracene, 9-methylthioanthracene, 9-Ethylthioanthracene and other compounds.

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

When the anthracene-based compound (F) is included in the chemically amplified positive photosensitive resin composition, the sensitivity of the chemically amplified positive photosensitive resin composition can be further improved. Additives ( G )

The chemically amplified positive photosensitive resin composition may further contain an additive (G) as long as the effect of the present invention is not affected. The additive (G) may be used singly or in combination of a plurality of types, depending on actual needs. The specific content of the additive (G) is described below.

The chemically amplified positive-type 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, polyvinyl ether, polyvinyl alcohol, and polyvinylpyrrole. Pyridone, polyvinylphenol, and copolymers thereof. Polyethylene resin is preferably polyethylene methyl ether because of its low glass transition point.

In addition, the chemically amplified positive photosensitive resin composition may further include a bonding aid as an additive (G) in order to improve the adhesion between the template and the metal substrate formed using the photosensitive resin composition.

Specific examples of the adjuvant include Cymel-300 or Cymel-303 made by CYTEC; Sanwa Chemical made MW-30MH, MW-30, MS-11, MS-001, MX-750 or MX-706 products such as melamine compounds; vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyl Trimethoxysilane, vinyltri (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoamino) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Propylpropyldimethylmethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxy Silane compounds such as methylsilane, 3-mercaptopropyltrimethoxysilane, and bis-1,2- (trimethoxysilyl) ethane.

Furthermore, the chemically amplified positive photosensitive resin composition may further contain a surfactant as an additive (G) in order to improve coating properties, defoaming properties, leveling properties, and the like. Specific examples of the surfactant include BM-1000, BM-1100 (all manufactured by BM Chmie), MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F183 (all manufactured by DIC Corporation), FLUORAD FC-135 , FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (all made by Sumitomo 3M), SURFLON S-112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLON S-145 (all It is a commercially available fluorine-based surfactant such as manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicone), but is not limited thereto.

In addition, the chemically amplified positive-type photosensitive resin composition may further contain an acid, an acid anhydride, or a high-boiling point solvent as an additive (G) in order to finely adjust the solubility of the developer.

Specific examples of acids and anhydrides 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, 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, etc. 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, propanetricarboxylic anhydride, maleic anhydride, hexahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, humic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimylene Tricarboxylic anhydride, diphenyl Benzophenone tetracarboxylic acid anhydride, ethylene glycol bis trimellitic anhydride, glycerol, trimellitic anhydride reference anhydride; and the like.

Further, as specific examples of the high-boiling-point solvent, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamidamine, N-methylpyrrolidone, dimethyl sulfene, benzyl ether, dihexyl ether, acetoacetone, isophorone, hexanoic acid, caprylic acid, 1-octanol , 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, vinyl carbonate, propylene carbonate, phenylcellulose Acetate, etc.

The chemically amplified positive photosensitive resin composition may further contain a sensitizer as an additive (G) in order to increase sensitivity. < Method for producing chemically amplified positive photosensitive resin composition >

The method for producing the chemically amplified positive-type photosensitive resin composition is not particularly limited, and the above-mentioned components can be obtained by mixing and stirring the components in a usual manner. Examples of a device that can be used when mixing and stirring the above-mentioned components include a dissolver, a homogenizer, and a three-roll mill. After the above components are uniformly mixed, the obtained mixture may be further filtered with a screen, a membrane filter, or the like. < Manufacturing method of a substrate with a mold >

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

As a preferred method, the method may include a lamination step of laminating a photosensitive resin layer composed of the above-mentioned chemically amplified positive photosensitive resin composition on a metal surface of a substrate having a metal surface; an exposure step; The photosensitive resin layer is irradiated with active light or radiation; and a developing step, which develops the exposed photosensitive resin layer to form a mold-attached substrate for forming a mold for a plated molded body.

