CN108241257B - Chemically amplified positive photosensitive resin composition, method for producing substrate with mold, and method for producing molded article by plating - Google Patents
Chemically amplified positive photosensitive resin composition, method for producing substrate with mold, and method for producing molded article by plating Download PDFInfo
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- CN108241257B CN108241257B CN201711391383.XA CN201711391383A CN108241257B CN 108241257 B CN108241257 B CN 108241257B CN 201711391383 A CN201711391383 A CN 201711391383A CN 108241257 B CN108241257 B CN 108241257B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Abstract
The invention provides a chemically amplified positive photosensitive resin composition having excellent sensitivity and rectangularity, a method for producing a substrate with a mold, and a method for producing an electroplated molding. The chemically amplified positive photosensitive resin composition comprises a resin obtained by copolymerization of a monomer mixture and containing an acid-releasable protecting group, a novolak resin, a photoacid generator and a solvent. Wherein the novolac resin is obtained by polycondensing a cresol-based aromatic hydroxyl compound and an aldehyde compound, and the area of cresol dinuclear bodies in the novolac resin is 0.5 to 6 percent based on 100 percent of the integrated area of the molecular weight of the novolac resin measured by a gel permeation chromatography.
Description
Technical Field
The present invention relates to a chemically amplified positive photosensitive resin composition, a method for producing a substrate with a mold, and a method for producing an electroplated molded article, and more particularly, to a chemically amplified positive photosensitive resin composition capable of improving rectangularity, a method for producing a substrate with a mold from the chemically amplified positive photosensitive resin composition, and a method for producing an electroplated molded article from the substrate with a mold.
Background
Nowadays, the photoelectric processing has become the mainstream of the precision microfabrication technology. The term "photo-electric processing" refers to a general term for a technique of coating a resist composition on a surface of a workpiece to form a resist layer, patterning the resist layer by photolithography, and then performing chemical etching, electrolytic etching, or electroforming mainly by electroplating using the patterned resist layer (resist pattern) as a mask to manufacture various precision parts such as a semiconductor package.
In recent years, with the miniaturization of electronic devices, high-density packaging technology for semiconductor packages has been rapidly advancing, and the packaging density of packages has been improved, such as multi-pin thin-film packaging, package size miniaturization, two-dimensional packaging technology using flip chip technology, and three-dimensional packaging technology. In such high-density packaging technology, as the connection terminals, for example, bump electrodes (assembly terminals) for connecting bumps or the like protruding toward the package, rewirings extending from peripheral terminals on the wafer, metal posts of the assembly terminals, and the like are arranged on the substrate with high precision.
Such a photo-electric processing system uses a resist composition, and as such a resist composition, a chemically amplified resist composition containing an acid generator is known (see patent documents 1 and 2, etc.). The chemically amplified resist composition is one which generates an acid from an acid generator by irradiation (exposure) with radiation, promotes the diffusion of the acid by heat treatment, and causes an acid-catalyzed reaction with a matrix resin or the like in the composition to change the alkali solubility.
Such a chemically amplified positive resist composition is used for forming a plating-formed body such as a bump or a metal post in a plating step. Specifically, a resist composition of chemical amplification type is used to form a resist layer having a desired film thickness on a support such as a metal substrate, and the resist layer is exposed and developed through a predetermined mask pattern to form a resist pattern used as a template, wherein a portion where a bump or a metal pillar is to be formed is selectively removed (peeled). Then, a conductor such as copper is embedded in the removed portion (non-resist portion) by plating, and then the resist pattern around the portion is removed, whereby a bump or a metal post can be formed.
However, the aforementioned chemically amplified positive resist composition has the disadvantages of poor sensitivity and poor rectangularity of the formed resist pattern, and is not acceptable in the industry. Therefore, it is an urgent need in the art to provide a chemically amplified positive photoresist composition capable of forming a photoresist pattern with excellent sensitivity and rectangularity.
Patent document
Patent document 1, japanese patent application laid-open No. 9-176112
Patent document 2 Japanese patent application laid-open No. 11-52562
Disclosure of Invention
In view of the above, the present invention provides a chemically amplified positive photosensitive resin composition, which can improve the problems of poor sensitivity and squareness.
The invention provides a chemical amplification type positive photosensitive resin composition, which comprises the following components: a resin (A), a novolac resin (B), a photoacid generator (C), and a solvent (D); the resin (A) is obtained by copolymerizing a monomer mixture and contains an acid-dissociable protecting group; the novolac resin (B) is obtained by polycondensing a cresol-based aromatic hydroxyl compound and an aldehyde compound, and the area of cresol dinuclear bodies in the novolac resin (B) is 0.5 to 6% based on 100% of the integrated area of the molecular weight of the novolac resin (B) measured by gel permeation chromatography.
In an embodiment of the present invention, the monomer mixture includes a first monomer (a 1), and the first monomer (a 1) has a structure represented by the following formula (a-1):
in the formula (A-1), L 1 Represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms; l is a radical of an alcohol 2 、L 3 、L 4 Each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, or L 3 、L 4 Are bonded to each other to form a hydrocarbon ring having 5 to 20 carbon atoms.
In an embodiment of the invention, the monomer mixture includes a second monomer (a 2), and the second monomer (a 2) includes a cyclic ether group.
In an embodiment of the invention, the chemically amplified positive photosensitive resin composition further includes a thiol compound (E), and the thiol compound (E) has a structure represented by the following formula (E-1):
in the formula (E-1), R 1 、R 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 3 Represents a single bond or an alkylene group having 1 to 10 carbon atoms, R 4 Represents a u-valent organic group; u represents an integer of 2 to 6.
In an embodiment of the invention, the chemically amplified positive photosensitive resin composition further includes an anthracene compound (F).
In one embodiment of the present invention, the novolac resin (B) is used in an amount of 20 to 150 parts by weight, the photoacid generator (C) is used in an amount of 0.5 to 5 parts by weight, and the solvent (D) is used in an amount of 30 to 360 parts by weight, based on 100 parts by weight of the total resin (a).
In one embodiment of the present invention, the first monomer (a 1) is used in an amount of 10 to 60 parts by weight, based on 100 parts by weight of the total amount of the monomer mixture.
In one embodiment of the present invention, the second monomer (a 2) is used in an amount of 5 to 35 parts by weight, based on 100 parts by weight of the total amount of the monomer mixture.
In one embodiment of the present invention, the thiol compound (E) is used in an amount of 0.3 to 3 parts by weight, based on 100 parts by weight of the total amount of the resin (a).
In one embodiment of the present invention, the anthracene compound (F) is used in an amount of 0.2 to 1.5 parts by weight, based on 100 parts by weight of the total resin (a).
The present invention also provides a method for manufacturing a substrate with a mold, comprising: a laminating step of laminating a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition on a metal surface of a substrate having the metal surface; an exposure step of irradiating the photosensitive resin layer with active light or radiation; and a developing step of developing the exposed photosensitive resin layer to form a mold for forming a plating molded body.
The present invention also provides a method for manufacturing an electroplated molded body, comprising: and a step of forming a plated molded body in the mold by plating the substrate with the mold, which is manufactured by the method for manufacturing a substrate with a mold.
In view of the above, the chemically amplified positive photosensitive resin composition of the present invention can improve rectangularity because the area of cresol dinuclear bodies in the novolac resin (B) is from 0.5% to 6%.
In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanied with figures are described in detail below.
Drawings
FIG. 1 is a schematic diagram illustrating the measurement of the rectangularity of a photoresist pattern.
The reference numbers illustrate:
100: substrate
120: photoresist pattern
122: light resistance part
124: non-photoresist portion
Lb: width of bottom
And Lt: width of top
Detailed Description
< chemically amplified positive photosensitive resin composition >
The invention provides a chemical amplification type positive photosensitive resin composition, which comprises the following components: a resin (A), a novolac resin (B), a photoacid generator (C) and a solvent (D), wherein the resin (A) is obtained by copolymerization of a monomer mixture and contains an acid-dissociable protecting group; the novolac resin (B) is obtained by polycondensing a cresol-based aromatic hydroxyl compound and an aldehyde compound, and the area of cresol dinuclear bodies in the novolac resin (B) is 0.5 to 6% based on 100% of the integrated area of the molecular weight of the novolac resin (B) measured by gel permeation chromatography. In addition, the chemically amplified positive photosensitive resin composition of the present invention may further comprise a thiol compound (E), an anthracene compound (F), and an additive (G).
The respective components of the chemically amplified positive photosensitive resin composition used in the present invention will be described in detail below.
In the following, acrylic acid and/or methacrylic acid is represented by (meth) acrylic acid, and acrylate and/or methacrylate is represented by (meth) acrylate; similarly, (meth) acryloyl represents acryloyl and/or methacryloyl.
