WO2020261979A1 - Photosensitive resin composition, patterned resin film and method for manufacturing same, and semiconductor circuit board - Google Patents

Photosensitive resin composition, patterned resin film and method for manufacturing same, and semiconductor circuit board Download PDF

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Publication number
WO2020261979A1
WO2020261979A1 PCT/JP2020/022677 JP2020022677W WO2020261979A1 WO 2020261979 A1 WO2020261979 A1 WO 2020261979A1 JP 2020022677 W JP2020022677 W JP 2020022677W WO 2020261979 A1 WO2020261979 A1 WO 2020261979A1
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group
resin composition
photosensitive resin
mass
photocation generator
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PCT/JP2020/022677
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French (fr)
Japanese (ja)
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宏和 榊原
哲也 根本
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Jsr株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to a photosensitive resin composition, a resin film having a pattern and a method for producing the same, and a semiconductor circuit board.
  • wide-gap semiconductors such as SiC and GaN, which have excellent characteristics at high frequencies and high temperatures, is being studied.
  • Wide-gap semiconductors exhibit their performance in the high-frequency region because their electron mobility is improved by the high electric field.
  • Examples of the insulating film corresponding to ion migration include a photosensitive resin composition in which the positional relationship between the imide group and the hydroxyl group of polyimide is adjusted, and an insulating film formed from a photosensitive resin composition in which the generation of residues is suppressed. It is known (Patent Documents 1 and 2).
  • the present invention provides a photosensitive resin composition capable of forming an insulating film in which the occurrence of ion migration is suppressed, and a resin film having a pattern in which the occurrence of ion migration is suppressed (hereinafter, also referred to as "patterned resin film"). ) And its manufacturing method, and an object of the present invention is to provide a semiconductor circuit board containing the patterned resin film.
  • the present inventors have conducted diligent studies to solve the above problems. As a result, they have found that the photosensitive resin composition having the following composition can solve the above-mentioned problems, and have completed the present invention.
  • the present invention is, for example, the following [1] to [8].
  • a photosensitive resin composition containing a resin (A) having a phenolic hydroxyl group, a cross-linking agent (B), and a photocation generator (C1) represented by the following formula (C1), and the photosensitive resin composition.
  • R 1 represents an unsubstituted or substituted hydrocarbon group
  • R 2 to R 7 each independently represent a hydrogen atom or an unsubstituted or substituted alkyl group
  • R 2 to R 7 At least one of them represents an unsubstituted or substituted alkyl group.
  • the photosensitive resin composition contains a photocation generator (C) and the content ratio of the photocation generator (C1) contained in the total photocation generator (C) is 90% by mass or more.
  • the photosensitive resin composition according to any one of the above [1] to [3].
  • a photosensitive resin composition capable of forming an insulating film in which the occurrence of ion migration is suppressed, a patterned resin film in which the occurrence of ion migration is suppressed and a method for producing the same, and the patterned resin film are included.
  • Each semiconductor circuit board can be provided.
  • FIG. 1 shows a base material for evaluating ion migration resistance.
  • FIG. 2 shows a photograph of an optical microscope of the substrate after the ion migration resistance evaluation of Experimental Example 2A.
  • FIG. 3 shows a photograph of an optical microscope of the substrate after the ion migration resistance evaluation of Comparative Experimental Example 2A.
  • the photosensitive resin composition of the present invention (hereinafter, also referred to as “composition of the present invention”) is represented by the resin (A) having a phenolic hydroxyl group, the cross-linking agent (B), and the formula (C1) described below. Contains a photocation generator (C1).
  • Resin (A) having a phenolic hydroxyl group examples include a polymer (a1) having a structural unit derived from a radically polymerizable monomer having a phenolic hydroxyl group, and a novolak resin (a2). ), Polybenzoxazole precursor, polyimide having a phenolic hydroxyl group, phenol-xylylene glycol condensed resin, cresol-xylylene glycol condensed resin, phenol-dicyclopentadiene condensed resin.
  • the polymer (a1) and the novolak resin (a2) are preferable from the viewpoint of curability of the composition.
  • Polymer (a1) examples include a single or copolymer of a radically polymerizable monomer having a phenolic hydroxyl group and a radically polymerizable monomer having a phenolic hydroxyl group. Examples thereof include a polymer of a radically polymerizable monomer containing a radically polymerizable monomer having a phenolic hydroxyl group, such as a copolymer of the above and other radically polymerizable monomers.
  • Examples of the radically polymerizable monomer having a phenolic hydroxyl group include hydroxystyrenes such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, and p-isopropenylphenol.
  • Hydroxy monomer A monomer obtained by substituting one or two or more hydrogen atoms bonded to the aromatic ring carbon of the hydroxystyrene monomer with alkyl, alkoxy, halogen, haloalkyl, nitro or cyano; vinyl hydroquinone, 5-vinyl pyrogallol, 6- Vinyl pyrogallol can be mentioned.
  • a monomer obtained by protecting the phenolic hydroxyl group of the monomer with an alkyl group, a silyl group or the like can also be mentioned.
  • the polymer (a1) having the phenolic hydroxyl group can be obtained by removing the protection after forming the polymer.
  • the monomer may be used alone or in combination of two or more.
  • Examples of other radically polymerizable monomers include styrene-based monomers such as styrene, ⁇ -methylstyrene, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether; aromatic rings of styrene-based monomers.
  • the monomer may be used alone or in combination of two or more.
  • the content ratio of the structural unit derived from the radically polymerizable monomer having a phenolic hydroxyl group is derived from the structural unit derived from the radically polymerizable monomer having a phenolic hydroxyl group and other radically polymerizable monomer. It is preferably 30 mol% or more, more preferably 40 to 95 mol%, based on the total content ratio with the structural unit of 100 mol%.
  • the polymer of the radically polymerizable monomer is preferably polyhydroxystyrene, m-hydroxystyrene / p-hydroxystyrene copolymer, hydroxystyrene / styrene copolymer, hydroxystyrene / vinylbenzyl glycidyl ether / styrene common weight.
  • hydroxystyrene-based polymers such as coalescence, hydroxystyrene / (3,4-epoxycyclohexyl) methylmethacrylate copolymer, and hydroxystyrene / (3,4-epoxycyclohexyl) methylmethacrylate / styrene copolymer.
  • the novolak resin (a2) can be obtained, for example, by condensing phenols and aldehydes in the presence of an acid catalyst.
  • phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-Xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethyl
  • aldehydes include formaldehyde, para
  • the novolak resin (a2) include phenol / formaldehyde condensed novolac resin, cresol / formaldehyde condensed novolak resin, cresol / salicylaldehyde condensed novolak resin, phenol-naphthol / formaldehyde condensed novolak resin, and novolak resin as a butadiene polymer.
  • examples thereof include a resin modified with a rubber-like polymer having a polymerizable vinyl group (for example, the resin described in JP-A-2010-015101).
  • the weight average molecular weight (Mw) of the resin (A) measured by the gel permeation chromatography method is usually obtained in terms of polystyrene from the viewpoints of resolution of the photosensitive resin composition, elastic modulus of the resin film and crack resistance. It is 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 5,000 to 50,000. The details of the method for measuring Mw are as described in Examples.
  • the resin (A) is preferably a resin that dissolves 0.001 mg / mL or more in a 2.38 mass% concentration of tetramethylammonium hydroxide aqueous solution (23 ° C.).
  • the composition of the present invention may contain one or more resins (A).
  • the content ratio of the resin (A) is usually 30 to 95% by mass, preferably 40 to 90% by mass, and more preferably 50 to 85% by mass in the solid content of 100% by mass of the composition of the present invention.
  • the content ratio of the resin (A) is within the above range, a composition capable of forming a resin film having excellent resolution tends to be obtained.
  • the solid content refers to all components other than the solvent described later.
  • the composition of the present invention contains a cross-linking agent (B).
  • the cross-linking agent (B) acts as a cross-linking component that reacts with the resin (A) or a component that reacts with each other by the action of the cation generated from the photo-cation generating agent (C1) upon receiving light irradiation.
  • the cross-linking agent (B) for example, the coating film obtained from the composition can be cured, and the chemical resistance and crack resistance of the patterned resin film formed can be improved.
  • crosslinking agent (B) for example, groups having at least two crosslinking agent represented by -R B1 -O-R B2, such as methylol groups and methoxymethyl groups (b1), crosslinked with at least two oxetane rings Agent, cross-linking agent having at least two oxylan rings, cross-linking agent having at least two oxazoline rings, cross-linking agent having at least two isocyanate groups (including blocked ones), cross-linking agent having at least two maleimide groups. Can be mentioned. Among these, the cross-linking agent (b1) is preferable.
  • R B1 is an alkanediyl group, preferably alkanediyl group having 1 to 10 carbon atoms
  • R B2 is a hydrogen atom or an alkyl group, preferably a hydrogen atom Alternatively, it is an alkyl group having 1 to 10 carbon atoms.
  • the alkanediyl group in R B1 for example, methylene group, and ethylene group
  • the alkyl group in R B2 for example, a methyl group, an ethyl group, a propyl group, a butyl group.
  • crosslinking agent (b1) for example, compounds having -R B1 -O-R B2 in 2 or more amino groups group is bonded, represented, methylol group-containing phenol compound, an alkyl methylol group-containing phenol compounds ..
  • Examples of the amino group to which the group represented by -R B1 -OR B2 is bonded include a group represented by the formula (b1-1) and a group represented by the formula (b1-2).
  • R B1 is an alkanediyl group, preferably an alkanediyl group having 1 to 10 carbon atoms
  • R B2 is a hydrogen atom or an alkyl group.
  • a hydrogen atom or an alkyl group having 1 to 10 carbon atoms Preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, m being 1 or 2, n being 0 or 1, m + n being 2, and * being a bond.
  • Examples of the cross-linking agent (b1) include nitrogen atom-containing compounds such as polymethylolated melamine, polymethylolated glycoluryl, polymethylollated guanamine, and polymethylolated urea; active methylol groups (N atoms) in the nitrogen atom-containing compound.
  • examples thereof include compounds in which all or part of the CH 2 OH group bonded to the compound is alkyl etherified.
  • examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, a propyl group, and a butyl group, which may be the same or different from each other.
  • the active methylol group which has not been alkyl etherized may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed.
  • cross-linking agent (b1) examples include the cross-linking agents described in JP-A-6-180501, JP-A-2006-178509, and JP-A-2012-226297.
  • melamine-based cross-linking agents such as polymethylated melamine, hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxymethyl melamine
  • Glycoluryl-based cross-linking agents such as methyl glycol uryl; 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] 2,4,8,10-tetraoxospiro [ 5.5]
  • Undecane 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) propyl] 2,4,8,10-tetraoxospiro [5.5]
  • Undecane examples thereof include guan
  • Examples of the methylol group-containing phenol compound and the alkylmethylol group-containing phenol compound include 2,6-dimethoxymethyl-4-t-butylphenol and 2,6-dimethoxymethyl-p-cresol.
  • the composition of the present invention can contain one or more cross-linking agents (B).
  • the content of the cross-linking agent (B) is usually 1 to 100 parts by mass, preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the resin (A). It is a department. When the content of the cross-linking agent (B) is within the above range, a patterned resin film having excellent chemical resistance and crack resistance tends to be formed.
  • the composition of the present invention contains the photocation generator (C1) represented by the formula (C1) described below as the photocation generator (C).
  • the photocation generator (C1) is a compound that receives light irradiation and photodecomposes to generate sulfonic acid.
  • the photocation generator (C1) absorbs light at a wavelength of 365 nm, for example, has a good acid generation rate, and mixes well with a resin (A) having a phenolic hydroxyl group and a low molecular weight phenol compound (D). Therefore, even if it is used in a small amount, a sufficient effect, for example, excellent sensitivity of the photosensitive resin composition is obtained.