The substrate on which the photosensitive resin layer is to be laminated is not particularly limited, and conventionally known ones 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, and aluminum are preferred, and copper is more preferred.

The photosensitive resin layer is laminated on a substrate in the following manner, for example. That is, a liquid chemically amplified positive photosensitive resin composition is coated on 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 photoresist pattern as a template with a desired film thickness. The film thickness of the photosensitive resin layer is not particularly limited, but it 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 coating method of the photosensitive resin composition on a substrate, methods such as a spin coating method, a slit coating method, a roll coating method, a screen printing method, and a spreading method can be adopted. The photosensitive resin layer is preferably pre-baked. The pre-baking conditions vary depending on the type, blending ratio, and coating film thickness of each component in the photosensitive resin composition, but it is 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 active light or radiation through a mask of a predetermined pattern, such as ultraviolet or visible light having a wavelength of 300 to 500 nm.

As a radiation source, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, and the like can be used. 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 radiation exposure amount varies depending on the composition of the photosensitive resin composition, the film thickness of the photosensitive resin layer, and the like. For example, when an ultra-high pressure mercury lamp is used, it is 100 to 10,000 mJ / cm ² . In addition, the radiation contains light that activates the photoacid generator (C) to generate an acid.

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

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

As the developing solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiamine, etc. can be used. Ethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, Aqueous solution of 1,5-diazabicyclo [4,3,0] -5-nonane and other bases. Further, an aqueous solution obtained by appropriately adding a water-soluble organic solvent such as methanol or ethanol or a surfactant to an aqueous solution of the alkali may be used as a developing solution.

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

After development, it is washed with running water for 30 to 90 seconds, and dried with an air spray gun or an oven. In this way, it is possible to manufacture a substrate with a mold having a photoresist pattern as a mold on the metal surface of the substrate having a metal surface. < Manufacturing method of electroplated compact >

The non-photoresistive portion (the portion removed by the developer) in the mold with the mold-attached substrate formed by the above method can be used to form a connection terminal such as a bump or a metal pillar by burying a conductor such as a metal by electroplating. Or the like. In addition, the plating method is not particularly limited, and various conventionally known methods can be adopted. As the plating solution, solder plating, copper plating, gold plating, and nickel plating solution are particularly suitably used. The residual mold is finally removed using a stripping solution or the like in accordance with a usual method.

According to the above method, a photoresist pattern that can be used as a mold while suppressing undercutting is formed. By using the substrate provided with the mold which can suppress the undercut as described above, it is possible to produce a plated molded body having excellent adhesion to the substrate.

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to the contents disclosed in these examples. < Example > Synthesis example of resin ( A )

The following describes synthesis examples A-1 to A-10 of the resin (A):

Synthesis Example A-1 A four-necked conical flask with a volume of 1000 ml was provided with a nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer. 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, 15 parts by weight of a compound represented by the formula (A-1-26) (abbreviated as (a11)), 10 parts by weight of methacrylic acid (abbreviated as (a41)), and 10 parts by weight of methacrylic acid 2-Hydroxyethyl ester (abbreviated as (a43)), 35 parts by weight of isobornyl methacrylate (abbreviated as (a44)), 30 parts by weight of benzyl methacrylate (abbreviated as (a46)), and 3.5 A part by weight of 2,2'-azobis-2-methylbutyronitrile (abbreviated as AMBN) was added to a four-necked conical flask, and the above mixed solution was slowly stirred. The reaction temperature during the entire polymerization process was maintained at 70 ° C., and the polymerization time continued for 6 hours. After the polymerization was completed, the polymerization product was taken out from the four-necked conical flask and the solvent was removed to obtain the resin (A-1).

Synthesis Examples A-2 to A-10 Synthesis Examples A-2 to A-10 were prepared in the same steps as in Synthesis Example A-1. The resins (A-2) to (A-10) were prepared except for the following changes: The reaction temperature, reaction time, types of ingredients, and usage amounts are listed in Table 1.