Resin (A)
The resin (A) is obtained by copolymerizing a monomer mixture and contains an acid-dissociable protecting group. Specifically, the monomer mixture may include a first monomer (a 1) having a structure represented by formula (A-1), a second monomer (a 2) containing a cyclic ether group, a monomer (a 3) having a structure represented by formula (A-2) or formula (A-3), and other monomers (a 4).
A first monomer (a 1) having a structure represented by the formula (A-1)
The first monomer (a 1) having a structure represented by formula (A-1) is shown below:
in the formula (A-1), L 1 Represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a linear or branched fluoroalkyl group having 1 to 6 carbon atoms; l is 2 、L 3 、L 4 Each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, or L 3 、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, a n-butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The fluorinated alkyl group means that a part or all of hydrogen atoms of the alkyl group are substituted with fluorine atoms.
When L is 3 、L 4 L when they are not bonded to each other to form a hydrocarbon ring 2 、L 3 、L 4 Preferably a linear or branched alkyl group having 2 to 4 carbon atoms.
L above 3 、L 4 May form an alicyclic group having 5 to 20 carbon atoms together with the carbon atoms to which both are bonded. Specific examples of such alicyclic groups include groups obtained by removing 1 or more hydrogen atoms from a polycyclic alkane such as a monocyclic alkane, bicyclic alkane, tricyclic alkane, or tetracycloalkane. Specifically, there may be mentioned a group obtained by removing 1 or more hydrogen atoms from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane or cyclooctane, or a polycycloalkane such as adamantane, norbornane, isobornene, tricyclodecane or tetracyclododecane. Particularly preferred is a group (which may further have a substituent) obtained by removing 1 or more hydrogen atoms from cyclohexane or adamantane.
Furthermore, when the above-mentioned L 3 、L 4 When the alicyclic group to be formed has a substituent on the ring skeleton, examples of the substituent include a polar group such as a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom (= O), or a linear or branched alkyl group having 1 to 4 carbon atoms. The polar group is preferably an oxygen atom (= O).
Specific examples of the first monomer (a 1) having a structure represented by the formula (A-1) include the following compounds represented by the formulae (A-1-1) to (A-1-33):
in the formulae (A-1-1) to (A-1-33), L 11 Represents a hydrogen atom or a methyl group.
The first monomer (a 1) is used in an amount of 10 to 60 parts by weight, preferably 12 to 55 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the total amount of the monomer mixture.
When the first monomer (a 1) having a structure represented by the formula (A-1) is included in the monomer mixture, the rectangularity of the chemically amplified positive photosensitive resin composition can be further improved.
A second monomer (a 2) containing a cyclic ether group
Specific examples of the second monomer (a 2) having a cyclic ether group include: three-membered rings such as glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, 6, 7-epoxyheptyl (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate, and 3, 4-epoxycyclohexylmethyl (meth) acrylate; <xnotran> 3- () (3- [ (meth) acryloyloxymethyl ] oxetane), 3- () -3- ,3- () -2- ,3- () -2- ,3- () -2- ,3- () -2- ,3- () -2,2- ,3- () -2,2,4- ,3- () -2,2,4,4- ,3- () ,3- () -3- ,2- -3- () ,3- () -2- ,3- () -2- ,3- () -2- ,2,2- -3- () ,3- () -2,2,4- , </xnotran> 3- (meth) acryloyloxyethyl-2,2,4,4-tetrafluoropropylene oxide, 2- (meth) acryloyloxymethyl propylene oxide, 2-methyl-2- (meth) acryloyloxymethyl propylene oxide, 3-methyl-2- (meth) acryloyloxymethyl propylene oxide, 4-methyl-2- (meth) acryloyloxymethyl propylene oxide, 2- (meth) acryloyloxymethyl-2-trifluoromethylpropylene oxide, 2- (meth) acryloyloxymethyl-3-trifluoromethylpropylene oxide, 2- (meth) acryloyloxymethyl-4-trifluoromethylpropylene oxide, 2- (meth) acryloyloxymethyl-2-pentafluoroethyl propylene oxide, 2- (meth) acryloyloxymethyl-3-pentafluoroethyl propylene oxide, 2- (meth) acryloyloxymethyl-4-pentafluoroethyl propylene oxide, 2- (meth) acryloyloxymethyl-2-phenylpropylene oxide, 2- (meth) acryloyloxymethyl-3-phenylpropylene oxide, 2- (meth) acryloyloxymethyl-4-phenylpropylene oxide, 2, 3-difluorooxypropyl-2, 3-difluoromethyloxymethyl-3-phenylpropylene oxide, 2- (meth) acryloyloxymethyl-3-difluorooxypropyl-2, <xnotran> 2,4- -2- () ,3,4- -2- () ,4,4- -2- () ,2- () -3,3,4- ,2- () -3,4,4- ,2- () -3,3,4,4- ,2- () ,2- () -2- ,2- () -4- ,2- () -2- ,2- () -3- ,2- () -4- ,2- () -2- ,2- () -3- ,2- () -4- ,2- () -2- ,2- () -3- , </xnotran> 2- (meth) acryloyloxyethyl-4-phenylepoxypropane, 2, 3-difluoro-2- (meth) acryloyloxyethyl epoxypropane, 2, 4-difluoro-2- (meth) acryloyloxyethyl epoxypropane 3, 3-difluoro-2- (meth) acryloyloxyethyl propylene oxide, 3, 4-difluoro-2- (meth) acryloyloxyethyl propylene oxide a four-membered ring of 4, 4-difluoro-2- (meth) acryloyloxyethyl propylene oxide, 2- (meth) acryloyloxyethyl-3, 4-trifluoropropylene oxide, 2- (meth) acryloyloxyethyl-3, 4-trifluoropropylene oxide, 2- (meth) acryloyloxyethyl-3, 4-tetrafluoropropylene oxide, or the like; tetrahydrofuran (meth) acrylate, caprolactone-modified tetrahydrofuran (meth) acrylate, (2-methyl-2-isobutyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate), (2-methyl-2-isobutyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate ((2-ethyl-2-methyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate), (1, 4-dioxaspiro [4,5] decan-2-yl) methyl (meth) acrylate ((1, 4-dioxaspiro [4,5] dec-2-yl) methyl (meth) acrylate), (2, 2-dimethyl-1, 3-dioxan-4-yl) methyl (meth) acrylate, and the like; and six-membered rings such as (meth) acryloylmorpholine, (meth) acryloyloylmorpholine, tetrahydropyranyl (meth) acrylate, and 2-methyltetrahydropyranyl (meth) acrylate. Among them, preferred are cyclic ether acrylate monomers having four or more members, and more preferred are cyclic ether acrylate monomers having five or more members.
The cyclic ether group-containing second monomer (a 2) may be used singly or in combination of two or more.
The second monomer (a 2) is used in an amount of 5 to 35 parts by weight, preferably 8 to 28 parts by weight, more preferably 10 to 25 parts by weight, based on 100 parts by weight of the total amount of the monomer mixture.
When the second monomer (a 2) containing a cyclic ether group is included in the monomer mixture, the sensitivity of the chemically amplified positive photosensitive resin composition can be further improved.
A monomer (a 3) having a structure represented by the formula (A-2) or the formula (A-3)
The monomer (a 3) having a structure represented by the formula (A-2) or the formula (A-3) is shown below:
in the formulae (A-2) and (A-3), L 5 ～L 10 Each independently represents 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 optionally substituted alicyclic group or alkyl group, p represents an integer of 0 to 4, and q represents 0 or 1.
Further, in the formulae (A-2) and (A-3), L 5 ～L 10 The definition of the linear or branched alkyl group and the linear or branched fluorinated alkyl group in the above formula (A-1) 1 The straight-chain or branched alkyl group and the straight-chain or branched fluorinated alkyl group are defined as the same, and are not described herein again.
When Y is an alicyclic group or an alkyl group, there may be mentioned a group in which 1 or more hydrogen atoms are removed from a polycyclic alkane such as a monocycloparaffin, bicycloalkane, tricycloalkane or tetracycloalkane. Specifically, there may be mentioned a group obtained by removing 1 or more hydrogen atoms from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane or cyclooctane, or a polycycloalkane such as adamantane, norbornane, isobornene, tricyclodecane or tetracyclododecane. Particularly preferred is a group (which may further have a substituent) wherein 1 or more hydrogen atoms are removed from adamantane.
When the alicyclic group represented by Y has a substituent on its ring skeleton, examples of the substituent include a polar group 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. The polar group is preferably an oxygen atom (= O).
When Y is an alkyl group, it is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 6 to 15 carbon atoms. The alkyl group is particularly preferably an alkoxyalkyl group, and examples of the alkoxyalkyl group include a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-n-propoxyethyl group, a 1-isopropoxyethyl group, a 1-n-butoxyethyl group, a 1-isobutoxyethyl group, a 1-tert-butoxyethyl group, a 1-methoxypropyl group, a 1-ethoxypropyl group, a 1-methoxy-1-methyl-ethyl group, and a 1-ethoxy-1-methylethyl group.