  • the cation derived from sulfonic acid is considered to promote, for example, a cross-linking reaction between the resin (A) and the cross-linking agent (B) and a reaction between the cross-linking agents (B). Therefore, by exposing the coating film formed from the composition of the present invention, a cation is generated from the photocation generator (C1) in the exposed portion, and the cross-linking reaction is promoted based on the action of the cation to form a cross-linked structure. Therefore, it is considered that the solubility in the developing solution is reduced.
  • the composition of the present invention an insulating film in which the occurrence of ion migration is suppressed can be produced, and the insulating film is suitable as an insulating film between electrodes and wirings in a semiconductor circuit board.
  • the present inventors speculate that the reason why ion migration is suppressed is as follows.
  • an onium salt such as a sulfonium salt is often used as a photocation generator.
  • the onium salt can also function as a thermal cation generator, so that an acid is generated in the high-temperature treatment step performed after exposure / development.
  • wiring such as copper wiring is oxidized, and it is considered that ion migration proceeds accordingly.
  • the onium salt is an ionic photocation generator and can also function as a thermal cation generator, it is considered that an acid is generated and the pH is lowered in a high temperature and high humidity environment. Therefore, instead of the ionic photocation generator, it is a nonionic photocation generator that does not easily function as a thermal cation generator, and the photocation generator does not remain in the patterned resin film after exposure and development.
  • the photocation generator (C1) which is a photocation generator that is easily photodecomposable, the ion migration can be carried out in the obtained insulating film while maintaining the excellent sensitivity of the photosensitive resin composition. Occurrence can be suppressed.
  • R 1 represents an unsubstituted or substituted hydrocarbon group
  • R 2 to R 7 each independently represent a hydrogen atom or an unsubstituted or substituted alkyl group, and among R 2 to R 7 , At least one represents an unsubstituted or substituted alkyl group.
  • R 1 unsubstituted or substituted hydrocarbon group
  • the unsubstituted hydrocarbon group in R 1 include aliphatic hydrocarbon groups such as alkyl groups and alkenyl groups; alicyclic-containing hydrocarbons such as cycloalkyl groups, cycloalkylalkyl groups and polycyclic saturated cyclic hydrocarbon groups.
  • Hydrogen group examples thereof include an aromatic ring-containing hydrocarbon group such as an aryl group and an aralkyl group.
  • the unsubstituted hydrocarbon group usually has 20 or less carbon atoms, preferably 10 or less carbon atoms.
  • alkyl group examples include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and the like. Examples thereof include sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group and decyl group.
  • alkenyl group examples include an alkenyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, and a 2-methyl-2-propenyl group.
  • the alkyl group and the alkenyl group may be a straight chain or a branched chain.
  • the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a cyclodecyl group;
  • examples of the cycloalkylalkyl group include a cyclohexylmethyl group and a cyclohexylethyl group;
  • Examples of the saturated cyclic hydrocarbon group include a norbornyl group, an adamantyl group, a tricyclodecyl group and a tetracyclododecyl group.
  • aryl group examples include an aryl group having 6 to 20 carbon atoms, and specifically, a phenyl group, a naphthyl group, a biphenyl group; 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4. , Alkylaryl groups such as 6-triisopropylphenyl group; cycloalkylaryl groups such as cyclohexylphenyl group.
  • aralkyl group examples include an aralkyl group having 7 to 20 carbon atoms, and specific examples thereof include a benzyl group, a phenethyl group, a diphenylmethyl group, and a triphenylmethyl group.
  • the substituted hydrocarbon group means a group in which at least one hydrogen atom in the unsubstituted hydrocarbon group is substituted with another group (substituent) other than the hydrocarbon group. Therefore, for example, an aralkyl group is classified as an unsubstituted hydrocarbon group.
  • the "unsubstituted hydrocarbon group” is sometimes simply referred to as the "hydrocarbon group”.
  • substituent in the substituted hydrocarbon group examples include a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group and an acyloxy group.
  • each substituent may be the same or different.
  • a halogenated hydrocarbon group in which at least one hydrogen atom in the unsubstituted hydrocarbon group is substituted with a halogen atom is preferable, an alkyl halide group and an aryl halide group are more preferable, and a halogen is more preferable. Hydrocarbon groups are more preferred.
  • examples of the halogen atom include fluorine, chlorine, bromine, and iodine.
  • alkyl halide group include perfluoroalkyl groups such as trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group and nonafluorobutyl group; 1,1-difluoroethyl group and 2,2,2-tri Fluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, fluoromethyl group, chloromethyl group , 2-Chloroethyl group, 2-bromoethyl group.
  • the aryl halide group include a pentafluoroaryl group, a trifluoromethylphenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
  • an unsubstituted hydrocarbon group or a halogenated hydrocarbon group in which at least one hydrogen atom in the unsubstituted hydrocarbon group is substituted with a halogen atom is preferable, more preferably an alkyl halide group, and further.
  • a perfluoroalkyl group is preferable, and a perfluoroalkyl group having 1 to 8 carbon atoms is particularly preferable.
  • R 2 to R 7 unsubstituted or substituted alkyl group
  • R 2 to R 7 examples include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, and more preferably 3 to 8 carbon atoms. Examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group and decyl group.
  • the alkyl group may be a straight chain or a branched chain.
  • the substituted alkyl group means a group in which at least one hydrogen atom in the unsubstituted alkyl group is substituted with another group (substituent) other than the alkyl group.
  • An "unsubstituted alkyl group” may simply be referred to as an "alkyl group”.
  • substituents examples include a cycloalkyl group, a polycyclic saturated cyclic hydrocarbon group, an aryl group, and an aralkyl group, and specific examples of these groups have been described above.
  • substituents include a cycloalkyl group, a polycyclic saturated cyclic hydrocarbon group, an aryl group, and an aralkyl group, and specific examples of these groups have been described above.
  • each substituent may be the same or different.
  • R 2 to R 7 a hydrogen atom or an unsubstituted alkyl group is preferable. Due to the large light absorption of the photocation generator (C1), especially at a wavelength of 365 nm, at least one of R 2 to R 7 exhibits an unsubstituted or substituted alkyl group. From the viewpoint of light absorption, it is preferable that R 4 is an unsubstituted or substituted alkyl group, R 2 to R 3 and R 5 to R 7 are hydrogen atoms, and R 4 is an unsubstituted alkyl group. Is more preferable.
  • the photocation generator (C1) can be produced by a conventionally known method, and examples thereof include the methods described in International Publication No. 2014/084269 and International Publication No. 2015/001804.
  • the composition of the present invention can contain one or more photocation generators (C1).
  • the content of the photocation generator (C1) in the composition of the present invention is usually 1 to 15 parts by mass, preferably 2 to 10 parts by mass, and more preferably 3 to 3 parts by mass with respect to 100 parts by mass of the cross-linking agent (B). It is 8 parts by mass.
  • the content of the photocation generator (C1) is at least the above lower limit value, the exposed portion is sufficiently cured and the heat resistance of the patterned resin film is likely to be improved.
  • the content of the photocation generator (C1) is not more than the above upper limit value, a patterned resin film having high resolution can be easily obtained without reducing the transparency to light used for exposure.
  • the content ratio of the photocation generator (C1) contained in the solid content of the composition of the present invention is 0.01 to 0.9% by mass, preferably the lower limit is 0.1% by mass and the upper limit is 0.1% by mass. 0.85% by mass, more preferably the lower limit is 0.3% by mass and the upper limit is 0.8% by mass. Since the photocation generator (C1) has a good acid generation rate with respect to light irradiation, the effect of the present invention can be obtained even if the lower limit value is the above value.
  • the photocation generator (C1) is a compound that is photodecomposed by light irradiation to generate sulfonic acid. Therefore, if the upper limit is the above value, it can be deposited into the patterned resin film by diffusion of sulfonic acid. It is possible to eliminate the residue and suppress the occurrence of ion migration.
  • the composition of the present invention can further contain a photocation generator other than the photocation generator (C1).
  • the photocation generator (C1) and other photocation generators are collectively referred to as "photocation generator (C)".
  • the content ratio of the photocation generator (C1) contained in the photocation generator (C) is preferably 90% by mass or more, more preferably 95% by mass or more. , More preferably 99% by mass or more.
  • a photosensitive acid generator that generates an acid by light irradiation is preferable, and examples thereof include onium salts, halogen-containing compounds, sulfonic compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds.
  • onium salt halogen-containing compound, sulfonic acid compound, sulfonic acid compound, sulfonimide compound and diazomethane compound
  • onium salt halogen-containing compound, sulfonic acid compound, sulfonic acid compound, sulfonimide compound and diazomethane compound
  • sulfonic acid compound sulfonic acid compound
  • sulfonimide compound sulfonimide compound
  • diazomethane compound include the compounds described in paragraphs [0074] to [0079] of JP-A-2014-186300. listed and these compounds are as described herein.
  • the composition of the present invention preferably further contains the low molecular weight phenol compound (D).
  • the low molecular weight phenol compound (D) represents a compound having a phenolic hydroxyl group and having a molecular weight of less than 1000, preferably less than 800.
  • the low-molecular-weight phenolic compound (D) has the same function as the resin (A) having a phenolic hydroxyl group, but since it is a low-molecular-weight compound, it is highly soluble in an alkaline developer, which will be described later.
  • the resolution of the sex resin composition can be improved. As a result, the content ratio of the photocation generator (C1) contained in the photosensitive resin composition can be reduced.
  • Examples of the low molecular weight phenol compound (D) include 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, and 1,1-bis (4-hydroxyphenyl) -1.
  • the composition of the present invention can contain one or more low molecular weight phenolic compounds (D).
  • the lower limit of the content of the low molecular weight phenol compound (D) with respect to 100 parts by mass of the resin (A) in the composition of the present invention is usually 1 part by mass, and the upper limit is usually 1 part by mass. It is 50 parts by mass.
  • the low-molecular-weight phenol component is in the above range, the polarity of the resin film is suppressed to a range in which ion migration does not pose a practical problem, the solubility in an alkaline developer is adjusted, and the resolution of the pattern is improved. be able to.
  • the composition of the present invention may contain other components as long as the object and properties of the present invention are not impaired.
  • other components include resins other than the resin (A) having a phenolic hydroxyl group, surfactants, leveling agents, adhesive aids, sensitizers, quenchers, crosslinked fine particles, and additives such as inorganic fillers. Be done.
  • adhesion aid examples include silane coupling agents such as tris (trimethoxysilylpropyl) isocyanurate and glycidoxypropyltrimethoxysilane.
  • silane coupling agents such as tris (trimethoxysilylpropyl) isocyanurate and glycidoxypropyltrimethoxysilane.
  • the surfactant examples include a fluorine-based surfactant, a silicone-based surfactant, and a polyalkylene oxide-based surfactant.
  • the lower limit of the content of the surfactant with respect to 100 parts by mass of the resin (A) in the composition of the present invention is usually 0.0001 parts by mass, and the upper limit is usually 1 part by mass.
  • the composition of the present invention preferably contains a solvent.
  • a solvent By using a solvent, the handleability of the composition of the present invention can be improved, and the viscosity and storage stability can be adjusted.
  • the solvent examples include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like.
  • Ethers other esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; 2-heptanone, 3 -Ketones such as heptanone, 4-heptanone, cyclohexanone; amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone; lactones such as ⁇ -butyrolactone; toluene, xylene Such as aromatic hydrocarbons.
  • ketones, lactones, lactic acid esters, propylene glycol monoalkyl ether acetates and propylene glycol monoalkyl ethers are preferable, and 2-heptanone, ⁇ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate and propylene glycol are preferable.
  • Monomethyl ether is more preferred.
  • composition of the present invention may contain one or more solvents.
  • the content ratio of the solvent in the composition of the present invention is usually 10 to 95% by mass, preferably 30 to 90% by mass.