The compounds corresponding to the abbreviations in the following Synthesis Examples A-1 to A-10 are shown below.

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

The synthesis examples B-1-1 to B-1-3 and B-2-1 to B-2-2 of the novolak resin (B) are explained below:

Synthesis Example B-1-1 A four-necked conical flask with a volume of 1000 ml was provided with a nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer. After introducing nitrogen, 64-89 g (0.6 mol) of m-cresol was added. -43.26 g (0.4 mole) of cresol, 0.5 g (0.0028 mole) of manganese acetate and 48.70 g (0.6 mole) of 37% by weight aqueous formaldehyde solution, slowly stirred and polymerized for 3 hours. Then, 1.38 g (0.01 mol) of salicylic acid was added to adjust the pH to 3.5, and dried under reduced pressure at a pressure of 300 mmHg for 30 minutes. Next, the reaction solution is slowly heated to 150 ° C. to remove the solvent, and a high-ortho novolac resin (B-1-1) can be obtained. The obtained high ortho novolac resin (B-1-1) was used to measure the number of methylated bonds by carbon nuclear magnetic resonance ( ¹³ C-NMR), and the methylated bonds of the following novolak resins were bonded to the ortho position. -The evaluation method of the ratio of the orthos is calculated as 18%.

Synthesis Example B-1-2 A four-necked conical flask with a volume of 1000 ml was provided with a nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer. After introducing nitrogen, o-cresol 5.40 g (0.05 mol) was added. -Cresol 64.89 g (0.6 mol), p-cresol 37.86 g (0.35 mol), manganese acetate 0.5 g (0.0028 mol) and 37% by weight aqueous formaldehyde solution 52.75 g (0.65 mol), slowly stir and Polymerize for 3 hours. Then, 1.10 g (0.008 mol) of salicylic acid was added to adjust the pH to 4.0, and it was dried under reduced pressure at a pressure of 300 mmHg for 30 minutes. Next, the reaction solution is slowly heated to 150 ° C. to remove the solvent, and a high-ortho novolac resin (B-1-2) can be obtained. The obtained high ortho novolac resin (B-1-2) was used to measure the number of methyl groups bonded by carbon nuclear magnetic resonance ( ¹³ C-NMR), and the methyl groups of the following novolak resin were bonded to the ortho position -The evaluation method of the ratio of adjacent positions calculates the ratio as 20%.

Synthesis Example B-1-3 A four-necked conical flask with a volume of 1000 ml was provided with a nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer. After introducing nitrogen, 64.89 g (0.6 mol) of m-cresol was added. -43.26 g (0.4 mole) of cresol, 0.5 g (0.0028 mole) of manganese acetate, and 56.82 g (0.7 mole) of 37% by weight aqueous formaldehyde solution, slowly stirred and polymerized for 3 hours. Then, 0.37 g (0.003 mol) of benzoic acid was added to adjust the pH value to 4.8, and dried under reduced pressure at a pressure of 300 mmHg for 30 minutes, and then 0.03 g (0.0002 mol) of dimethyl sulfate was added. Next, the reaction solution is slowly heated to 150 ° C. to remove the solvent, and a high ortho novolac resin (B-1-3) can be obtained. The obtained high ortho novolac resin (B-1-3) was measured by carbon nuclear magnetic resonance ( ¹³ C-NMR) for the number of methyl groups, and the methyl group of the following novolac resin was bonded to the ortho position. -The evaluation method of the ratio of the adjacent positions is calculated as 25%.