Specific examples of the monomer (a 3) having a structure represented by formula (A-2) or formula (A-3) include the following compounds represented by formulae (A-2-1) to (A-2-24) and (A-3-1) to (A-3-15):
in the formulae (A-2-1) to (A-2-24) and (A-3-1) to (A-3-15), L 11 Represents a hydrogen atom or a methyl group.
Other monomers (a 4)
The monomer mixture may further contain another monomer (a 4) other than the first monomer (a 1), the second monomer (a 2) and the monomer (a 3) as long as the effect of the present invention is not impaired. The other monomer (a 4) is, for example, a well-known radical polymerizable compound or an anion polymerizable compound.
Examples of the polymerizable compound include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid, etc.; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α -methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α -methylhydroxystyrene, and α -ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated dienes such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.
Further, as the polymerizable compound, there can be mentioned (meth) acrylates having an acid-non-dissociative aliphatic polycyclic group, vinyl-containing aromatic compounds, and the like. The acid-nondissociable aliphatic polycyclic group is particularly preferably tricyclodecyl, adamantyl, tetracyclododecyl, isobornyl, norbornyl and the like, from the viewpoint of easy industrial availability. These aliphatic polycyclic groups may have a straight or branched alkyl group having 1 to 5 carbon atoms as a substituent.
Specific examples of the (meth) acrylic esters having an acid-non-dissociable aliphatic polycyclic group include compounds represented by the following formulae (A-4-1) to (A-4-5):
in the formulae (A-4-1) to (A-4-5), L 11 Represents a hydrogen atom or a methyl group.
The other monomer (a 4) is used in an amount of 20 to 85 parts by weight, preferably 25 to 80 parts by weight, more preferably 30 to 75 parts by weight, based on 100 parts by weight of the total amount of the monomer mixture.
Method for producing resin (A)
Solvents used in the preparation of resin (a) include, but are not limited to, (1) alcohol compounds: methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, or 3-phenyl-1-propanol, etc.; (2) ether compound: tetrahydrofuran, and the like; (3) glycol ether compound: ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the like; (4) ethylene glycol alkyl ether acetate: ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether acetate, and the like; (5) diethylene glycol compounds: diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, and the like; (6) dipropylene glycol-based compound: dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, and the like; (7) propylene glycol monoalkyl ether compounds: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and the like; (8) propylene glycol alkyl ether acetate compounds: propylene glycol methyl ether acetate (Propylene glycol monomethyl ether acetate), propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, and the like; (9) propylene glycol alkyl ether propionate compounds: propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, and the like; (10) aromatic hydrocarbon compound: toluene, xylene, etc.; (11) ketone compounds: methyl ethyl ketone, cyclohexanone, diacetone alcohol, etc.; (12) ester compounds: <xnotran> , , , ,2- ,2- -2- ,2- -2- , , , , , , ,3- ,3- ,3- ,3- ,2- -3- , , , , , , , , , , , , , , , ,3- ,2- ,2- ,2- ,2- ,2- ,2- ,2- ,2- ,2- ,2- ,2- ,2- ,3- ,3- ,3- ,3- ,3- ,3- , </xnotran> Propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, etc., and these solvents may be used alone or in admixture.
The polymerization initiator used in the preparation of the resin (A) includes, but is not limited to, azo compounds or peroxides, and may be used alone or in combination.
Azo compounds are exemplified by, but not limited to: 2,2' -azobisisobutyronitrile, 2' -Azobis (2, 4-dimethylvaleronitrile) [2,2' -Azobis (2, 4-dimethylvaleronitrile) ], 2' -Azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2' -Azobis-2-methylbutyronitrile [2,2' -Azobis-2-methylbutyronitrile ], 4' -Azobis (4-cyanovaleric acid), dimethyl 2,2' -Azobis (2-methylpropionate), 2' -Azobis (4-methoxy-2, 4-dimethylvaleronitrile) and the like.
Peroxides such as, but not limited to: dibenzoyl peroxide, lauroyl peroxide, t-butylperoxy t-valerate, 1-bis (t-butylperoxy) cyclohexane, hydrogen peroxide, and the like.
The reaction temperature for preparing the resin (A) is 40 to 120 ℃ and the polymerization time is 3 to 12 hours.
The weight average molecular weight of the resin (A) is 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) is obtained by condensation of a cresol-based aromatic hydroxy compound and an aldehyde.
In an embodiment of the present invention, the phenolic aromatic hydroxy compound is: cresols such as m-cresol (m-cresol), p-cresol (p-cresol), and o-cresol (o-cresol); xylenols (xylenol) such as 2, 3-xylenol, 2, 5-xylenol, 3, 5-xylenol and 3, 4-xylenol. The above-mentioned compounds may be used singly or in combination.
The novolak resin (B) of the present invention can be obtained by polycondensation of other aromatic hydroxy compounds and aldehydes without affecting the physical properties of the positive photosensitive resin composition.
In an embodiment of the invention, the other aromatic hydroxy compounds are: phenol (phenol); alkylphenols (alkyl phenols) such as m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3, 5-trimethylphenol, 2,3, 5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol and 6-tert-butyl-3-methylphenol; alkoxyphenols (alkoxy phenols) such as p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol and m-propoxyphenol; isopropenylphenols (isopropenylphenols) such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, and 2-ethyl-4-isopropenylphenol; aryl phenols (aryl phenols) of phenylphenol (phenyl phenol); polyhydroxybenzenes (polyhydroxybenzenes) such as 4,4' -dihydroxybiphenyl, bisphenol A, m-dihydroxybenzene (resorcinol), p-dihydroxybenzene (hydroquinone), and 1,2, 3-benzenetrisol (pyrogallol).
In the specific embodiment of the present invention, the aldehydes condensed with the cresol-based aromatic hydroxy compound are: formaldehyde, paraformaldehyde (paraformaldehyde), trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde (acrolein), crotonaldehyde (crotonaldehyde), cyclohexanaldehyde (cyclo hexanaldehyde), furaldehyde (furfurfuraldehyde), furylacrolein (furylacrolein), benzaldehyde (terpthalol aldehyde), phenylacetaldehyde, α -phenylpropionaldehyde, β -phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, and the like. The aldehydes may be used singly or in combination. Among them, the aldehyde is preferably formaldehyde. Preferably, the novolak resin (B) is obtained by condensation reaction under normal pressure in the presence of a catalyst of a conventional organic acid and/or inorganic acid such as hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid, etc., and by dehydration and removal of unreacted monomers. The term "cresol dinuclear body" as used herein refers to a compound formed by bonding two m/p/o cresol monomers through methylene groups, m-m, o-o, p-p, etc.
In one embodiment of the invention, the level of cresol dinuclear bodies is controlled by fractionation techniques or vacuum distillation. One embodiment of the fractionation technique is to dissolve the synthesized novolak resin in a good solvent and then to precipitate the novolak resin in a poor solvent. In addition, the vacuum distillation method is to distill the novolac resin under reduced pressure at a temperature above 230 ℃ and preferably above 250 ℃ and under a pressure below 1.3kPa during the synthesis of the novolac resin.
The novolak resin (B) according to the present invention has an area of cresol dinuclear bodies of 0.5 to 6%, preferably 0.5 to 5.5%, more preferably 0.5 to 5.0%, based on 100% of the integrated area of the molecular weight of the novolak resin (B) as measured by gel permeation chromatography. If the area of the cresol dinuclear body is less than 0.5 percent, the cost of the treatment process is too high; when the area of the cresol dinuclear body is more than 6%, the rectangularity is poor.
The method for determining the molecular weight of the novolak resin (B) according to the present invention is not limited, and in the specific embodiment of the present invention, the gel permeation chromatography integrates the signal that the molecular weight of the novolak resin (B) is between 200 and 150,000, and obtains an integrated molecular weight distribution curve in terms of the molecular weight and the cumulative weight percentage; wherein gel permeation chromatography is used
A 717plus sample injection instrument; agilent
Prepared 79911GP-501, 79911GP-502, 79911GP-503 or 79911GP-504 tubular column and
2414RI Detector (r); mobile phase: tetrahydrofuran; flow rate: 1.0mL/min; injection amount: 100 mu L of the solution; measuring temperature: 40 ℃; measuring time: 60 minutes; the molecular weight standard is polystyrene.
The weight average molecular weight of the novolac resin (B) is 4,000 to 36,000; preferably 5,000 to 30,000; more preferably 6,000 to 24,000.
The novolak resin (B) is used in an amount of 20 to 150 parts by weight, preferably 25 to 140 parts by weight, more preferably 30 to 130 parts by weight, based on 100 parts by weight of the total resin (a).