  • the composition of the present invention can be produced by uniformly mixing each component constituting the composition. Further, in order to remove foreign substances, each of the above components can be uniformly mixed, and then the obtained mixture can be filtered with a filter or the like.
  • the method for producing a resin film having a pattern (patterned resin film) of the present invention is a step of forming a coating film of the composition of the present invention on a substrate (1) and a step of selectively exposing the coating film (a step of selectively exposing the coating film). It has 2) and a step (3) of developing the coating film after the exposure.
  • the composition of the present invention is applied onto the substrate so that the thickness of the finally obtained patterned resin film is usually 0.1 to 100 ⁇ m.
  • the substrate after applying the composition is usually heated at 50 to 140 ° C. for 10 to 360 seconds using an oven or a hot plate. In this way, a coating film made of the composition of the present invention is formed on the substrate.
  • the substrate examples include silicon wafers, compound semiconductor wafers, wafers with metal thin films, glass substrates, quartz substrates, ceramic substrates, aluminum substrates, and substrates having electrodes, wirings, semiconductor chips, etc. on the surface of these substrates. ..
  • the electrodes and wiring consist of metals such as copper, nickel, aluminum, and gold, for example.
  • Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, and an inkjet method.
  • step (2) for example, a contact aligner, a stepper, or a scanner is used to selectively expose the coating film.
  • a contact aligner for example, a contact aligner, a stepper, or a scanner is used to selectively expose the coating film.
  • "Selectively” specifically means through a photomask in which a predetermined mask pattern is formed.
  • the exposure light examples include ultraviolet rays and visible light, and usually, light having a wavelength of 200 to 500 nm such as i-line (365 nm) is used.
  • the irradiation amount by exposure varies depending on the type and content ratio of each component in the composition of the present invention, the thickness of the coating film, and the like, but is usually 100 to 10000 mJ / cm 2 .
  • heat treatment baking after exposure
  • the conditions for heat treatment after exposure vary depending on the type and content ratio of each component in the composition of the present invention, the thickness of the coating film, and the like, but are usually 70 to 250 ° C., preferably 80 to 200 ° C., and usually 1 ⁇ 60 minutes.
  • a desired patterned resin film is formed on the substrate by developing the coating film after exposure with an alkaline developer to dissolve and remove the non-exposed portion.
  • the developing method examples include a shower developing method, a spray developing method, a dipping developing method, and a paddle developing method.
  • the developing conditions are, for example, 5 to 40 ° C. for 1 to 10 minutes.
  • the alkaline developer is, for example, an alkaline aqueous solution prepared by dissolving an alkaline compound such as sodium hydroxide, potassium hydroxide, aqueous ammonia, tetramethylammonium hydroxide, or choline in water so as to have a concentration of 1 to 10% by mass. Can be mentioned.
  • An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.
  • the shape of the pattern in the patterned resin film is not particularly limited as long as it has a concavo-convex structure, and examples thereof include a line and space pattern, a dot pattern, a hole pattern, and a lattice pattern.
  • the patterned resin film is sufficiently subjected to heat treatment (post-baking) as necessary in order to sufficiently exhibit the characteristics as an insulating film. It can have a step (4) of curing.
  • the curing conditions are not particularly limited, but it is usually heated at 100 to 250 ° C., preferably 150 to 250 ° C. for 30 minutes to 10 hours depending on the use of the patterned resin film.
  • the patterned resin film obtained by the production method of the present invention can be suitably used as an insulating film contained in a semiconductor circuit board.
  • the insulating film is, for example, a surface protective film, an interlayer insulating film, and a flattening film.
  • a semiconductor circuit board including a resin film (patterned resin film) having the above-mentioned pattern can be manufactured. Since the semiconductor circuit board has a patterned resin film formed from the composition of the present invention described above, preferably a patterned insulating film such as a surface protective film, an interlayer insulating film and a flattening film, the semiconductor circuit board can be used as a high frequency circuit board. It is useful.
  • the semiconductor circuit board of the present invention is suitable as a semiconductor circuit board using a wide-gap semiconductor such as SiC or GaN.
  • Electrodes and / or wiring in semiconductor circuit boards are made of metals such as copper, nickel, aluminum, and gold, for example.
  • the patterned resin film of the present invention as the insulating film between these electrodes and / or wiring, the occurrence of the above-mentioned ion migration can be satisfactorily suppressed.
  • Example 1A to Example 18A, Comparative Example 1A to Comparative Example 3A The photosensitive resin compositions of Examples 1A to 18A and Comparative Examples 1A to 3A were produced by uniformly mixing each component of the type and amount shown in Table 1 below. Details of each component shown in Table 1 are as follows. The unit of the numerical value of each component in Table 1 is the mass part.
  • B-1 1,3,4,6-tetrakis (methoxymethyl) glycoluryl
  • C1-1 Compound represented by the following formula (C1-1)
  • C-1 Compound represented by the following formula (C-1)
  • C1-2 Compound represented by the following formula (C1-2)
  • C1-3 Compound represented by the following formula (C1-3)
  • C1-4 Compound represented by the following formula (C1-4) C1-5: The following formula (C1-5)
  • C1-1 Compound shown in
  • D-1 1,1-bis (4-hydroxy-2,5-dimethylphenyl) propan-2-one
  • E-1 tris (trimethoxysilylpropyl) isocyanurate
  • E-2 fluorine-based surfactant (commodity) Name "NBX-15", manufactured by Neos Co., Ltd.)
  • F-1 Ethyl lactate
  • F-2 2-Heptanone
  • Example 1B The photosensitive resin composition of Example 1A shown in Table 2 was spin-coated on a silicon wafer substrate by a coater developer (product name "MARK-8") manufactured by Tokyo Electron Limited, and then heated at 110 ° C. for 180 seconds. A coating film was formed. The coating film was exposed to a wavelength of 365 nm using a stepper (manufactured by Nikon Corporation, model “NSR-i10D”) via a pattern mask. The exposed coating film was heated at 125 ° C. for 180 seconds and then immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 120 seconds for development.
  • MARK-8 coater developer
  • the evaluation results are shown in Table 2.
  • Example 2B to Example 18B, and Comparative Example 1B to Comparative Example 3B In Example 1B, a resin film having a pattern was produced in the same manner as in Example 1B except that the photosensitive resin composition shown in Table 2 was used, and the sensitivity was evaluated. The evaluation results are shown in Table 2.
  • the coating film is entirely exposed with a stepper (manufactured by Nikon Corporation, model "NSR-i10D") at the exposure amount shown in "Sensitivity" of Table 2 in Example 1B, and the coating film after exposure is 180 at 125 ° C. It was heated for 1 second, immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 120 seconds, and then heated at 200 ° C. for 1 hour to prepare a substrate for ion migration resistance evaluation.
  • the substrate for ion migration resistance evaluation was subjected to a high-speed accelerated life test (HAST test) under the conditions of a temperature of 130 ° C., a humidity of 85%, and an applied voltage of 15 V with a model "AEI, EHS-221MD” manufactured by Tabei Espec Co., Ltd. Ion migration resistance was evaluated with the time when the value was 10 11 ⁇ or less as the occurrence time of ion migration.
  • HAST test high-speed accelerated life test
  • Example 1A a substrate for evaluating ion migration resistance was prepared in the same manner as in Experimental Example 1A except that the photosensitive resin composition shown in Table 3 was used, and the ion migration resistance was evaluated. The evaluation results are shown in Table 3.
  • FIG. 2 shows a photograph of an optical microscope of the substrate after the ion migration resistance evaluation of Experimental Example 2A.
  • FIG. 3 shows a photograph of an optical microscope of the substrate after the ion migration resistance evaluation of Comparative Experimental Example 2A.
  • Substrate 2 Comb electrode 3: Substrate

Abstract

Provided is a photosensitive resin composition that is capable of forming an insulating film in which the occurrence of ion migration is suppressed.　A photosensitive resin composition according to the present invention contains: (A) a resin comprising a phenolic hydroxyl group; (B) a cross-linking agent; and (C1) a specific photocation generator, the proportion of the photocation generator (C1) in the solid content of the photosensitive resin composition being 0.01 to 0.9% by mass.

Description

感光性樹脂組成物、パターンを有する樹脂膜およびその製造方法、ならびに半導体回路基板Photosensitive resin composition, resin film having a pattern and its manufacturing method, and semiconductor circuit board
　本発明は、感光性樹脂組成物、パターンを有する樹脂膜およびその製造方法、ならびに半導体回路基板に関する。 The present invention relates to a photosensitive resin composition, a resin film having a pattern and a method for producing the same, and a semiconductor circuit board.
　第５世代移動通信システムで用いられる回路素子では、高周波および高温での特性に優れているＳｉＣやＧａＮなどのワイドギャップ半導体の適用が検討されている。ワイドギャップ半導体は、高電界により電子移動度が向上するので、高周波領域においてその性能を発揮する。 For circuit elements used in 5th generation mobile communication systems, the application of wide-gap semiconductors such as SiC and GaN, which have excellent characteristics at high frequencies and high temperatures, is being studied. Wide-gap semiconductors exhibit their performance in the high-frequency region because their electron mobility is improved by the high electric field.
　ところで、回路素子の電極や配線材料のイオン化およびそれに伴う電極や配線間のイオンの移動（イオンマイグレーション）は、電界強度の増大により起こりやすくなることが知られている。よって、高電界および高周波領域で適用するワイドギャップ半導体を用いた回路素子はイオンマイグレーションを起こしやすくなることから、電極や配線間にある絶縁膜はイオンマイグレーションを起こしにくいことが好ましい。 By the way, it is known that ionization of electrodes and wiring materials of circuit elements and accompanying movement of ions between electrodes and wiring (ion migration) are likely to occur due to an increase in electric field strength. Therefore, since a circuit element using a wide-gap semiconductor applied in a high electric field and a high frequency region is likely to cause ion migration, it is preferable that the insulating film between the electrodes and wiring is unlikely to cause ion migration.
　イオンマイグレーションに対応した絶縁膜としては、例えば、ポリイミドのイミド基と水酸基との位置関係を調節した感光性樹脂組成物や、残渣の発生を抑制した感光性樹脂組成物から形成される絶縁膜が知られている（特許文献１～２）。 Examples of the insulating film corresponding to ion migration include a photosensitive resin composition in which the positional relationship between the imide group and the hydroxyl group of polyimide is adjusted, and an insulating film formed from a photosensitive resin composition in which the generation of residues is suppressed. It is known (Patent Documents 1 and 2).
特開２０１９－０１２１８１号公報Japanese Unexamined Patent Publication No. 2019-012181 特開２０１８－１９７８３３号公報JP-A-2018-197833
　本発明は、イオンマイグレーションの発生を抑制した絶縁膜の形成が可能な感光性樹脂組成物を提供すること、イオンマイグレーションの発生を抑制したパターンを有する樹脂膜（以下「パターン化樹脂膜」ともいう）およびその製造方法を提供すること、ならびに前記パターン化樹脂膜を含む半導体回路基板を提供することを目的とする。 The present invention provides a photosensitive resin composition capable of forming an insulating film in which the occurrence of ion migration is suppressed, and a resin film having a pattern in which the occurrence of ion migration is suppressed (hereinafter, also referred to as "patterned resin film"). ) And its manufacturing method, and an object of the present invention is to provide a semiconductor circuit board containing the patterned resin film.
　本発明者らは前記課題を解決するため鋭意検討を行った。その結果、下記組成の感光性樹脂組成物が前記課題を解決できることを見出し、本発明を完成するに至った。
　本発明は、例えば以下の［１］～［８］である。 The present inventors have conducted diligent studies to solve the above problems. As a result, they have found that the photosensitive resin composition having the following composition can solve the above-mentioned problems, and have completed the present invention.
The present invention is, for example, the following [1] to [8].