Synthesis Example B-2-1 A four-necked conical flask with a volume of 1000 ml was provided with a nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer. After introducing nitrogen, 64-89 g (0.6 mol) of m-cresol was added. -43.26 g (0.4 mole) of cresol, 1.80 g (0.02 mole) of oxalic acid, and 48.70 g (0.6 mole) of 37% by weight aqueous formaldehyde solution, slowly stirred and polymerized for 3 hours. Then, the reaction solution is heated to 150 ° C. to remove the solvent, and a novolac resin (B-2-1) can be obtained. The obtained novolak resin (B-2-1) was subjected to carbon nuclear magnetic resonance ( ¹³ C-NMR) measurement of the number of methyl groups bonded, and the methyl groups of the following novolak resin were bonded to the ortho-ortho position The proportional evaluation method calculates its ratio to 16%.

Synthesis Example B-2-2 A four-necked conical flask with a volume of 1000 ml was provided with a nitrogen inlet, a stirrer, a heater, a condenser tube, and a thermometer. After introducing nitrogen, 64-89 g (0.6 mol) of m-cresol was added. -32.45 g (0.3 mole) of cresol, 12.22 g (0.1 mole) of 2,5-xylenol, 0.90 g (0.01 mole) of oxalic acid, and 44.64 g (0.55 mole) of 37% by weight aqueous formaldehyde solution, slowly Stir and polymerize for 3 hours. Then, the reaction solution is heated to 150 ° C. to remove the solvent, and a novolac resin (B-2-2) can be obtained. The obtained novolak resin (B-2-2) was subjected to carbon nuclear magnetic resonance ( ¹³ C-NMR) measurement of the number of methyl groups bonded, and the methyl groups of the following novolak resin were bonded to the ortho-ortho position The proportion of the evaluation method is calculated as 14%. Examples of chemically amplified positive photosensitive resin composition

Examples 1 to 14 and Comparative Examples 1 to 4 of the chemically amplified positive photosensitive resin composition are described below:

Example 1 100 parts by weight of the resin (A-1) obtained in the aforementioned Synthesis Example A-1, 35 parts by weight of the high-ortho novolac resin (B-1-1) obtained in Synthesis Example B-1-1, 0.2 parts by weight of the photoacid generator C-1 (hereinafter referred to as C-1) and 0.3 parts by weight of 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-triazine (hereinafter (Referred to as C-2), after adding 30 parts by weight of propylene glycol methyl ether acetate (hereinafter referred to as D-1), dissolve and mix with a shaker mixer to prepare a chemically amplified positive photosensitive resin composition The chemically amplified positive-type photosensitive resin composition was evaluated by each of the following measurement and evaluation methods, and the results are shown in Table 2.

Examples 2 to 14 Examples 2 to 14 use the same operation method as the method for manufacturing the chemically amplified positive-type photosensitive resin composition of Example 1, except that Examples 2 to 14 are the same. Table 2 and Table 3 change the types and amounts of raw materials in the chemically amplified positive photosensitive resin composition, and their formulations and the following evaluation results.

Comparative Examples 1 to 6 Comparative Examples 1 to 4 use the same operation method as the method for producing the chemically amplified positive-type photosensitive resin composition of Example 1, except that Comparative Examples 1 to 4 are As shown in Table 3, the type and amount of the raw materials in the chemically amplified positive photosensitive resin composition were changed, and the formula and the following evaluation results were changed.

The compounds corresponding to the reference numerals in Tables 2 and 3 are shown below.

[Table 2]

[table 3] Evaluation method

a. The methylated ortho-ortho bond ratio of novolac resin was measured using carbon nuclear magnetic resonance ( ¹³ C-NMR) (manufactured by Bruker, model AV400), and the methylated amount of novolak resin was measured according to the following The formula calculates the ortho-ortho bond ratio in the novolac resin. Ortho-adjacent bond ratio (%) = ((adjacent-adjacent key) / [(adjacent-adjacent key) + (adjacent-paragraph key) + (para-ae-position key)] } × 100% ortho-ortho-bond: the number of ortho-ortho-bonds of this methyl group. Ortho-para-bonds: The number of the ortho-para para bonds. Para-para bond: the number of the methyl group in para-para bond.