Photoacid generators (C)
The photoacid generator (C) is a compound that generates an acid upon irradiation with active light or radiation, and is not particularly limited as long as it is a compound that can directly or indirectly generate an acid by light. The photoacid generators (C) are preferably the acid generators of the first to fifth embodiments described below. Hereinafter, preferred photoacid generators (C) to be suitably used in the photosensitive resin composition will be described in the first to fifth embodiments.
As a first embodiment of the photoacid generator (C), a compound represented by the following formula (C-1) can be mentioned:
in the formula (C-1), X 1 Represents a valence of g, g being 1 or 2.h represents the number of repeating units of the structure in brackets. W 1 Is a reaction with X 1 A bonded organic group representing the number of carbon atomsIs an aryl group of 6 to 30, a heterocyclic group of 4 to 30 carbon atoms, an alkyl group of 1 to 30 carbon atoms, an alkenyl group of 2 to 30 carbon atoms or an alkynyl group of 2 to 30 carbon atoms, W 1 Can be substituted by at least 1 selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro, and halogen. W 1 The number of (a) is g + h (g-1) +1,W 1 May be the same or different from each other. And 2 or more W 1 Can be bonded directly to each other or via-O-, -S-, -SO 2 -、-NH-、-NW 2 -, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or an phenylene group bonded to form a group containing X 1 The ring structure of (a). 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-1 a):
in the formula (C-1 a), X 4 Represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a 2-valent hetero group having 8 to 20 carbon atoms, X 4 May be substituted with at least 1 selected from the group consisting of 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, a nitro group, and a halogen. X 5 represents-O-, -S-) -SO-, -SO 2 -、-NH-、-NW 2 -, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or an phenylene group. h represents the number of repeating units of the structure in brackets. h + 1X 4 And h X 5 May be the same or different. W 2 Is the same as defined above.
(X 3 ) - As the counter ion (counter ion) of the onium, there may be mentioned fluoroalkyl fluorophosphate anion represented by the following formula (C-1 b) orA borate anion represented by the following formula (C-1C):
[(W 3 ) j PF 6-j ] - formula (C-1 b)
In the formula (C-1 b), W 3 Represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. j represents the number thereof and is an integer of 1 to 5. j W 3 May be the same or different.
In the formula (C-1C), W 4 ～W 7 Each independently represents a fluorine atom or a phenyl group, and a part or all of hydrogen atoms in the phenyl group may be substituted by at least 1 selected from the group consisting of a fluorine atom and a trifluoromethyl group.
As the onium ion in the compound represented by the formula (C-1), examples thereof include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonium) phenyl ] sulfide, bis [4- { bis [4- (2-hydroxyethoxy) phenyl ] sulfonium } phenyl ] sulfide, bis {4- [ bis (4-fluorophenyl) sulfonium ] phenyl } sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 7-isopropyl-9-oxy-10-thia-9, 10-dihydroanthracen-2-ylbis-p-tolylsulfonium, 7-isopropyl-9-oxy-10-thia-9, 10-dihydroanthracen-2-ylbis-phenylsulfinium, 2- [ (diphenyl) sulfonium ] thianthrenone, 4- [4- (4-tert-butylbenzoyl) thiophenyl ] phenyl-di-p-tolylsulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, diphenylphenylacetylsulfonium, 4-hydroxyphenylmethylsulfanyl, 2-naphthylmethylcarbonylethylthiophenyl (1-4-phenylethynylthio) diphenylsulfonium, 4- (4-hydroxyphenylmethylthiophenyl) phenylsulfonium, 4- (4-hydroxyphenylmethylthiophenyl) sulfonium, 4- (4-phenylthiophenyl) diphenylsulfonium, 4-diphenylacetyl) diphenylsulfonium, 4-diphenylmethylthiophenyl [ 3-phenylsulfonium ] sulfonium, and 3-phenylthiophenyl ] sulfonium, [4- (4-acetylphenylthio) phenyl ] diphenylsulfonium, octadecylmethylbenzacetylsulfonium, diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-dodecyloxy) phenyliodonium, 4- (2-hydroxytetradecyloxy) phenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, or 4-isobutylphenyl (p-tolyl) iodonium.
Among the onium ions in the compound represented by the formula (C-1), preferred onium ions include sulfonium ions represented by the following formula (C-1 d):
in the formula (C-1 d), W 8 Each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, a halogen atom, an optionally substituted aryl group and an arylcarbonyl group. X 2 X in the formula (C-1) 2 The same meaning is used.
Specific examples of the sulfonium ion represented by the formula (C-1 d) include 4- (phenylthio) phenyldiphenylsulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl ] 4-diphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl ] 3-diphenylsulfonium, [4- (4-acetylphenylthio) phenyl ] diphenylsulfonium, and diphenyl [4- (p-triphenylthio) phenyl ] diphenylsulfonium.
In the fluoroalkyl fluorophosphate anion represented by the formula (C-1 b), W is 3 Represents an alkyl group substituted with a fluorine atom, and preferably has 1 to 8 carbon atoms, and more preferably has 1 to 4 carbon atoms. Specific examples of the alkyl group include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group and the like; further, in the case of cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, the ratio of hydrogen atoms in the alkyl group substituted by fluorine atoms is usually 80% or more, preferably 90% or more, more preferably 100%. If the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium fluoroalkyl fluorophosphate represented by the above formula (C-1) is lowered.
Particularly preferred is W 3 A linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%, and a specific example thereof is CF 3 、CF 3 CF 2 、(CF 3 ) 2 CF、CF 3 CF 2 CF 2 、CF 3 CF 2 CF 2 CF 2 、(CF 3 ) 2 CFCF 2 、CF 3 CF 2 (CF 3 )CF、(CF 3 ) 3 C。W 3 The number j of (a) is an integer of 1 to 5, preferably 2 to 4, particularly preferably 2 or 3.
As a specific example of a preferred fluoroalkyl fluorophosphate anion, there can be mentioned [ (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 ] - Of 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 a preferred specific example of the borate anion represented by the above formula (C-1C), tetrakis (pentafluorophenyl) borate ([ B (C) is mentioned 6 F 5 ) 4 ] - ) And tetrakis [ (trifluoromethyl) phenyl group]Borate ([ B (C)) 6 H 4 CF 3 ) 4 ] - ) Difluoro bis (pentafluorophenyl) borate ([ (C) 6 F 5 ) 2 BF 2 ] - ) Trifluoro-pentafluorophenyl borate ([ (C) 6 F 5 )BF 3 ] - ) Tetrakis (difluorophenyl) borate ([ B (C)) 6 H 3 F 2 ) 4 ] - ) And the like. Of these, tetrakis (pentafluorophenyl) borate ([ B (C) is particularly preferred 6 F 5 ) 4 ] - )。
<xnotran> (A) , 2,4- ( ) -6- -1,3,5- ,2,4- ( ) -6- [2- (2- ) ] ,2,4- ( ) -6- [2- (5- -2- ) ] ,2,4- ( ) -6- [2- (5- -2- ) ] ,2,4- ( ) -6- [2- (5- -2- ) ] ,2,4- ( ) -6- [2- (3,5- ) ] ,2,4- ( ) -6- [2- (3,5- ) ] ,2,4- ( ) -6- [2- (3,5- ) ] ,2,4- ( ) -6- [2- (3- -5- ) ] ,2,4- ( ) -6- [2- (3- -5- ) ] , </xnotran> 2, 4-bis (trichloromethyl) -6- [2- (3, 4-methylenedioxyphenyl) vinyl ] sym-triazine, 2, 4-bis (trichloromethyl) -6- (3, 4-methylenedioxyphenyl) sym-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl sym-triazine, 2, 4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl sym-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl sym-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- [2- (2-furyl) vinyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- [2- (2-dimethoxyvinyl ] -4, 3, 5-bis (trichloromethyl) -1,3, 5-triazine, 2- [2- (2-furyl) vinyl ] -4, 3, 5-bis (trichloromethyl) -1, 5-triazine, halogen-containing triazine compounds such as 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-triazine, tris (1, 3-dibromopropyl) -1,3, 5-triazine, tris (2, 3-dibromopropyl) -1,3, 5-triazine and the like, and triazine compounds containing halogen represented by the following formula (C-2) such as tris (2, 3-dibromopropyl) isocyanurate and the like.
In the formula (C-2), W 9 ～W 11 Each independently represents a haloalkyl group.
The third embodiment of the photoacid generator (C) includes α - (p-toluenesulfonyloxyimino) -phenylacetonitrile, α - (benzenesulfonyloxyimino) -2, 4-dichlorophenylacetonitrile, α - (benzenesulfonyloxyimino) -2, 6-dichlorophenylacetonitrile, α - (2-chlorobenzenesulfonylyloxyimino) -4-methoxyphenylacetonitrile, α - (ethylsulfonyloxyimino) -1-chloroprenylacetonitrile, and a sulfonic acid oxime group-containing compound represented by the following formula (C-3).