　［１］フェノール性水酸基を有する樹脂（Ａ）、架橋剤（Ｂ）、および下記式（Ｃ１）に示す光カチオン発生剤（Ｃ１）を含有する感光性樹脂組成物であり、前記感光性樹脂組成物の固形分中に含まれる前記光カチオン発生剤（Ｃ１）の含有割合が、０．０１～０．９質量％である、感光性樹脂組成物。 [1] A photosensitive resin composition containing a resin (A) having a phenolic hydroxyl group, a cross-linking agent (B), and a photocation generator (C1) represented by the following formula (C1), and the photosensitive resin composition. A photosensitive resin composition in which the content ratio of the photocation generator (C1) contained in the solid content of the product is 0.01 to 0.9% by mass.
Figure JPOXMLDOC01-appb-C000002
 ［式（Ｃ１）中、Ｒ1は非置換または置換の炭化水素基を示し、Ｒ2～Ｒ7はそれぞれ独立に水素原子、または非置換もしくは置換のアルキル基を示し、Ｒ2～Ｒ7のうち少なくとも一つは非置換または置換のアルキル基を示す。］
Figure JPOXMLDOC01-appb-C000002
 [In formula (C1), R 1 represents an unsubstituted or substituted hydrocarbon group, R 2 to R 7 each independently represent a hydrogen atom or an unsubstituted or substituted alkyl group, and R 2 to R 7 At least one of them represents an unsubstituted or substituted alkyl group. ]
　［２］前記架橋剤（Ｂ）１００質量部に対する前記光カチオン発生剤（Ｃ１）の含有量が、１～１５質量部である、前記［１］に記載の感光性樹脂組成物。
　［３］前記架橋剤（Ｂ）が、－ＲB1－Ｏ－ＲB2で表される基を少なくとも２個有する架橋剤（ｂ１）（式中、ＲB1はアルカンジイル基であり、ＲB2は水素原子またはアルキル基である）である、前記［１］または［２］に記載の感光性樹脂組成物。 [2] The photosensitive resin composition according to the above [1], wherein the content of the photocation generator (C1) with respect to 100 parts by mass of the cross-linking agent (B) is 1 to 15 parts by mass.
[3] The crosslinking agent (B), having at least two cross-linking agent (b1) (wherein a group represented by -R B1 -O-R B2, R B1 is an alkane diyl group, R B2 is The photosensitive resin composition according to the above [1] or [2], which is a hydrogen atom or an alkyl group).
　［４］前記感光性樹脂組成物が光カチオン発生剤（Ｃ）を含有し、全光カチオン発生剤（Ｃ）中に含まれる前記光カチオン発生剤（Ｃ１）の含有割合が９０質量％以上である、前記［１］～［３］のいずれかに記載の感光性樹脂組成物。 [4] When the photosensitive resin composition contains a photocation generator (C) and the content ratio of the photocation generator (C1) contained in the total photocation generator (C) is 90% by mass or more. The photosensitive resin composition according to any one of the above [1] to [3].
　［５］さらに、低分子フェノール化合物（Ｄ）を含有する、前記［１］～［４］のいずれかに記載の感光性樹脂組成物。
　［６］前記［１］～［５］のいずれかに記載の感光性樹脂組成物の塗膜を基板上に形成する工程（１）、前記塗膜を選択的に露光する工程（２）、および前記露光後の塗膜を現像する工程（３）を有する、パターンを有する樹脂膜の製造方法。 [5] The photosensitive resin composition according to any one of the above [1] to [4], which further contains the low molecular weight phenol compound (D).
[6] A step of forming a coating film of the photosensitive resin composition according to any one of the above [1] to [5] on a substrate (1), a step of selectively exposing the coating film (2). A method for producing a resin film having a pattern, which comprises the step (3) of developing the coating film after exposure.
　［７］前記［６］に記載の製造方法により形成された、パターンを有する樹脂膜。
　［８］前記［７］に記載のパターンを有する樹脂膜を含む半導体回路基板。 [7] A resin film having a pattern formed by the production method according to the above [6].
[8] A semiconductor circuit board including a resin film having the pattern according to the above [7].
　本発明によれば、イオンマイグレーションの発生を抑制した絶縁膜の形成が可能な感光性樹脂組成物、イオンマイグレーションの発生を抑制したパターン化樹脂膜およびその製造方法、ならびに前記パターン化樹脂膜を含む半導体回路基板を、それぞれ提供することができる。 According to the present invention, a photosensitive resin composition capable of forming an insulating film in which the occurrence of ion migration is suppressed, a patterned resin film in which the occurrence of ion migration is suppressed and a method for producing the same, and the patterned resin film are included. Each semiconductor circuit board can be provided.
図１は、イオンマイグレーション耐性評価用の基材を示す。FIG. 1 shows a base material for evaluating ion migration resistance. 図２は、実験例２Ａのイオンマイグレーション耐性評価後の基板の光学顕微鏡の写真を示す。FIG. 2 shows a photograph of an optical microscope of the substrate after the ion migration resistance evaluation of Experimental Example 2A. 図３は、比較実験例２Ａのイオンマイグレーション耐性評価後の基板の光学顕微鏡の写真を示す。FIG. 3 shows a photograph of an optical microscope of the substrate after the ion migration resistance evaluation of Comparative Experimental Example 2A.
　以下、本発明を実施するための形態について好適態様も含めて説明する。
　［感光性樹脂組成物］
　本発明の感光性樹脂組成物（以下「本発明の組成物」ともいう）は、以下に説明する、フェノール性水酸基を有する樹脂（Ａ）、架橋剤（Ｂ）、および式（Ｃ１）に示す光カチオン発生剤（Ｃ１）を含有する。 Hereinafter, modes for carrying out the present invention will be described including preferred embodiments.
[Photosensitive resin composition]
The photosensitive resin composition of the present invention (hereinafter, also referred to as “composition of the present invention”) is represented by the resin (A) having a phenolic hydroxyl group, the cross-linking agent (B), and the formula (C1) described below. Contains a photocation generator (C1).
　＜フェノール性水酸基を有する樹脂（Ａ）＞
　フェノール性水酸基を有する樹脂（Ａ）（以下「樹脂（Ａ）」ともいう）としては、例えば、フェノール性水酸基を有するラジカル重合性モノマー由来の構造単位を有する重合体（ａ１）、ノボラック樹脂（ａ２）、ポリベンゾオキサゾール前駆体、フェノール性水酸基を有するポリイミド、フェノール－キシリレングリコール縮合樹脂、クレゾール－キシリレングリコール縮合樹脂、フェノール－ジシクロペンタジエン縮合樹脂が挙げられる。これらの中でも、組成物の硬化性の観点から、前記重合体（ａ１）、およびノボラック樹脂（ａ２）が好ましい。 <Resin (A) having a phenolic hydroxyl group>
Examples of the resin (A) having a phenolic hydroxyl group (hereinafter, also referred to as “resin (A)”) include a polymer (a1) having a structural unit derived from a radically polymerizable monomer having a phenolic hydroxyl group, and a novolak resin (a2). ), Polybenzoxazole precursor, polyimide having a phenolic hydroxyl group, phenol-xylylene glycol condensed resin, cresol-xylylene glycol condensed resin, phenol-dicyclopentadiene condensed resin. Among these, the polymer (a1) and the novolak resin (a2) are preferable from the viewpoint of curability of the composition.
　≪重合体（ａ１）≫
　フェノール性水酸基を有するラジカル重合性モノマー由来の構造単位を有する重合体（ａ１）としては、例えば、フェノール性水酸基を有するラジカル重合性モノマーの単独または共重合体、フェノール性水酸基を有するラジカル重合性モノマーとその他のラジカル重合性モノマーとの共重合体などの、フェノール性水酸基を有するラジカル重合性モノマーを含むラジカル重合性モノマーの重合体が挙げられる。 ≪Polymer (a1) ≫
Examples of the polymer (a1) having a structural unit derived from a radically polymerizable monomer having a phenolic hydroxyl group include a single or copolymer of a radically polymerizable monomer having a phenolic hydroxyl group and a radically polymerizable monomer having a phenolic hydroxyl group. Examples thereof include a polymer of a radically polymerizable monomer containing a radically polymerizable monomer having a phenolic hydroxyl group, such as a copolymer of the above and other radically polymerizable monomers.
　フェノール性水酸基を有するラジカル重合性モノマーとしては、例えば、ｏ－ヒドロキシスチレン、ｍ－ヒドロキシスチレン、ｐ－ヒドロキシスチレン、ｏ－イソプロペニルフェノール、ｍ－イソプロペニルフェノール、ｐ－イソプロペニルフェノール等のヒドロキシスチレン系モノマー；ヒドロキシスチレン系モノマーの芳香環炭素に結合した１または２以上の水素原子をアルキル、アルコキシ、ハロゲン、ハロアルキル、ニトロまたはシアノに置換してなるモノマー；ビニルヒドロキノン、５－ビニルピロガロール、６－ビニルピロガロールが挙げられる。また、前記モノマーのフェノール性水酸基をアルキル基やシリル基等で保護してなるモノマーを挙げることもできる。前記のフェノール性水酸基を保護してなるモノマーを用いる場合、重合体を形成後、当該保護を外すことでフェノール性水酸基を有する重合体（ａ１）とすることができる。前記モノマーは１種で用いてもよく、２種以上を併用してもよい。 Examples of the radically polymerizable monomer having a phenolic hydroxyl group include hydroxystyrenes such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, and p-isopropenylphenol. Hydroxy monomer: A monomer obtained by substituting one or two or more hydrogen atoms bonded to the aromatic ring carbon of the hydroxystyrene monomer with alkyl, alkoxy, halogen, haloalkyl, nitro or cyano; vinyl hydroquinone, 5-vinyl pyrogallol, 6- Vinyl pyrogallol can be mentioned. Further, a monomer obtained by protecting the phenolic hydroxyl group of the monomer with an alkyl group, a silyl group or the like can also be mentioned. When the above-mentioned monomer that protects the phenolic hydroxyl group is used, the polymer (a1) having the phenolic hydroxyl group can be obtained by removing the protection after forming the polymer. The monomer may be used alone or in combination of two or more.
　その他のラジカル重合性モノマーとしては、例えば、スチレン、α－メチルスチレン、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル等のスチレン系モノマー；スチレン系モノマーの芳香環炭素に結合した１または２以上の水素原子をアルキル、アルコキシ、ハロゲン、ハロアルキル、ニトロまたはシアノに置換してなるモノマー；ブタジエン、イソプレン、クロロプレン等のジエン；不飽和モノカルボン酸、不飽和ジカルボン酸およびそのハーフエステル等の不飽和カルボン酸；ｏ－ビニル安息香酸、ｍ－ビニル安息香酸、ｐ－ビニル安息香酸またはこれらのモノマーの芳香環炭素に結合した１もしくは２以上の水素原子をアルキル、アルコキシ、ハロゲン、ハロアルキル、ニトロもしくはシアノに置換してなるモノマー；（メタ）アクリル酸グリシジル等の（メタ）アクリル酸エステル、（メタ）アクリロニトリル、アクロレイン、塩化ビニル、塩化ビニリデン、弗化ビニル、弗化ビニリデン、Ｎ－ビニルピロリドン、ビニルピリジン、酢酸ビニル、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－（メタ）アクリロイルフタルイミド、（３，４－エポキシシクロヘキシル）メチル（メタ）アクリレートが挙げられる。前記モノマーは１種で用いてもよく、２種以上を併用してもよい。 Examples of other radically polymerizable monomers include styrene-based monomers such as styrene, α-methylstyrene, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether; aromatic rings of styrene-based monomers. Monomers made by substituting one or more hydrogen atoms bonded to carbon with alkyl, alkoxy, halogen, haloalkyl, nitro or cyano; dienes such as butadiene, isoprene, chloroprene; unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and Unsaturated carboxylic acids such as the half ester; o-vinyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid or one or more hydrogen atoms bonded to the aromatic ring carbon of these monomers are alkylated, alkoxy, etc. Monomers made by substituting halogen, haloalkyl, nitro or cyano; (meth) acrylic acid esters such as glycidyl (meth) acrylate, (meth) acrylonitrile, achlorine, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, Examples thereof include N-vinylpyrrolidone, vinylpyridine, vinyl acetate, N-phenylmaleimide, N-cyclohexylmaleimide, N- (meth) acryloylphthalimide, and (3,4-epoxycyclohexyl) methyl (meth) acrylate. The monomer may be used alone or in combination of two or more.