b. Sensitivity The chemically amplified positive photosensitive resin compositions of the examples and comparative examples were coated on 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 pre-baked at 110 ° C. for 6 minutes. After pre-baking, pattern exposure was performed with g-line, h-line, and i-line using a mask of a hole pattern with a diameter of 60 μm and an exposure device Titan 2 (manufactured by Ultratech), and the exposure amount was changed stepwise. Next, the substrate was placed on a hot plate and subjected to post-exposure heating (PEB) at 100 ° C for 3 minutes. Thereafter, a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution was dropped onto the photosensitive resin layer, and the mixture was allowed to stand at 23 ° C. for 60 seconds, and development was repeated 4 times. After that, washing with flowing water was performed, and then nitrogen was blown to obtain a thick film photoresist pattern having a contact hole pattern with a diameter of 50 μm. Then, the exposure amount without pattern residues, that is, the minimum exposure amount required for forming a thick film photoresist pattern, is determined 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 △: 150 mJ / cm ² ≦ exposure amount <200 mJ / cm ² ╳: exposure amount ≧ 200 mJ / cm ²

c. Rectangularity Please refer to FIG. 1, which is a schematic diagram of measuring the rectangularity of the photoresist pattern. After the photosensitive resin layer coated on the substrate 100 is subjected to the above-mentioned exposure and development steps, a photoresist pattern 120 having a photoresist portion 122 and a non-photoresist portion 124 is formed. Observe the cross-sectional shape of the photoresist pattern with the optimal exposure, measure the bottom width L _b and the top width L _t , and calculate the value of L _t / L _b as an index of 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 results

As can be seen from Tables 2 and 3, compared with the chemically amplified positive photosensitive resin composition (Example 1-14) containing a high ortho novolac resin (B-1), it does not contain a high ortho novolac The chemically amplified positive photosensitive resin composition of resin (B-1) (Comparative Example 2-4) has poor rectangularity; the chemically amplified positive photosensitive resin composition containing resin (A) (Example) 1-14) In comparison, the sensitivity of the chemically amplified positive photosensitive resin composition (Comparative Examples 1, 4) not containing the resin (A) was not good.

At the same time, when the monomer mixture used for the copolymerization of the resin (A) contains a monomer (a1) having a structure represented by the formula (A-1) (Example 1-7), its rectangularity is more improved. good. In addition, when the monomer mixture (a2) (Example 2-8) containing a cyclic ether group is further included in the monomer mixture, the sensitivity performance is better.

In addition, when a chemically amplified positive photosensitive resin composition contains a thiol compound (E) (Examples 2-4, 6, 8, 12, 13), its rectangularity is also better.

In addition, when the chemically amplified positive photosensitive resin composition contains an anthracene-based compound (F) (Examples 2, 3, 6-8, 13, 14), its sensitivity performance is also better.

In summary, the chemically amplified positive photosensitive resin composition of the present invention contains a high ortho novolac resin (B-1) having 18% to 25% of methyl groups bonded to the ortho-ortho position. ), It can improve the problem of poor rectangularity.

On the other hand, if the resin (A) in the chemically amplified positive photosensitive resin composition of the present invention is obtained by copolymerizing a monomer mixture containing a specific monomer, or the chemically amplified positive photosensitive resin of the present invention When the thiol compound (E) is further contained in the composition, the obtained photoresist pattern can further obtain better rectangularity.

In addition, if the resin (A) in the chemically amplified positive photosensitive resin composition of the present invention is obtained by copolymerizing a monomer mixture containing a specific monomer (a2), or the chemically amplified positive photosensitive composition of the present invention When the anthracene compound (F) is further contained in the resin composition, the prepared photoresist pattern can further obtain better sensitivity.

Although the present invention has been disclosed as above with the examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application.