In the formula (C-3), W 12 Represents a 1-, 2-or 3-valent organic group, W 13 Represents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic compound group, and n represents the number of repeating units in a bracket.
In the above formula (C-3), the aromatic compound group represents a group of a compound which gives an aromatic compound a specific physical or chemical property, and examples thereof include an aryl group such as a phenyl group or a naphthyl group, and a heteroaryl group such as a furyl group or a thienyl group. These may also have 1 or more suitable substituents on the ring, such as halogen atoms, alkyl groups, alkoxy groups, nitro groups, and the like. And W 13 Particularly preferred is an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. Especially W 12 Is an aromatic compound radical, W 13 Is a compound of an alkyl group having 1 to 4 carbon atomsThe compound is preferred.
When n =1, an acid generator represented by the formula (C-3) includes W 12 Is any one of phenyl, methylphenyl and methoxyphenyl, W 13 Specific examples of the compound which is a methyl group include α - (methylsulfonyloxyimino) -1-phenylacetonitrile, (-methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, (-methylsulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile, (-2- (propylsulfonyloxyimino) -2, 3-dihydroxythiophen-3-ylidene](o-tolyl) acetonitrile, and the like. When n =2, specific examples of the acid generator represented by the formula (C-3) include acid generators represented by the following formulae (C-3-1) to (C-3-8):
in addition, as a fourth embodiment of the photoacid generator (C), an onium salt having a naphthalene ring as a cationic moiety can be mentioned. The term "having a naphthalene ring" refers to having a structure derived from naphthalene, which means a structure of at least 2 rings and maintains the aromaticity thereof. The naphthalene ring may have a substituent 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, or the like. The structure derived from the naphthalene ring may be a 1-valent group (free valence is 1), or a 2-valent group (free valence is 2) or more, preferably a 1-valent group (in this case, the free valence is calculated by subtracting the moiety bonded to the substituent described above). The number of naphthalene rings is preferably 1 to 3.
As the cation moiety of such onium salts having a naphthalene ring as the cation moiety, a structure represented by the following formula (C-4) is preferred:
in the formula (C-4), W 14 ～W 16 At least 1 of them represents a group represented by the following formula (C-4 a), and the others represent a linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted phenyl group, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Or, W 14 ～W 16 One of them is a group represented by the following formula (C-4 a), and the remaining two are each independently a carbon atom number W 14 ～W 16 Linear or branched alkylene groups, the ends of which may be bonded to form a ring.
In the formula (C-4 a), W 17 、W 18 Each independently represents a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms, and 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 independently represent an integer of 0 to 2, and l + m is 3 or less. When W is 17 When plural, they may be the same or different from each other. When W 18 When plural, they may be the same as or different from each other.
W mentioned above 14 ～W 16 Among them, the number of the group represented by the above formula (C-4 a) is preferably 1 from the viewpoint of stability of the compound, and the remainder is a linear or branched alkylene group having 1 to 6 carbon atoms, and the terminals of these groups may be bonded to form a ring. In this case, the 2 alkylene groups may contain a sulfur atom to form a 3-to 9-membered ring. The number of atoms constituting the ring (sulfur-containing atoms) is preferably 5 to 6.
Examples of the substituent which the alkylene group may have include an oxygen atom (in this case, a carbonyl group is formed together with a carbon atom constituting the alkylene group), a hydroxyl group, and the like.
Examples of the substituent 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 alkyl group having 1 to 6 carbon atoms.
As such a cationic moiety, those represented by the following formulae (C-4 b) and (C-4C) are suitable, and those represented by the following formula (C-4C) are particularly preferred.
As such a cationic moiety, an iodonium salt or a sulfonium salt may be used; sulfonium salts are preferred from the viewpoint of acid generation efficiency.
Therefore, an anion portion suitable as an onium salt having a naphthalene ring as a cation portion is preferably an anion capable of forming a sulfonium salt.
As the anion portion of such an acid generator, a fluoroalkyl sulfonic acid ion or an aryl sulfonic acid ion in which a part or all of hydrogen atoms are fluorinated is used.
The alkyl group in the fluoroalkylsulfonic acid ion may be linear, branched or cyclic having 1 to 20 carbon atoms, and preferably has 1 to 10 carbon atoms depending on the volume size of the acid to be produced and the diffusion distance thereof. Particularly, the branched or ring-shaped one is preferable because of the short diffusion distance. Further, methyl, ethyl, propyl, butyl, octyl and the like are preferable because they can be synthesized at low cost.
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. Particularly, an aryl group having 6 to 10 carbon atoms is preferable because it can be synthesized at low cost. Preferable specific examples thereof include phenyl, tosyl, ethylphenyl, naphthyl and methylnaphthyl.
In the above fluoroalkyl sulfonic acid ion or aryl sulfonic acid ion, the fluorination rate when part or all of the hydrogen atoms are fluorinated is preferably 10 to 100%, more preferably 50 to 100%, and particularly preferably the fluorination rate is such that all of the hydrogen atoms are replaced with fluorine atoms, because the strength of the acid is enhanced. Specific examples of such a compound include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate and perfluorobenzenesulfonate.
Among these, preferable examples of the anionic moiety include those represented by the following formula (C-4 d):
W 20 SO 3 - formula (C-4 d)
In the formula (C-4 d), W 20 Are represented by the following formulae (C-4 e), (C-4 f) and (C-4 g).
-C x F 2x+1 Formula (C-4 e)
In the formula (C-4 e), x represents an integer of 1 to 4. In the formula (C-4 f), 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 alkoxy group having 1 to 6 carbon atoms, and y represents an integer of 1 to 3. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.
As the anion moiety, nitrogen-containing ones represented by the following formulas (C-4 h) and (C-4 i) can be used.
In the formula (C-4 h) or the formula (C-4 i), X a Represents a linear or branched alkylene group in which at least 1 hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6, preferably 3 to 5, and most preferably 3 carbon atoms. And, Y a 、Z a Each independently represents a linear or branched alkyl group in which at least 1 hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10, preferably 1 to 7, and more preferably 1 to 3 carbon atoms.
X a The number of carbon atoms of the alkylene group of (2), or Y a 、Z a The smaller the number of carbon atoms of the alkyl group (b), the better the solubility in an organic solvent.
And, X a Alkylene group of or Y a 、Z a Among the alkyl groups of (3), the larger the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, and thus preferred. Fluorine atom in the alkylene group or alkyl groupThe ratio of (A) to (B), i.e., the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, most preferably a perfluoroalkylene or perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
As onium salts having a naphthalene ring in the cationic moiety, those having the following formulae (C-4 j) and (C-4 k) are suitable:
further, as a fifth embodiment of the photoacid generator (C), bis (sulfonyl) diazomethanes such as bis (p-toluenesulfonyl) diazomethane, bis (1, 1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (2, 4-dimethylphenylsulfonyl) diazomethane; nitrobenzyl derivatives such as 2-nitrobenzyl p-toluenesulfonate, 2, 6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl toluenesulfonate, dinitrobenzyl toluenesulfonate, nitrobenzyl sulfonate, nitrobenzyl carbonate and dinitrobenzyl carbonate; sulfonic acid esters such as pyrogallol trifluoromethanesulfonate, pyrogallol trimethylbenzenesulfonate, phenylmethyl toluenesulfonate, phenylmethyl sulfonate, N-methanesulfonyloxy succinimide, N-trichloromethylsulfonyloxy succinimide, N-phenylsulfonyloxy maleimide and N-methanesulfonyloxy phthalimide; trifluoromethanesulfonates such as N-hydroxyphthalimide and N-hydroxynaphthalimide; onium salts such as iodonium hexafluorophosphate, a (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tertiary-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, a (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, a (p-tertiary-butylphenyl) diphenylsulfonium trifluoromethanesulfonate, and the like; benzoin tosylates such as benzoin tosylate and α -methyl benzoin tosylate; other examples of the salt include diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, and benzyl carbonate.
The photoacid generator (C) may be used alone or in combination of 2 or more.
Also, the photoacid generator (C) is used in an amount of 0.5 to 5 parts by weight, preferably 0.6 to 4.5 parts by weight, more preferably 0.7 to 4 parts by weight, based on 100 parts by weight of the total amount of the resin (a).
Solvent (D)
The type of the solvent (D) is not particularly limited as long as the object of the present invention is not impaired, and can be suitably selected from organic solvents conventionally used for 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; polyhydric alcohols such as ethylene glycol, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol, diethylene glycol dimethyl ether, monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether of dipropylene glycol monoacetate, and derivatives thereof; cyclic ethers such as dioxane; esters such as ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and propylene glycol methyl ether acetate; aromatic hydrocarbons such as toluene and xylene; and so on. These may be used alone or in combination of 2 or more.