　前記ラジカル重合性モノマーの重合体において、フェノール性水酸基を有するラジカル重合性モノマー由来の構造単位の含有割合は、フェノール性水酸基を有するラジカル重合性モノマー由来の構造単位とその他のラジカル重合性モノマー由来の構造単位との含有割合の合計１００モル％に対して、好ましくは３０モル％以上、より好ましくは４０～９５モル％である。 In the polymer of the radically polymerizable monomer, the content ratio of the structural unit derived from the radically polymerizable monomer having a phenolic hydroxyl group is derived from the structural unit derived from the radically polymerizable monomer having a phenolic hydroxyl group and other radically polymerizable monomer. It is preferably 30 mol% or more, more preferably 40 to 95 mol%, based on the total content ratio with the structural unit of 100 mol%.
　前記ラジカル重合性モノマーの重合体としては、好ましくは、ポリヒドロキシスチレン、ｍ－ヒドロキシスチレン／ｐ－ヒドロキシスチレン共重合体、ヒドロキシスチレン／スチレン共重合体、ヒドロキシスチレン／ビニルベンジルグリシジルエーテル／スチレン共重合体、ヒドロキシスチレン／（３，４－エポキシシクロヘキシル）メチルメタクリレート共重合体、ヒドロキシスチレン／（３，４－エポキシシクロヘキシル）メチルメタクリレート／スチレン共重合体等のヒドロキシスチレン系重合体が挙げられる。 The polymer of the radically polymerizable monomer is preferably polyhydroxystyrene, m-hydroxystyrene / p-hydroxystyrene copolymer, hydroxystyrene / styrene copolymer, hydroxystyrene / vinylbenzyl glycidyl ether / styrene common weight. Examples thereof include hydroxystyrene-based polymers such as coalescence, hydroxystyrene / (3,4-epoxycyclohexyl) methylmethacrylate copolymer, and hydroxystyrene / (3,4-epoxycyclohexyl) methylmethacrylate / styrene copolymer.
　≪ノボラック樹脂（ａ２）≫
　ノボラック樹脂（ａ２）は、例えば、フェノール類とアルデヒド類とを酸触媒の存在下で縮合させることにより得ることができる。フェノール類としては、例えば、フェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、ｏ－エチルフェノール、ｍ－エチルフェノール、ｐ－エチルフェノール、ｏ－ブチルフェノール、ｍ－ブチルフェノール、ｐ－ブチルフェノール、２，３－キシレノール、２，４－キシレノール、２，５－キシレノール、２，６－キシレノール、３，４－キシレノール、３，５－キシレノール、２，３，５－トリメチルフェノール、３，４，５－トリメチルフェノール、カテコール、レゾルシノール、ピロガロール、α－ナフトール、β－ナフトールが挙げられる。アルデヒド類としては、例えば、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、サリチルアルデヒドが挙げられる。 ≪Novolak resin (a2) ≫
The novolak resin (a2) can be obtained, for example, by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-Xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethyl Examples thereof include phenol, catechol, resorcinol, pyrogallol, α-naphthol and β-naphthol. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and salicylaldehyde.
　ノボラック樹脂（ａ２）の具体例としては、フェノール／ホルムアルデヒド縮合ノボラック樹脂、クレゾール／ホルムアルデヒド縮合ノボラック樹脂、クレゾール／サリチルアルデヒド縮合ノボラック樹脂、フェノール－ナフトール／ホルムアルデヒド縮合ノボラック樹脂、ノボラック樹脂をブタジエン系重合体などの重合性ビニル基を有するゴム状ポリマーで変性してなる樹脂（例えば、特開２０１０－０１５１０１号公報に記載の樹脂）が挙げられる。 Specific examples of the novolak resin (a2) include phenol / formaldehyde condensed novolac resin, cresol / formaldehyde condensed novolak resin, cresol / salicylaldehyde condensed novolak resin, phenol-naphthol / formaldehyde condensed novolak resin, and novolak resin as a butadiene polymer. Examples thereof include a resin modified with a rubber-like polymer having a polymerizable vinyl group (for example, the resin described in JP-A-2010-015101).
　≪樹脂（Ａ）の構成≫
　樹脂（Ａ）のゲルパーミエーションクロマトグラフィー法により測定される重量平均分子量（Ｍｗ）は、感光性樹脂組成物の解像性、樹脂膜の弾性率およびクラック耐性の観点から、ポリスチレン換算で、通常１，０００～２００，０００、好ましくは２，０００～１００，０００、さらに好ましくは５，０００～５０，０００である。Ｍｗの測定方法の詳細は、実施例に記載したとおりである。 << Composition of resin (A) >>
The weight average molecular weight (Mw) of the resin (A) measured by the gel permeation chromatography method is usually obtained in terms of polystyrene from the viewpoints of resolution of the photosensitive resin composition, elastic modulus of the resin film and crack resistance. It is 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 5,000 to 50,000. The details of the method for measuring Mw are as described in Examples.
　樹脂（Ａ）は、２．３８質量％濃度のテトラメチルアンモニウムハイドロキサイド水溶液（２３℃）に、０．００１ｍｇ／ｍＬ以上溶解する樹脂であることが好ましい。
　本発明の組成物は、１種または２種以上の樹脂（Ａ）を含有することができる。 The resin (A) is preferably a resin that dissolves 0.001 mg / mL or more in a 2.38 mass% concentration of tetramethylammonium hydroxide aqueous solution (23 ° C.).
The composition of the present invention may contain one or more resins (A).
　樹脂（Ａ）の含有割合は、本発明の組成物の固形分１００質量％中、通常３０～９５質量％、好ましくは４０～９０質量％、より好ましくは５０～８５質量％である。樹脂（Ａ）の含有割合が前記範囲にあると、解像度に優れた樹脂膜を形成可能な組成物が得られる傾向にある。固形分は、後述する溶剤以外の全成分をいう。 The content ratio of the resin (A) is usually 30 to 95% by mass, preferably 40 to 90% by mass, and more preferably 50 to 85% by mass in the solid content of 100% by mass of the composition of the present invention. When the content ratio of the resin (A) is within the above range, a composition capable of forming a resin film having excellent resolution tends to be obtained. The solid content refers to all components other than the solvent described later.
　＜架橋剤（Ｂ）＞
　本発明の組成物は、架橋剤（Ｂ）を含有する。架橋剤（Ｂ）は、光照射を受けて光カチオン発生剤（Ｃ１）から発生するカチオンの作用により、樹脂（Ａ）と反応する架橋成分、または架橋剤同士で反応する成分として作用する。架橋剤（Ｂ）を用いることにより、例えば、前記組成物から得られる塗膜を硬化させたり、形成されるパターン化樹脂膜の薬品耐性およびクラック耐性を向上させたりすることができる。 <Crosslinking agent (B)>
The composition of the present invention contains a cross-linking agent (B). The cross-linking agent (B) acts as a cross-linking component that reacts with the resin (A) or a component that reacts with each other by the action of the cation generated from the photo-cation generating agent (C1) upon receiving light irradiation. By using the cross-linking agent (B), for example, the coating film obtained from the composition can be cured, and the chemical resistance and crack resistance of the patterned resin film formed can be improved.
　架橋剤（Ｂ）としては、例えば、メチロール基およびメトキシメチル基等の－ＲB1－Ｏ－ＲB2で表される基を少なくとも２個有する架橋剤（ｂ１）、オキセタン環を少なくとも２つ有する架橋剤、オキシラン環を少なくとも２つ有する架橋剤、オキサゾリン環を少なくとも２つ有する架橋剤、イソシアネート基を少なくとも２つ有する架橋剤（ブロック化されたものを含む）、マレイミド基を少なくとも２つ有する架橋剤が挙げられる。これらの中でも、架橋剤（ｂ１）が好ましい。 As the crosslinking agent (B), for example, groups having at least two crosslinking agent represented by -R B1 -O-R B2, such as methylol groups and methoxymethyl groups (b1), crosslinked with at least two oxetane rings Agent, cross-linking agent having at least two oxylan rings, cross-linking agent having at least two oxazoline rings, cross-linking agent having at least two isocyanate groups (including blocked ones), cross-linking agent having at least two maleimide groups. Can be mentioned. Among these, the cross-linking agent (b1) is preferable.
　架橋剤（ｂ１）における前記式中、ＲB1は、アルカンジイル基であり、好ましくは炭素数１～１０のアルカンジイル基であり、ＲB2は、水素原子またはアルキル基であり、好ましくは水素原子または炭素数１～１０のアルキル基である。 In the formula in the cross-linking agent (b1), R B1 is an alkanediyl group, preferably alkanediyl group having 1 to 10 carbon atoms, R B2 is a hydrogen atom or an alkyl group, preferably a hydrogen atom Alternatively, it is an alkyl group having 1 to 10 carbon atoms.
　ＲB1におけるアルカンジイル基としては、例えば、メチレン基、エチレン基が挙げられ、ＲB2におけるアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基が挙げられる。 The alkanediyl group in R B1, for example, methylene group, and ethylene group, the alkyl group in R B2, for example, a methyl group, an ethyl group, a propyl group, a butyl group.
　架橋剤（ｂ１）としては、例えば、－ＲB1－Ｏ－ＲB2で表される基が結合したアミノ基を２個以上有する化合物、メチロール基含有フェノール化合物、アルキルメチロール基含有フェノール化合物が挙げられる。 As the crosslinking agent (b1), for example, compounds having -R B1 -O-R B2 in 2 or more amino groups group is bonded, represented, methylol group-containing phenol compound, an alkyl methylol group-containing phenol compounds ..
　－ＲB1－Ｏ－ＲB2で表される基が結合したアミノ基は、例えば、式（ｂ１－１）で表される基、式（ｂ１－２）で表される基が挙げられる。 Examples of the amino group to which the group represented by -R B1 -OR B2 is bonded include a group represented by the formula (b1-1) and a group represented by the formula (b1-2).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（ｂ１－１）および式（ｂ１－２）中、ＲB1は、アルカンジイル基であり、好ましくは炭素数１～１０のアルカンジイル基であり、ＲB2は、水素原子またはアルキル基であり、好ましくは水素原子または炭素数１～１０のアルキル基であり、ｍは１または２であり、ｎは０または１であり、ｍ＋ｎは２であり、＊は結合手である。 In formulas (b1-1) and (b1-2), R B1 is an alkanediyl group, preferably an alkanediyl group having 1 to 10 carbon atoms, and R B2 is a hydrogen atom or an alkyl group. , Preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, m being 1 or 2, n being 0 or 1, m + n being 2, and * being a bond.
　架橋剤（ｂ１）としては、例えば、ポリメチロール化メラミン、ポリメチロール化グリコールウリル、ポリメチロール化グアナミン、ポリメチロール化ウレア等の窒素原子含有化合物；前記窒素原子含有化合物中の活性メチロール基（Ｎ原子に結合したＣＨ2ＯＨ基）の全部または一部がアルキルエーテル化された化合物が挙げられる。ここで、アルキルエーテルを構成するアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基が挙げられ、これらは互いに同一であってもよいし、異なっていてもよい。また、アルキルエーテル化されていない活性メチロール基は、一分子内で自己縮合していてもよく、二分子間で縮合して、その結果、オリゴマー成分が形成されていてもよい。 Examples of the cross-linking agent (b1) include nitrogen atom-containing compounds such as polymethylolated melamine, polymethylolated glycoluryl, polymethylollated guanamine, and polymethylolated urea; active methylol groups (N atoms) in the nitrogen atom-containing compound. Examples thereof include compounds in which all or part of the CH 2 OH group bonded to the compound is alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, a propyl group, and a butyl group, which may be the same or different from each other. Further, the active methylol group which has not been alkyl etherized may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed.