100‧‧‧ substrate

120‧‧‧Photoresist pattern

122‧‧‧Photoresistance Department

124‧‧‧Non-photoresistance

L _b ‧‧‧ bottom width

L _t ‧‧‧Top width

FIG. 1 is a schematic diagram of measuring the rectangularity of a photoresist pattern.

Claims (13)

A chemically amplified positive photosensitive resin composition comprising: a resin (A), which is obtained by copolymerizing a monomer mixture and contains an acid dissociative protective group; a novolac resin (B); A photoacid generator (C); and a solvent (D), the novolak resin (B) includes a high ortho novolac resin (B-1), and the high ortho novolac resin (B-1) has 18% to 25% of the methyl groups are ortho-ortho. The chemically amplified positive-type photosensitive resin composition according to item 1 of the scope of the patent application, wherein the monomer mixture includes a monomer (a1), and the monomer (a1) has a formula (A-1) ) Shows the structure: Formula (A-1) In 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 group having 1 to 6 carbon atoms. Linear or branched fluorinated alkyl; L ² , L ³ , and L ⁴ each independently represent a linear or branched alkyl having 1 to 6 carbon atoms, or a carbon having 1 to 6 carbon atoms 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 item 1 of the scope of the patent application, wherein the monomer mixture includes a monomer (a2), and the monomer (a2) contains a cyclic ether group. The chemically amplified positive photosensitive resin composition according to item 1 of the scope of the patent application, further comprising a thiol compound (E), wherein the thiol compound (E) has the following formula (E-1) Structure: Formula (E-1) In 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 atom having 1 to 10 carbon atoms. Alkyl, R ⁴ represents a u-valent organic group; u represents an integer of 2 to 6. The chemically amplified positive photosensitive resin composition according to item 1 of the scope of the patent application, further including an anthracene compound (F). The chemically amplified positive photosensitive resin composition according to item 1 of the scope of the patent application, wherein the content of the novolac resin (B) is 20 based on the total amount of the resin (A) used and 20 The content of the photoacid generator (C) is 0.5 to 5 parts by weight, and the content of the solvent (D) is 30 to 360 parts by weight. The chemically amplified positive-type photosensitive resin composition according to item 1 of the scope of patent application, wherein the high ortho novolac resin (B-1) is 100 parts by weight based on the total amount of the resin (A) used. ) Is contained in an amount of 20 to 120 parts by weight. The chemically-amplified positive-type photosensitive resin composition according to item 2 of the scope of patent application, wherein the total amount of the monomer mixture is 100 parts by weight, and the content of the monomer (a1) is 10 parts by weight To 60 parts by weight. The chemically-amplified positive-type photosensitive resin composition according to item 3 of the scope of patent application, wherein the total amount of the monomer mixture is 100 parts by weight, and the content of the monomer (a2) is 5 parts by weight To 30 parts by weight. The chemically-amplified positive-type photosensitive resin composition according to item 4 of the scope of the patent application, wherein the content of the thiol compound (E) is 0.3 based on the total amount of the resin (A) used, which is 100 parts by weight. Parts by weight to 3 parts by weight. The chemically amplified positive-type photosensitive resin composition according to item 5 of the scope of application for a patent, wherein the content of the anthracene-based compound (F) is 0.2 based on 100 parts by weight of the total amount of the resin (A) used. Part by weight to 1.5 parts by weight. A manufacturing method of a substrate with a mold, comprising: a step of laminating on the metal surface of the substrate having a metal surface, the layer being chemically amplified by the method according to any one of the first to eleventh aspects of the patent application scope; A photosensitive resin layer composed of a positive photosensitive resin composition; an exposure step of irradiating the photosensitive resin layer with active light or radiation; and a development step of developing the photosensitive resin layer after exposure, and A mold for forming a plated molded body was prepared. A method for manufacturing an electroplated molded body, comprising: performing plating on a substrate with a mold manufactured by the method for manufacturing a substrate with a mold according to Item 12 of the scope of patent application, and forming electroplating in the mold. Steps of forming body.