The solvent (D) is used in an amount of 30 to 360 parts by weight, preferably 40 to 300 parts by weight, more preferably 50 to 240 parts by weight, based on 100 parts by weight of the total amount of the resin (a).
Thiol Compound (E)
The thiol compound (E) has a structure represented by the following formula (E-1):
in the formula (E-1), R 1 、R 2 Each independently represents a hydrogen atomOr an alkyl group having 1 to 4 carbon atoms, R 3 Represents a single bond or an alkylene group having 1 to 10 carbon atoms, R 4 Represents a u-valent organic group; u represents an integer of 2 to 6.
When R is 1 、R 2 When the alkyl group is used, the alkyl group may be linear or branched, and is preferably linear. When R is 1 、R 2 When an alkyl group is used, the number of carbon atoms in the alkyl group is preferably 1 to 4, particularly preferably 1 or 2, and most preferably 1. As R 1 、R 2 The combination of (1) is preferably a hydrogen atom and the other is an alkyl group, and particularly preferably a hydrogen atom and the other is a methyl group.
When R is 3 When the alkylene group is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. When R is 3 When the alkylene group 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, most preferably 1.
R 4 The u-valent organic group defined is specifically a 2-6-valent aliphatic group which may contain an atom other than carbon. As R 4 Examples of the atom other than carbon which may be contained include a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. R 4 The structure of the aliphatic group may be straight chain, branched chain or cyclic, or may be a combination of these structures.
Among the thiol compounds (E) represented by the formula (E-1), more preferred are compounds represented by the following formula (E-2):
in the formula (E-2), R 4 U is as defined for formula (E-1), R 5 Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Specific examples of the thiol compound (E) include, but are not limited to, the following formulas (E-3) to (E-16):
the thiol compound (E) is used in an amount of 0.3 to 3 parts by weight, preferably 0.4 to 2.8 parts by weight, more preferably 0.5 to 2.5 parts by weight, based on 100 parts by weight of the total amount of the resin (A).
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 Compound (F)
The anthracene compound (F) includes, but is not limited to, the following specific examples: anthracene (anthrylene), 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-10-methylanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene, 2-tert-butyl-9, 10-diethoxyanthracene, 2, 3-dimethyl-9, 10-diethoxyanthracene, 9-ethoxy-10-methylanthracene, 9, 10-dipropoxyanthracene, 9, 10-diisopropoxylanthracene, 2-ethyl-9, 10-dipropoxyanthracene, 2-tert-butyl-9, 10-dipropoxyanthracene 2, 3-dimethyl-9, 10-dipropoxyanthracene, 9-isopropoxy-10-methylanthracene, 9, 10-dimethylphenoxyanthracene, 2-ethyl-9, 10-dimethylphenoxyanthracene, 2-tert-butyl-9, 10-xyloxyanthracene, 2, 3-dimethyl-9, 10-xyloxyanthracene, 9-tolyloxy-10-methylanthracene, 9, 10-di-alpha-methyltolyloxyanthracene, 2-ethyl-9, 10-di-alpha-methyltolyloxyanthracene, 2-tert-butyl-9, 10-di-alpha-methyltolyloxyanthracene, 2, 3-dimethyl-9, 10-di-alpha-methyltolyloxyanthracene, 9- (alpha-methyltolyloxy) -10-methylanthracene, 9, 10-diphenylanthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9-methylanthracene, 9-bromoanthracene, 9-methylthioanthracene, 9-ethylthioanthracene, etc.
The anthracene compound (F) is used in an amount of 0.2 to 1.5 parts by weight, preferably 0.25 to 1.3 parts by weight, more preferably 0.3 to 1.1 parts by weight, based on 100 parts by weight of the total resin (a). When the chemically amplified positive photosensitive resin composition includes the anthracene compound (F), the sensitivity of the chemically amplified positive photosensitive resin composition can be further improved.
Additive (G)
The chemically amplified positive photosensitive resin composition may further contain an additive (G) alone or in combination as long as the effect of the present invention is not impaired, and the additive (G) may be used alone or in combination of two or more. The following describes the details of the additive (G).
The chemically amplified positive photosensitive resin composition may further contain a polyethylene resin as an additive (G) for improving moldability. Specific examples of the polyethylene resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol, and copolymers thereof. The polyethylene resin is preferably polyvinylmethylether, because of its low glass transition point.
In addition, in order to improve the adhesion between the metal substrate and the template formed by using the photosensitive resin composition, the chemically amplified positive photosensitive resin composition may further contain an adhesion promoter as an additive (G). Specific examples of the adhesion promoter include those commercially available from CYTEC corporation under the type of Cymel-300 or Cymel-303; thirdly, chemically manufacturing melamine compounds such as commodities with the types of MW-30MH, MW-30, MS-11, MS-001, MX-750 or MX-706; silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and bis-1, 2- (trimethoxysilyl) ethane.
The chemically amplified positive photosensitive resin composition may further contain a surfactant as an additive (G) in order to improve coatability, defoaming property, leveling property, and the like. Specific examples of the surfactant include commercially available fluorine-based surfactants such as BM-1000, BM-1100 (both of BM Chemie), MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F183 (both of DIC), FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (both of Sumitomo 3M), SURFON S-112, SURFON S-113, SURFON S-131, SURFON S-141, SURFON S-145 (both of Asahi Nippon), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (both of Toray Silicone), but are not limited thereto.
In addition, the chemically amplified positive photosensitive resin composition may further contain an acid, an acid anhydride, or a high boiling point solvent as an additive (G) for fine adjustment of the solubility in the developer.
Specific examples of the acid and the acid anhydride include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; hydroxymonocarboxylic acids such as 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, and syringic acid; polycarboxylic acids such as 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, and 1,2,5, 8-naphthalenetetracarboxylic acid; anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, propanetricarboxylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, humic anhydride, 1,2,3, 4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitic anhydride, and glycerol trimellitic anhydride; and the like.
Specific examples of the high boiling point solvent include N-methylformamide, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidinone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ -butyrolactone, vinyl carbonate, propylene carbonate, and phenylsuccinacetate.
In addition, the chemically amplified positive photosensitive resin composition may further contain a sensitizer as an additive (G) in order to improve sensitivity.
< method for producing chemically amplified positive photosensitive resin composition >
The method for producing the chemically amplified positive photosensitive resin composition is not particularly limited, and the above-mentioned components can be mixed and stirred by a usual method. Examples of the apparatus that can be used when mixing and stirring the above-mentioned components include a dissolver, a homogenizer, and a triple roll mill. After the above components are uniformly mixed, the resulting mixture may be further filtered by a screen, a membrane filter, or the like.
< method for producing substrate with mold >
The method for forming a resist pattern as a mold for forming a plating molded body on a metal surface of a substrate having a metal surface by using the chemically amplified positive photosensitive resin composition is not particularly limited.
Preferred examples of the method include a method comprising: a laminating step of laminating a photosensitive resin layer made of the chemically amplified positive photosensitive resin composition on a metal surface of a substrate having the metal surface; an exposure step of irradiating the photosensitive resin layer with active light or radiation; and a developing step of developing the exposed photosensitive resin layer to form a mold for forming a plating molded body.
The substrate on which the photosensitive resin layer is to be laminated is not particularly limited, and conventionally known substrates can be used, and examples thereof include a substrate for electronic components and a substrate having a predetermined wiring pattern formed thereon. For the substrate, one having a metal surface is used; as the metal species constituting the metal surface, copper, gold, aluminum are preferable, and copper is more preferable.
The photosensitive resin layer is laminated on the substrate in the following manner, for example. That is, a liquid chemically amplified positive photosensitive resin composition is applied to 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 a resist pattern serving as a template can be formed with a desired film thickness. The thickness of the photosensitive resin layer is not particularly limited, but is preferably 10 μm or more, more preferably 10 to 150 μm, particularly preferably 20 to 120 μm, most preferably 20 to 100 μm.
As a method for coating the photosensitive resin composition on the substrate, a spin coating method, a slit coating method, a roll coating method, a screen printing method, a dispensing method, or the like can be used. The photosensitive resin layer is preferably pre-baked. The prebaking conditions vary depending on the kind, blending ratio, coating thickness and the like of each component in the photosensitive resin composition, but are usually 70 to 150 ℃, preferably 80 to 140 ℃ and 2 to 60 minutes or so.
The photosensitive resin layer formed as described above is selectively irradiated (exposed) with active light or radiation, for example, ultraviolet light or visible light having a wavelength of 300 to 500nm, through a mask having a predetermined pattern.
As a radiation source, a low-pressure mercury lamp or high-pressure mercury can be usedLamps, ultra-high pressure mercury lamps, metal halide lamps, argon lasers, and the like. The radiation includes microwave, infrared ray, visible ray, ultraviolet ray, X-ray, γ -ray, electron beam, proton beam, neutron beam, ion beam, and the like. The amount of radiation exposure varies depending on the composition of the photosensitive resin composition, the thickness of the photosensitive resin layer, etc., and is, for example, 100 to 10000mJ/cm when using an ultra-high pressure mercury lamp 2 . The radiation includes light for activating the photoacid generator (C) to generate an acid.