　架橋剤（ｂ１）の具体例としては、例えば、特開平６－１８０５０１号公報、特開２００６－１７８０５９号公報および特開２０１２－２２６２９７号公報に記載の架橋剤が挙げられる。具体的には、ポリメチロール化メラミン、ヘキサメトキシメチルメラミン、ヘキサエトキシメチルメラミン、ヘキサプロポキシメチルメラミン、ヘキサブトキシメチルメラミン等のメラミン系架橋剤；ポリメチロール化グリコールウリル、テトラメトキシメチルグリコールウリル、テトラブトキシメチルグリコールウリル等のグリコールウリル系架橋剤；３，９－ビス［２－（３，５－ジアミノ－２，４，６－トリアザフェニル）エチル］２，４，８，１０－テトラオキソスピロ［５．５］ウンデカン、３，９－ビス［２－（３，５－ジアミノ－２，４，６－トリアザフェニル）プロピル］２，４，８，１０－テトラオキソスピロ［５．５］ウンデカン等のグアナミンをメチロール化した化合物、および当該化合物中の活性メチロール基の全部または一部をアルキルエーテル化した化合物等のグアナミン系架橋剤が挙げられる。 Specific examples of the cross-linking agent (b1) include the cross-linking agents described in JP-A-6-180501, JP-A-2006-178509, and JP-A-2012-226297. Specifically, melamine-based cross-linking agents such as polymethylated melamine, hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxymethyl melamine; Glycoluryl-based cross-linking agents such as methyl glycol uryl; 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] 2,4,8,10-tetraoxospiro [ 5.5] Undecane, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) propyl] 2,4,8,10-tetraoxospiro [5.5] Undecane Examples thereof include guanamine-based cross-linking agents such as compounds obtained by methylolating guanamine such as, and compounds in which all or part of the active methylol group in the compound is alkyl etherified.
　メチロール基含有フェノール化合物およびアルキルメチロール基含有フェノール化合物としては、例えば、２，６－ジメトキシメチル－４－ｔ－ブチルフェノール、２，６－ジメトキシメチル－ｐ－クレゾールが挙げられる。 Examples of the methylol group-containing phenol compound and the alkylmethylol group-containing phenol compound include 2,6-dimethoxymethyl-4-t-butylphenol and 2,6-dimethoxymethyl-p-cresol.
　本発明の組成物は、１種または２種以上の架橋剤（Ｂ）を含有することができる。
　本発明の組成物において、架橋剤（Ｂ）の含有量は、樹脂（Ａ）１００質量部に対して、通常１～１００質量部、好ましくは５～５０質量部、より好ましくは１０～４０質量部である。架橋剤（Ｂ）の含有量が前記範囲にあると、薬品耐性およびクラック耐性に優れるパターン化樹脂膜を形成できる傾向にある。 The composition of the present invention can contain one or more cross-linking agents (B).
In the composition of the present invention, the content of the cross-linking agent (B) is usually 1 to 100 parts by mass, preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the resin (A). It is a department. When the content of the cross-linking agent (B) is within the above range, a patterned resin film having excellent chemical resistance and crack resistance tends to be formed.
　＜光カチオン発生剤（Ｃ）＞
　本発明の組成物は、光カチオン発生剤（Ｃ）として、以下に記載する式（Ｃ１）に示す光カチオン発生剤（Ｃ１）を含有する。 <Photocation generator (C)>
The composition of the present invention contains the photocation generator (C1) represented by the formula (C1) described below as the photocation generator (C).
　光カチオン発生剤（Ｃ１）は、光照射を受けて光分解し、スルホン酸を発生する化合物である。光カチオン発生剤（Ｃ１）は、例えば波長３６５ｎｍの光に対する吸収が大きく、良好な酸発生率を有し、フェノール性水酸基を有する樹脂（Ａ）や低分子フェノール化合物（Ｄ）と良好に混和するため、少量の使用でも充分な効果、例えば感光性樹脂組成物の優れた感度、を奏する。前記スルホン酸由来のカチオンは、例えば、樹脂（Ａ）と架橋剤（Ｂ）との架橋反応や、架橋剤（Ｂ）同士の反応を促進すると考えられる。したがって、本発明の組成物から形成される塗膜を露光することで、露光部に光カチオン発生剤（Ｃ１）からカチオンが発生し、このカチオンの作用に基づき架橋反応が促進され架橋構造が形成されて、現像液への溶解性が低下すると考えられる。 The photocation generator (C1) is a compound that receives light irradiation and photodecomposes to generate sulfonic acid. The photocation generator (C1) absorbs light at a wavelength of 365 nm, for example, has a good acid generation rate, and mixes well with a resin (A) having a phenolic hydroxyl group and a low molecular weight phenol compound (D). Therefore, even if it is used in a small amount, a sufficient effect, for example, excellent sensitivity of the photosensitive resin composition is obtained. The cation derived from sulfonic acid is considered to promote, for example, a cross-linking reaction between the resin (A) and the cross-linking agent (B) and a reaction between the cross-linking agents (B). Therefore, by exposing the coating film formed from the composition of the present invention, a cation is generated from the photocation generator (C1) in the exposed portion, and the cross-linking reaction is promoted based on the action of the cation to form a cross-linked structure. Therefore, it is considered that the solubility in the developing solution is reduced.
　本発明では、光カチオン発生剤（Ｃ１）を用いることにより、前述したイオンマイグレーションの発生を抑制することができたと考えられる。したがって、本発明の組成物を用いることにより、イオンマイグレーションの発生が抑制された絶縁膜を製造することができ、前記絶縁膜は半導体回路基板における電極や配線間にある絶縁膜として好適である。
イオンマイグレーションが抑制される理由について、本発明者らは以下のように推測している。 In the present invention, it is considered that the occurrence of the above-mentioned ion migration could be suppressed by using the photocation generator (C1). Therefore, by using the composition of the present invention, an insulating film in which the occurrence of ion migration is suppressed can be produced, and the insulating film is suitable as an insulating film between electrodes and wirings in a semiconductor circuit board.
The present inventors speculate that the reason why ion migration is suppressed is as follows.
　絶縁膜形成用の感光性樹脂組成物では、従来、スルホニウム塩等のオニウム塩を光カチオン発生剤として使用することが多い。ここで、露光・現像後にパターン化樹脂膜中に未反応のオニウム塩が残ると、オニウム塩は熱カチオン発生剤としても機能し得るため、露光・現像後に行う高温での処理工程で酸が発生し、その結果、銅配線等の配線が酸化され、それに伴いイオンマイグレーションが進行すると考えられる。 In the photosensitive resin composition for forming an insulating film, an onium salt such as a sulfonium salt is often used as a photocation generator. Here, if an unreacted onium salt remains in the patterned resin film after exposure / development, the onium salt can also function as a thermal cation generator, so that an acid is generated in the high-temperature treatment step performed after exposure / development. As a result, wiring such as copper wiring is oxidized, and it is considered that ion migration proceeds accordingly.
　高周波回路などに用いられる回路基板では、高周波かつ発熱による高温環境においてイオンマイグレーションが起きやすく、さらに、配線間が狭くなるためイオンマイグレーションによる断線が顕在化しやすい。 In circuit boards used for high-frequency circuits, ion migration is likely to occur in a high-frequency and high-temperature environment due to heat generation, and since the wiring space is narrowed, disconnection due to ion migration is likely to become apparent.
　イオンマイグレーションが進行する要因としては、イオンの存在、ｐＨの低下が関係していることが知られている。オニウム塩は、イオン系の光カチオン発生剤であり、また熱カチオン発生剤としても機能し得ることから、高温高湿環境下では酸が発生しｐＨが下がると考えられる。そこで、イオン系の光カチオン発生剤の代わりに、熱カチオン発生剤として機能しにくいノニオン系の光カチオン発生剤であり、また、露光・現像後にパターン化樹脂膜中に光カチオン発生剤が残らないように光分解がしやすい光カチオン発生剤である前記光カチオン発生剤（Ｃ１）を少量用いることで、感光性樹脂組成物の優れた感度を維持しつつ、得られる絶縁膜において前記イオンマイグレーションの発生を抑制することができる。 It is known that the presence of ions and the decrease in pH are related to the progress of ion migration. Since the onium salt is an ionic photocation generator and can also function as a thermal cation generator, it is considered that an acid is generated and the pH is lowered in a high temperature and high humidity environment. Therefore, instead of the ionic photocation generator, it is a nonionic photocation generator that does not easily function as a thermal cation generator, and the photocation generator does not remain in the patterned resin film after exposure and development. By using a small amount of the photocation generator (C1), which is a photocation generator that is easily photodecomposable, the ion migration can be carried out in the obtained insulating film while maintaining the excellent sensitivity of the photosensitive resin composition. Occurrence can be suppressed.
　なお、以上の説明は推測であって本発明を何ら限定するものではない。 The above explanation is speculative and does not limit the present invention in any way.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　式（Ｃ１）中、Ｒ1は非置換または置換の炭化水素基を示し、Ｒ2～Ｒ7はそれぞれ独立に水素原子、または非置換もしくは置換のアルキル基を示し、Ｒ2～Ｒ7のうち少なくとも一つは非置換または置換のアルキル基を示す。 In formula (C1), R 1 represents an unsubstituted or substituted hydrocarbon group, R 2 to R 7 each independently represent a hydrogen atom or an unsubstituted or substituted alkyl group, and among R 2 to R 7 , At least one represents an unsubstituted or substituted alkyl group.
　≪Ｒ 1 ：非置換または置換の炭化水素基≫
　Ｒ1における非置換の炭化水素基としては、例えば、アルキル基、アルケニル基などの脂肪族炭化水素基；シクロアルキル基、シクロアルキルアルキル基、多環式飽和環状炭化水素基などの脂環含有炭化水素基；アリール基、アラルキル基などの芳香環含有炭化水素基が挙げられる。非置換の炭化水素基の炭素数は、通常２０以下、好ましくは１０以下である。 ≪R 1 : unsubstituted or substituted hydrocarbon group≫
Examples of the unsubstituted hydrocarbon group in R 1 include aliphatic hydrocarbon groups such as alkyl groups and alkenyl groups; alicyclic-containing hydrocarbons such as cycloalkyl groups, cycloalkylalkyl groups and polycyclic saturated cyclic hydrocarbon groups. Hydrogen group; Examples thereof include an aromatic ring-containing hydrocarbon group such as an aryl group and an aralkyl group. The unsubstituted hydrocarbon group usually has 20 or less carbon atoms, preferably 10 or less carbon atoms.
　アルキル基としては、例えば、炭素数１～２０、好ましくは炭素数１～１０のアルキル基が挙げられ、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec－ブチル基、tert－ブチル基、ペンチル基、ヘキシル基、オクチル基、ノニル基、デシル基が挙げられる。 Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and the like. Examples thereof include sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group and decyl group.
　アルケニル基としては、例えば、炭素数２～２０、好ましくは炭素数２～１０のアルケニル基が挙げられ、具体的には、ビニル基、アリル基、２－メチル－２－プロペニル基が挙げられる。 Examples of the alkenyl group include an alkenyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, and a 2-methyl-2-propenyl group.
　アルキル基、アルケニル基は、直鎖であっても分岐鎖であってもよい。
　シクロアルキル基としては、例えば、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基が挙げられ；シクロアルキルアルキル基としては、例えば、シクロヘキシルメチル基、シクロヘキシルエチル基が挙げられ；多環式飽和環状炭化水素基としては、例えば、ノルボルニル基、アダマンチル基、トリシクロデシル基、テトラシクロドデシル基が挙げられる。 The alkyl group and the alkenyl group may be a straight chain or a branched chain.
Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a cyclodecyl group; examples of the cycloalkylalkyl group include a cyclohexylmethyl group and a cyclohexylethyl group; Examples of the saturated cyclic hydrocarbon group include a norbornyl group, an adamantyl group, a tricyclodecyl group and a tetracyclododecyl group.
　アリール基としては、例えば、炭素数６～２０のアリール基が挙げられ、具体的には、フェニル基、ナフチル基、ビフェニル基；４－メチルフェニル基、２，３－ジメチルフェニル基、２，４，６－トリイソプロピルフェニル基などのアルキルアリール基；シクロヘキシルフェニル基などのシクロアルキルアリール基が挙げられる。 Examples of the aryl group include an aryl group having 6 to 20 carbon atoms, and specifically, a phenyl group, a naphthyl group, a biphenyl group; 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4. , Alkylaryl groups such as 6-triisopropylphenyl group; cycloalkylaryl groups such as cyclohexylphenyl group.
　アラルキル基としては、例えば、炭素数７～２０のアラルキル基が挙げられ、具体的には、ベンジル基、フェネチル基、ジフェニルメチル基、トリフェニルメチル基が挙げられる。 Examples of the aralkyl group include an aralkyl group having 7 to 20 carbon atoms, and specific examples thereof include a benzyl group, a phenethyl group, a diphenylmethyl group, and a triphenylmethyl group.
　置換の炭化水素基とは、非置換の炭化水素基中の少なくとも１つの水素原子を炭化水素基以外の別の基（置換基）に置換した基を意味する。したがって、例えばアラルキル基は非置換の炭化水素基に分類する。「非置換の炭化水素基」を単に「炭化水素基」ということがある。 The substituted hydrocarbon group means a group in which at least one hydrogen atom in the unsubstituted hydrocarbon group is substituted with another group (substituent) other than the hydrocarbon group. Therefore, for example, an aralkyl group is classified as an unsubstituted hydrocarbon group. The "unsubstituted hydrocarbon group" is sometimes simply referred to as the "hydrocarbon group".
　置換の炭化水素基における置換基としては、例えば、ハロゲン原子、ヒドロキシ基、アルコキシ基、アリールオキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシロキシ基、アルキルチオ基、アリールチオ基、複素環式基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基が挙げられる。置換の炭化水素基が２個以上の置換基を有する場合、各々の置換基は同一であっても異なっていてもよい。 Examples of the substituent in the substituted hydrocarbon group include a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group and an acyloxy group. , Alkylthio group, arylthio group, heterocyclic group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group. When the substituent hydrocarbon group has two or more substituents, each substituent may be the same or different.
　置換の炭化水素基としては、前記非置換の炭化水素基中の少なくとも１つの水素原子をハロゲン原子に置換したハロゲン化炭化水素基が好ましく、ハロゲン化アルキル基、ハロゲン化アリール基がより好ましく、ハロゲン化アルキル基がさらに好ましい。 As the substituted hydrocarbon group, a halogenated hydrocarbon group in which at least one hydrogen atom in the unsubstituted hydrocarbon group is substituted with a halogen atom is preferable, an alkyl halide group and an aryl halide group are more preferable, and a halogen is more preferable. Hydrocarbon groups are more preferred.
　ここでハロゲン原子としては、例えば、フッ素、塩素、臭素、ヨウ素が挙げられる。ハロゲン化アルキル基としては、例えば、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、ノナフルオロブチル基などのパーフルオロアルキル基；１，１－ジフルオロエチル基、２，２，２－トリフルオロエチル基、１，１，２，２－テトラフルオロプロピル基、３，３，３－トリフルオロプロピル基、２，２，３，３，３－ペンタフルオロプロピル基、フルオロメチル基、クロロメチル基、２－クロロエチル基、２－ブロモエチル基が挙げられる。ハロゲン化アリール基としては、例えば、ペンタフルオロアリール基、トリフルオロメチルフェニル基、３，５－ジ（トリフルオロメチル）フェニル基が挙げられる。 Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Examples of the alkyl halide group include perfluoroalkyl groups such as trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group and nonafluorobutyl group; 1,1-difluoroethyl group and 2,2,2-tri Fluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, fluoromethyl group, chloromethyl group , 2-Chloroethyl group, 2-bromoethyl group. Examples of the aryl halide group include a pentafluoroaryl group, a trifluoromethylphenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
　Ｒ1としては、非置換の炭化水素基、または前記非置換の炭化水素基中の少なくとも１つの水素原子をハロゲン原子に置換したハロゲン化炭化水素基が好ましく、より好ましくはハロゲン化アルキル基、さらに好ましくはパーフルオロアルキル基、特に好ましくは炭素数１～８のパーフルオロアルキル基である。 As R 1 , an unsubstituted hydrocarbon group or a halogenated hydrocarbon group in which at least one hydrogen atom in the unsubstituted hydrocarbon group is substituted with a halogen atom is preferable, more preferably an alkyl halide group, and further. A perfluoroalkyl group is preferable, and a perfluoroalkyl group having 1 to 8 carbon atoms is particularly preferable.
　≪Ｒ 2 ～Ｒ 7 ：非置換または置換のアルキル基≫
　Ｒ2～Ｒ7における非置換のアルキル基としては、例えば、炭素数１～２０、好ましくは炭素数１～１４、より好ましくは炭素数３～８のアルキル基が挙げられ、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec－ブチル基、tert－ブチル基、ペンチル基、ヘキシル基、オクチル基、ノニル基、デシル基が挙げられる。アルキル基は、直鎖であっても分岐鎖であってもよい。 ≪R 2 to R 7 : unsubstituted or substituted alkyl group≫
Examples of the unsubstituted alkyl group in R 2 to R 7 include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, and more preferably 3 to 8 carbon atoms. Examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group and decyl group. The alkyl group may be a straight chain or a branched chain.
　置換のアルキル基とは、非置換のアルキル基中の少なくとも１つの水素原子をアルキル基以外の別の基（置換基）に置換した基を意味する。「非置換のアルキル基」を単に「アルキル基」ということがある。 The substituted alkyl group means a group in which at least one hydrogen atom in the unsubstituted alkyl group is substituted with another group (substituent) other than the alkyl group. An "unsubstituted alkyl group" may simply be referred to as an "alkyl group".
　前記置換基としては、例えば、シクロアルキル基、多環式飽和環状炭化水素基、アリール基、アラルキル基が挙げられ、これらの基の具体例は前述した。置換のアルキル基が２個以上の置換基を有する場合、各々の置換基は同一であっても異なっていてもよい。 Examples of the substituent include a cycloalkyl group, a polycyclic saturated cyclic hydrocarbon group, an aryl group, and an aralkyl group, and specific examples of these groups have been described above. When the substituted alkyl group has two or more substituents, each substituent may be the same or different.
　Ｒ2～Ｒ7としては、水素原子または非置換のアルキル基が好ましい。
　光カチオン発生剤（Ｃ１）の光吸収、特に波長３６５ｎｍにおける光吸収が大きいことから、Ｒ2～Ｒ7のうち少なくとも一つは非置換または置換のアルキル基を示す。光吸収性の観点から、Ｒ4が非置換または置換のアルキル基であり、Ｒ2～Ｒ3およびＲ5～Ｒ7が水素原子であることが好ましく、Ｒ4が非置換のアルキル基であることがより好ましい。 As R 2 to R 7 , a hydrogen atom or an unsubstituted alkyl group is preferable.
Due to the large light absorption of the photocation generator (C1), especially at a wavelength of 365 nm, at least one of R 2 to R 7 exhibits an unsubstituted or substituted alkyl group. From the viewpoint of light absorption, it is preferable that R 4 is an unsubstituted or substituted alkyl group, R 2 to R 3 and R 5 to R 7 are hydrogen atoms, and R 4 is an unsubstituted alkyl group. Is more preferable.
　光カチオン発生剤（Ｃ１）は、従来公知の方法により製造することができ、例えば、国際公開第２０１４／０８４２６９号、国際公開第２０１５／００１８０４号に記載の方法が挙げられる。 The photocation generator (C1) can be produced by a conventionally known method, and examples thereof include the methods described in International Publication No. 2014/084269 and International Publication No. 2015/001804.
　本発明の組成物は、１種または２種以上の光カチオン発生剤（Ｃ１）を含有することができる。
　本発明の組成物における光カチオン発生剤（Ｃ１）の含有量は、架橋剤（Ｂ）１００質量部に対して、通常１～１５質量部、好ましくは２～１０質量部、より好ましくは３～８質量部である。光カチオン発生剤（Ｃ１）の含有量が前記下限値以上であると、露光部の硬化が充分となり、パターン化樹脂膜の耐熱性が向上しやすい。光カチオン発生剤（Ｃ１）の含有量が前記上限値以下であると、露光に用いられる光に対する透明性が低下することなく、解像度が高いパターン化樹脂膜が得られやすい。 The composition of the present invention can contain one or more photocation generators (C1).
The content of the photocation generator (C1) in the composition of the present invention is usually 1 to 15 parts by mass, preferably 2 to 10 parts by mass, and more preferably 3 to 3 parts by mass with respect to 100 parts by mass of the cross-linking agent (B). It is 8 parts by mass. When the content of the photocation generator (C1) is at least the above lower limit value, the exposed portion is sufficiently cured and the heat resistance of the patterned resin film is likely to be improved. When the content of the photocation generator (C1) is not more than the above upper limit value, a patterned resin film having high resolution can be easily obtained without reducing the transparency to light used for exposure.
　本発明の組成物の固形分中に含まれる光カチオン発生剤（Ｃ１）の含有割合は、０．０１～０．９質量％であり、好ましくは下限値が０．１質量％、上限値が０．８５質量％、より好ましくは下限値が０．３質量％、上限値が０．８質量％である。光カチオン発生剤（Ｃ１）は光照射に対する良好な酸発生率を有するため、下限値が前記値であっても本発明の効果が得られる。一方、光カチオン発生剤（Ｃ１）は光照射を受けて光分解し、スルホン酸を発生する化合物であるため、上限値が前記値であれば、スルホン酸の拡散によるパターン化樹脂膜中への残存をなくすことができ、イオンマイグレーションの発生を抑制することができる。 The content ratio of the photocation generator (C1) contained in the solid content of the composition of the present invention is 0.01 to 0.9% by mass, preferably the lower limit is 0.1% by mass and the upper limit is 0.1% by mass. 0.85% by mass, more preferably the lower limit is 0.3% by mass and the upper limit is 0.8% by mass. Since the photocation generator (C1) has a good acid generation rate with respect to light irradiation, the effect of the present invention can be obtained even if the lower limit value is the above value. On the other hand, the photocation generator (C1) is a compound that is photodecomposed by light irradiation to generate sulfonic acid. Therefore, if the upper limit is the above value, it can be deposited into the patterned resin film by diffusion of sulfonic acid. It is possible to eliminate the residue and suppress the occurrence of ion migration.
　本発明の組成物は、光カチオン発生剤（Ｃ１）以外の他の光カチオン発生剤をさらに含有することができる。光カチオン発生剤（Ｃ１）および他の光カチオン発生剤を併せて「光カチオン発生剤（Ｃ）」という。上述した本発明の効果の観点から、光カチオン発生剤（Ｃ）中に含まれる前記光カチオン発生剤（Ｃ１）の含有割合は、好ましくは９０質量％以上であり、より好ましくは９５質量％以上、さらに好ましくは９９質量％以上である。 The composition of the present invention can further contain a photocation generator other than the photocation generator (C1). The photocation generator (C1) and other photocation generators are collectively referred to as "photocation generator (C)". From the viewpoint of the above-mentioned effect of the present invention, the content ratio of the photocation generator (C1) contained in the photocation generator (C) is preferably 90% by mass or more, more preferably 95% by mass or more. , More preferably 99% by mass or more.