After the exposure, the photosensitive resin layer is heated by a known method to promote the diffusion of acid, and the alkali solubility of the photosensitive resin layer is changed in the exposed portion of the photosensitive resin film.
Then, the exposed photosensitive resin layer is developed according to the conventional method, and the soluble portion is dissolved and removed to form a predetermined resist pattern. In this case, an alkaline aqueous solution is used as the developer.
As the developer, for example, an aqueous solution of a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1, 8-diazabicyclo [5,4,0] -7-undecene, 1, 5-diazabicyclo [4,3,0] -5-nonane, or the like can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the alkali may be used as the developer.
The developing 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 developing method may be any of a liquid coating method, a dipping method, a paddle method, a jet developing method, and the like.
After the development, the resultant is washed with running water for 30 to 90 seconds and dried with an air gun, an oven, or the like. Thus, a substrate with a mold having a resist pattern as a mold on a metal surface of a substrate having a metal surface can be manufactured.
< method for producing electroplated molded article >
By embedding a conductor such as a metal in the non-resist portion (a portion removed with a developer) of the mold of the substrate with a mold formed by the above method, a plating molded body such as a connection terminal such as a bump or a metal post can be formed. The plating method is not particularly limited, and various conventionally known methods can be used. The plating solution is particularly preferably solder plating, copper plating, gold plating, or nickel plating. The residual mold is finally removed by a stripping liquid or the like according to a conventional method.
According to the above method, a resist pattern which can be used as a mold while suppressing undercut is formed. By using the substrate having the mold capable of suppressing undercut, a plated molded article excellent in adhesion to the substrate can be produced.
The present invention will be described in detail with reference to examples, but the present invention is not limited to the disclosure of these examples.
< example >
Synthesis example of resin (A)
Synthesis examples A-1 to A-10 of the resin (A) are described below:
synthesis example A-1
A four-neck conical flask with a volume of 1000 ml is provided with a nitrogen inlet, a stirrer, a heater, a condenser tube and a thermometer. Then, 50 parts by weight of diethylene glycol dimethyl ether was added, and the oil bath temperature was raised to 70 ℃. Next, 15 parts by weight of a compound represented by the formula (a-1-26) (referred to simply as (a 11)), 10 parts by weight of methacrylic acid (referred to simply as (a 41)), 10 parts by weight of 2-hydroxyethyl methacrylate (referred to simply as (a 43)), 35 parts by weight of isobornyl methacrylate (referred to simply as (a 44)), 30 parts by weight of benzyl methacrylate (referred to simply as (a 46)), and 3.5 parts by weight of 2,2' -azobis-2-methylbutyronitrile (referred to simply as AMBN) were added to a four-necked flask, and the above mixed solution was slowly stirred. The reaction temperature during the whole polymerization was maintained at 70 ℃ and the polymerization time was continued for 6 hours, and after completion of the polymerization, the polymerization product was taken out from the four-necked flask, and the solvent was removed to obtain resin (A-1).
Synthesis examples A-2 to A-10
Synthesis examples A-2 to A-10 resins (A-2) to (A-10) were prepared in the same procedure as in Synthesis example A-1, except that: the reaction temperature, reaction time, kinds of components and amounts used were changed and are described in Table 1.
The compounds corresponding to the abbreviations in the following synthetic examples A-1 to A-10 are as follows.
[ Table 1]
Example of Synthesis of novolak resin (B)
The novolak resin (B) was synthesized according to the components shown in table 2 and table 3 below.
[ Table 2]
[ Table 3]
Synthesis of Novolac resin (B-1)
A four-necked flask having a capacity of 1,000 ml was equipped with a nitrogen inlet, a stirrer, a heater, a condenser and a thermometer, and nitrogen was introduced and fed with a feed composition comprising: 0.7 mol of m-cresol, 0.3 mol of p-cresol, 0.65 mol of formaldehyde and 0.02 mol of oxalic acid. The contents of the four-necked erlenmeyer flask were stirred and the oil bath temperature was raised to 100 ℃. The reaction temperature during the polycondensation is maintained at 100 ℃ for 6 hours. After completion of polycondensation, the solvent was devolatilized to obtain a novolak resin (B-1).
Synthesis of Novolac resin (B-2) and (B-3)
The same procedure as for the operation of the novolak resin (B-1) was conducted except that the kind and the mixing amount of the aromatic hydroxy compound, the amount of the aldehyde, the amount of the acidic catalyst, and the reaction temperature, the formulation thereof and the reaction conditions were changed as shown in Table 2.
Synthesis of Novolac resin (B-4)
100 parts by weight of the novolak resin (B-1) obtained above was dissolved in 300 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and the solution was stirred at room temperature until completely dissolved. Then, the mixture was poured into 2,000 parts by weight of Ethylbenzene (Ethylbenzene) and stirred for 30 minutes, and then the precipitate was taken out and the solvent was devolatilized to obtain a novolak resin (B-4).
Synthesis of Novolac resin (B-5)
100 parts by weight of the novolak resin (B-1) obtained above was dissolved in 300 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and the solution was stirred at room temperature until completely dissolved. Then, the mixture was poured into 3,000 parts by weight of cumene and stirred for 30 minutes, and then the precipitate was taken out and the solvent was devolatilized to obtain a novolak resin (B-5).
Synthesis of Novolac resin (B-6)
100 parts by weight of the novolak resin (B-2) obtained above was dissolved in 300 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and the mixture was stirred at room temperature until completely dissolved. Then, the mixture was poured into 2,000 parts by weight of cumene, and the mixture was stirred for 30 minutes, and then the precipitate was taken out, and the solvent was devolatilized, and then the above dissolving, precipitating, and devolatilizing steps were repeated to obtain a novolak resin (B-6).
Synthesis of Novolac resin (B-7)
100 parts by weight of the novolak resin (B-3) obtained above was dissolved in 300 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and the solution was stirred at room temperature until completely dissolved. Then, the mixture was poured into 2,000 parts by weight of ethylbenzene and 1,000 parts by weight of cumene, and stirred for 30 minutes, and then the precipitate was taken out, and after the solvent was devolatilized, the above-mentioned dissolving, precipitating, and devolatilizing steps were repeated to obtain a novolak resin (B-7).
Area of cresol dinuclear bodies in novolak resin (B)
Operating in a gel permeation chromatography by integrating the signal of novolak resin (B) having a molecular weight of 200 to 150,000 and obtaining an integrated molecular weight distribution curve in terms of molecular weight and cumulative weight percentage; wherein the gel permeation chromatography is performed using
A 717plus sample injection instrument; agilent
Prepared 79911GP-501, 79911GP-502, 79911GP-503 or 79911GP-504 tubular column and
2414RI Detector (r); mobile phase: tetrahydrofuran; flow rate: 1.0mL/min; injection amount: 100 mu L of the solution; measuring temperature: at 40 ℃; measuring time: 60 minutes; the molecular weight standard is polystyrene.
The percentage of the area of cresol dinuclear bodies in the novolak resin (B) was measured based on 100% of the integrated area of the molecular weight of the novolak resin (B) measured by gel permeation chromatography.
The results are shown in tables 2 and 3.
Examples of chemically amplified positive photosensitive resin compositions
Examples 1 to 14 and comparative examples 1 to 4 of the chemically amplified positive photosensitive resin composition are described below:
example 1
A chemically amplified positive photosensitive resin composition was prepared by adding 30 parts by weight of propylene glycol methyl ether acetate (hereinafter referred to as D-1) to 100 parts by weight of the resin (A-1) obtained in Synthesis example A-1, 20 parts by weight of the novolak resin (B-4), 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-piperonyl-1, 3, 5-triazine (hereinafter referred to as C-2) and then dissolving and mixing them in a shaking mixer, and the results of the evaluation were shown in Table 4.
Example 2 to example 14
Examples 2 to 14 used the same operation method as the method for producing the chemically amplified positive photosensitive resin composition of example 1, except that the types and the amounts of the raw materials used in the chemically amplified positive photosensitive resin composition were changed, and the formulations and the following evaluation results were shown in tables 4 and 5 in examples 2 to 14.
Comparative examples 1 to 4
Comparative examples 1 to 4 were prepared by the same method as the method for preparing the chemically amplified positive photosensitive resin composition of example 1, except that the types and amounts of the raw materials used in the chemically amplified positive photosensitive resin composition were changed in comparative examples 1 to 4, and the formulations and the following evaluation results were shown in table 5.
[ Table 4]
[ Table 5]
The compounds identified by the reference numerals in tables 4 and 5 are shown below.
Evaluation method
a. Sensitivity of the device
The chemically amplified positive photosensitive resin compositions of examples and comparative examples were applied to a 6-inch copper substrate using a spin coater to form a photosensitive resin layer having a thickness of 50 μm. Thereafter, the photosensitive resin layer was prebaked at 110 ℃ for 6 minutes. After the pre-baking, pattern exposure was performed with g-line, h-line, and i-line using a mask having a hole pattern of 60 μm in diameter and an exposure device Titan 2 (manufactured by Ultratech), and the exposure amount was changed stepwise. Subsequently, the substrate was placed on a hot plate, and post-exposure heating (PEB) was performed at 100 ℃ for 3 minutes. Thereafter, a 2.38% aqueous tetramethylammonium hydroxide (TMAH) solution was dropped onto the photosensitive resin layer, and the layer was left at 23 ℃ for 60 seconds, and development was repeated 4 times. Thereafter, the resist was washed with running water and then nitrogen gas was blown to obtain a thick film resist pattern having a contact hole pattern with a diameter of 50 μm.
Then, the exposure amount without pattern residue, that is, the minimum exposure amount required for forming the thick film resist pattern is obtained as an index of sensitivity. The evaluation criteria are as follows:
very good: the exposure is less than 100mJ/cm 2
○：100mJ/cm 2 Exposure ≦ 150mJ/cm 2
△：150mJ/cm 2 Exposure is ≦ 200mJ/cm 2
Gamma rays: exposure ≧ 200mJ/cm 2
b. Rectangularity
Referring to fig. 1, fig. 1 is a schematic diagram illustrating the rectangularity of a photoresist pattern. After the exposure and development steps, the photosensitive resin layer applied to the substrate 100 is formed into a resist pattern 120 having a resist portion 122 and a non-resist portion 124. Observing the cross-sectional shape of the photoresist pattern with the optimal exposure, and measuring the bottom width L b And a top width L t And calculating L t /L b The value serves as an indicator 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 4 and 5, the chemical amplification type positive photosensitive resin compositions (comparative examples 1 and 3) containing the novolak resin (B) in which the area of the cresol dinuclear bodies is more than 6% (B-1 to B-3) are inferior in rectangularity to the chemical amplification type positive photosensitive resin compositions (examples 1 to 14) containing the novolak resin (B) in which the area of the cresol dinuclear bodies is 0.5% to 6% (B-4 to B-7).
Meanwhile, when the first monomer (a 1) having a structure represented by the formula (A-1) (examples 1 to 8) is contained in the monomer mixture for copolymerization of the resin (A), the rectangularity thereof is more excellent. In addition, when the monomer mixture further includes the second monomer (a 2) containing a cyclic ether group (examples 2 to 9), the sensitivity is more excellent.
In addition, when the thiol compound (E) (examples 2 to 4,6, 8, 12, and 13) is contained in the chemically amplified positive photosensitive resin composition, the rectangularity is more excellent.
In addition, when the chemically amplified positive photosensitive resin composition contains the anthracene compound (F) (examples 2,3, 6 to 8, 13, and 14), the sensitivity performance is also more excellent.
As described above, the chemically amplified positive photosensitive resin composition of the present invention can improve rectangularity because the area of cresol dinuclear bodies in the novolac resin (B) is 0.5 to 6%.
Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention.
Claims (11)
1. A chemically amplified positive photosensitive resin composition comprising:
a resin obtained by copolymerizing a monomer mixture and containing an acid-dissociable protecting group;
a novolak resin obtained by condensing a cresol-based aromatic hydroxyl compound with an aldehyde compound, wherein the area of cresol dinuclear bodies in the novolak resin is 0.5 to 6% based on 100% of the integrated area of the molecular weight of the novolak resin measured by gel permeation chromatography;
a photoacid generator;
a solvent; and
an anthracene compound;
wherein the novolac resin has a weight average molecular weight of 4,000 to 36,000,
the novolac resin is used in an amount of 20 to 150 parts by weight, based on 100 parts by weight of the total resin,
the cresol dinuclear body is formed by bonding two m/p/o cresol monomers by taking methylene as a bond and combining m-m, o-o and p-p.
2. The chemical amplification type positive photosensitive resin composition according to claim 1, wherein the monomer mixture comprises a first monomer having a structure represented by the following formula (a-1):
in the formula (A-1), L 1 Represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a linear or branched alkyl group having 1 to 6 carbon atomsBranched fluorinated alkyl groups; l is 2 、L 3 、L 4 Each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, or L 3 、L 4 Are bonded to each other to form a hydrocarbon ring having 5 to 20 carbon atoms.
3. The chemically amplified positive photosensitive resin composition of claim 1, wherein the monomer mixture comprises a second monomer, and the second monomer contains a cyclic ether group.
4. The chemically amplified positive photosensitive resin composition according to claim 1, further comprising a thiol compound having a structure represented by the following formula (E-1):
in the formula (E-1), R 1 、R 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 3 Represents a single bond or an alkylene group having 1 to 10 carbon atoms, R 4 Represents a u-valent organic group; u represents an integer of 2 to 6.
5. The chemical amplification type positive photosensitive resin composition according to claim 1, wherein the photoacid generator is used in an amount of 0.5 to 5 parts by weight, and the solvent is used in an amount of 30 to 360 parts by weight, based on 100 parts by weight of the total resin used.
6. The chemical amplification type positive photosensitive resin composition of claim 2, wherein the first monomer is used in an amount of 10 to 60 parts by weight based on 100 parts by weight of the total amount of the monomer mixture.
7. The chemical amplification type positive photosensitive resin composition according to claim 3, wherein the second monomer is used in an amount of 5 to 35 parts by weight based on 100 parts by weight of the total amount of the monomer mixture.
8. The chemically amplified positive photosensitive resin composition according to claim 4, wherein the thiol compound is used in an amount of 0.3 to 3 parts by weight based on 100 parts by weight of the total resin.
9. The chemically amplified positive photosensitive resin composition according to claim 1, wherein the anthracene compound is used in an amount of 0.2 to 1.5 parts by weight based on 100 parts by weight of the total resin.
10. A method for manufacturing a substrate with a mold, comprising:
a laminating step of laminating a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 9 on a metal surface of a substrate having the metal surface;
an exposure step of irradiating the photosensitive resin layer with active light or radiation; and
and a developing step of developing the exposed photosensitive resin layer to form a mold for forming a plating molded body.
11. A method for manufacturing a molded object by plating, comprising:
a step of forming a plated molded body in the mold by plating the mold-attached substrate manufactured by the method for manufacturing a mold-attached substrate according to claim 10.
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| WO2020121967A1 (en) * | 2018-12-12 | 2020-06-18 | Jsr株式会社 | Photosensitive resin composition, method for producing resist pattern film, and method for producing shaped plating structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI226509B (en) * | 2000-09-12 | 2005-01-11 | Fuji Photo Film Co Ltd | Positive resist composition |
| JP2011209682A (en) * | 2009-10-16 | 2011-10-20 | Fujifilm Corp | Photosensitive resin composition, method of forming cured film, cured film, organic el display device and liquid crystal display device |
| TW201144943A (en) * | 2010-06-15 | 2011-12-16 | Chi Mei Corp | Positive photosensitive resin composition and method of forming pattern with the same composition |
| TW201602721A (en) * | 2014-03-20 | 2016-01-16 | Tokyo Ohka Kogyo Co Ltd | Chemically amplified positive-type photosensitive resin composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI453543B (en) * | 2012-05-16 | 2014-09-21 | Chi Mei Corp | Positive photosensitive resin composition and its application |
| TW201518862A (en) * | 2013-09-13 | 2015-05-16 | Fujifilm Corp | Photo-sensitive resin composition, method for manufacturing cured film, cured film, liquid crystal display device and organic EL display device |
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2016
- 2016-12-27 TW TW105143354A patent/TWI681253B/en active
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- 2017-12-21 CN CN201711391383.XA patent/CN108241257B/en active Active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI226509B (en) * | 2000-09-12 | 2005-01-11 | Fuji Photo Film Co Ltd | Positive resist composition |
| JP2011209682A (en) * | 2009-10-16 | 2011-10-20 | Fujifilm Corp | Photosensitive resin composition, method of forming cured film, cured film, organic el display device and liquid crystal display device |
| TW201144943A (en) * | 2010-06-15 | 2011-12-16 | Chi Mei Corp | Positive photosensitive resin composition and method of forming pattern with the same composition |
| TW201602721A (en) * | 2014-03-20 | 2016-01-16 | Tokyo Ohka Kogyo Co Ltd | Chemically amplified positive-type photosensitive resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108241257A (en) | 2018-07-03 |
| TWI681253B (en) | 2020-01-01 |
| SG10201710688SA (en) | 2018-07-30 |
| TW201823862A (en) | 2018-07-01 |
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