　他の光カチオン発生剤としては、光照射により酸を発生する感光性酸発生剤が好ましく、例えば、オニウム塩、ハロゲン含有化合物、スルホン化合物、スルホン酸化合物、スルホンイミド化合物、ジアゾメタン化合物が挙げられる。 As the other photocation generator, a photosensitive acid generator that generates an acid by light irradiation is preferable, and examples thereof include onium salts, halogen-containing compounds, sulfonic compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds.
　オニウム塩、ハロゲン含有化合物、スルホン化合物、スルホン酸化合物、スルホンイミド化合物およびジアゾメタン化合物の具体例としては、例えば、特開２０１４－１８６３００号公報の段落［００７４］～［００７９］に記載された化合物が挙げられ、これらの化合物は本明細書に記載されているものとする。 Specific examples of the onium salt, halogen-containing compound, sulfonic acid compound, sulfonic acid compound, sulfonimide compound and diazomethane compound include the compounds described in paragraphs [0074] to [0079] of JP-A-2014-186300. Listed and these compounds are as described herein.
　＜低分子フェノール化合物（Ｄ）＞
　本発明の組成物は、好ましくは低分子フェノール化合物（Ｄ）をさらに含有する。
　低分子フェノール化合物（Ｄ）は、フェノール性水酸基を有する、分子量が１０００未満、好ましくは８００未満の化合物を示す。低分子フェノール化合物（Ｄ）は、フェノール性水酸基を有する樹脂（Ａ）と同様の機能を有しているが、低分子であることから、後述のアルカリ性現像液への溶解性が高いため、感光性樹脂組成物の解像性を向上させることができる。その結果、感光性樹脂組成物中に含まれる光カチオン発生剤（Ｃ１）の含有割合を減らすことができる。 <Low molecular weight phenol compound (D)>
The composition of the present invention preferably further contains the low molecular weight phenol compound (D).
The low molecular weight phenol compound (D) represents a compound having a phenolic hydroxyl group and having a molecular weight of less than 1000, preferably less than 800. The low-molecular-weight phenolic compound (D) has the same function as the resin (A) having a phenolic hydroxyl group, but since it is a low-molecular-weight compound, it is highly soluble in an alkaline developer, which will be described later. The resolution of the sex resin composition can be improved. As a result, the content ratio of the photocation generator (C1) contained in the photosensitive resin composition can be reduced.
　低分子フェノール化合物（Ｄ）としては、例えば、４，４'－ジヒドロキシジフェニルメタン、４，４'－ジヒドロキシジフェニルエーテル、トリス（４－ヒドロキシフェニル）メタン、１，１－ビス（４－ヒドロキシフェニル）－１－フェニルエタン、トリス（４－ヒドロキシフェニル）エタン、１，３－ビス［１－（４－ヒドロキシフェニル）－１－メチルエチル］ベンゼン、１，４－ビス［１－（４－ヒドロキシフェニル）－１－メチルエチル］ベンゼン、４，６－ビス［１－（４－ヒドロキシフェニル）－１－メチルエチル］－１，３－ジヒドロキシベンゼン、１，１－ビス（４－ヒドロキシフェニル）－１－［４－｛１－（４－ヒドロキシフェニル）－１－メチルエチル｝フェニル］エタン、１，１，２，２－テトラ（４－ヒドロキシフェニル）エタン１－［α，α－ビス（４－ヒドロキシフェニル）エチル］－４－［α'－メチル－α'－（４'－ヒドロキシフェニル）エチル］ベンゼン、１，１－ビス（４－ヒドロキシ－２，５－ジメチルフェニル）プロパン－２－オンが挙げられる。 Examples of the low molecular weight phenol compound (D) include 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, and 1,1-bis (4-hydroxyphenyl) -1. -Phenyl ethane, tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl)- 1-Methylethyl] benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1-[ 4- {1- (4-Hydroxyphenyl) -1-methylethyl} phenyl] ethane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane 1- [α, α-bis (4-hydroxyphenyl) ) Ethyl] -4- [α'-methyl-α'-(4'-hydroxyphenyl) ethyl] benzene, 1,1-bis (4-hydroxy-2,5-dimethylphenyl) propan-2-one. Be done.
　本発明の組成物は、１種または２種以上の低分子フェノール化合物（Ｄ）を含有することができる。
　低分子フェノール化合物（Ｄ）を用いる場合、本発明の組成物における樹脂（Ａ）１００質量部に対する低分子フェノール化合物（Ｄ）の含有量の下限値は通常１質量部であり、上限値は通常５０質量部である。低分子フェノール成分が上記範囲であると、樹脂膜の極性をイオンマイグレーションが実用上問題とならない範囲に抑制しつつ、アルカリ性現像液への溶解性を調整したり、パターンの解像性を向上させることができる。 The composition of the present invention can contain one or more low molecular weight phenolic compounds (D).
When the low molecular weight phenol compound (D) is used, the lower limit of the content of the low molecular weight phenol compound (D) with respect to 100 parts by mass of the resin (A) in the composition of the present invention is usually 1 part by mass, and the upper limit is usually 1 part by mass. It is 50 parts by mass. When the low-molecular-weight phenol component is in the above range, the polarity of the resin film is suppressed to a range in which ion migration does not pose a practical problem, the solubility in an alkaline developer is adjusted, and the resolution of the pattern is improved. be able to.
　＜その他の成分＞
　本発明の組成物は、上述した各成分の他、本発明の目的および特性を損なわない範囲で、その他の成分を含有することができる。その他の成分としては、例えば、フェノール性水酸基を有する樹脂（Ａ）以外の樹脂、界面活性剤、レベリング剤、接着助剤、増感剤、クエンチャー、架橋微粒子、無機フィラー等の添加剤が挙げられる。 <Other ingredients>
In addition to the above-mentioned components, the composition of the present invention may contain other components as long as the object and properties of the present invention are not impaired. Examples of other components include resins other than the resin (A) having a phenolic hydroxyl group, surfactants, leveling agents, adhesive aids, sensitizers, quenchers, crosslinked fine particles, and additives such as inorganic fillers. Be done.
　接着助剤としては、例えば、トリス（トリメトキシシリルプロピル）イソシアヌレート、およびグリシドキシプロピルトリメトキシシラン等のシランカップリング剤が挙げられる。接着助剤を用いる場合、本発明の組成物における樹脂（Ａ）１００質量部に対する接着助剤の含有量の下限値は通常１質量部であり、上限値は通常５０質量部である。 Examples of the adhesion aid include silane coupling agents such as tris (trimethoxysilylpropyl) isocyanurate and glycidoxypropyltrimethoxysilane. When an adhesive aid is used, the lower limit of the content of the adhesive aid with respect to 100 parts by mass of the resin (A) in the composition of the present invention is usually 1 part by mass, and the upper limit is usually 50 parts by mass.
　界面活性剤としては、例えば、フッ素系界面活性剤、シリコーン系界面活性剤、ポリアルキレンオキシド系界面活性剤が挙げられる。界面活性剤を用いる場合、本発明の組成物における樹脂（Ａ）１００質量部に対する界面活性剤の含有量の下限値は通常０．０００１質量部であり、上限値は通常１質量部である。 Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and a polyalkylene oxide-based surfactant. When a surfactant is used, the lower limit of the content of the surfactant with respect to 100 parts by mass of the resin (A) in the composition of the present invention is usually 0.0001 parts by mass, and the upper limit is usually 1 part by mass.
　＜溶剤＞
　本発明の組成物は、溶剤を含有することが好ましい。溶剤を用いることで、本発明の組成物の取扱い性を向上させたり、粘度および保存安定性を調節したりすることができる。 <Solvent>
The composition of the present invention preferably contains a solvent. By using a solvent, the handleability of the composition of the present invention can be improved, and the viscosity and storage stability can be adjusted.
　溶剤としては、例えば、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート等のエチレングリコールモノアルキルエーテルアセテート類；プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル等のプロピレングリコールモノアルキルエーテル類；プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジプロピルエーテル、プロピレングリコールジブチルエーテル等のプロピレングリコールジアルキルエーテル類；プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート等のプロピレングリコールモノアルキルエーテルアセテート類；エチルセロソルブ、ブチルセロソルブ等のセロソルブ類；ブチルカルビトール等のカルビトール類；乳酸メチル、乳酸エチル、乳酸ｎ－プロピル、乳酸イソプロピル等の乳酸エステル類；酢酸エチル、酢酸ｎ－プロピル、酢酸イソプロピル、酢酸ｎ－ブチル、酢酸イソブチル、酢酸ｎ－アミル、プロピオン酸イソプロピル、プロピオン酸ｎ－ブチル、プロピオン酸イソブチル等の脂肪族カルボン酸エステル類；３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、ピルビン酸メチル、ピルビン酸エチル等の他のエステル類；２－ヘプタノン、３－ヘプタノン、４－ヘプタノン、シクロヘキサノン等のケトン類；Ｎ－ジメチルホルムアミド、Ｎ－メチルアセトアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン等のアミド類；γ－ブチロラクトン等のラクトン類；トルエン、キシレン等の芳香族炭化水素類が挙げられる。 Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like. Propylene glycol monoalkyl ethers; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Propropylene glycol monoalkyl ether acetates such as monopropyl ether acetate and propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; methyl lactate, ethyl lactate, n-propyl lactate, lactic acid Lactic acid esters such as isopropyl; aliphatic carboxylic acids such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isopropyl propionate, n-butyl propionate and isobutyl propionate. Ethers; other esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; 2-heptanone, 3 -Ketones such as heptanone, 4-heptanone, cyclohexanone; amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone; lactones such as γ-butyrolactone; toluene, xylene Such as aromatic hydrocarbons.
　これらの中でも、ケトン類、ラクトン類、乳酸エステル類、プロピレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテル類が好ましく、２－ヘプタノン、γ－ブチロラクトン、乳酸エチル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルがより好ましい。 Among these, ketones, lactones, lactic acid esters, propylene glycol monoalkyl ether acetates and propylene glycol monoalkyl ethers are preferable, and 2-heptanone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate and propylene glycol are preferable. Monomethyl ether is more preferred.
　本発明の組成物は、１種または２種以上の溶剤を含有することができる。
　本発明の組成物における溶剤の含有割合は、通常１０～９５質量％、好ましくは３０～９０質量％である。 The composition of the present invention may contain one or more solvents.
The content ratio of the solvent in the composition of the present invention is usually 10 to 95% by mass, preferably 30 to 90% by mass.
　＜感光性樹脂組成物の製造方法＞
　本発明の組成物は、当該組成物を構成する各成分を均一に混合することにより製造することができる。また、異物を取り除くために、前記各成分を均一に混合した後、得られた混合物をフィルター等で濾過することができる。 <Manufacturing method of photosensitive resin composition>
The composition of the present invention can be produced by uniformly mixing each component constituting the composition. Further, in order to remove foreign substances, each of the above components can be uniformly mixed, and then the obtained mixture can be filtered with a filter or the like.
　［パターンを有する樹脂膜およびその製造方法］
　本発明の、パターンを有する樹脂膜（パターン化樹脂膜）の製造方法は、本発明の組成物の塗膜を基板上に形成する工程（１）、前記塗膜を選択的に露光する工程（２）、および前記露光後の塗膜を現像する工程（３）を有する。本発明の組成物を用いることにより、イオンマイグレーションの発生が抑制され、薬品耐性およびクラック耐性が高く、解像度の高いパターン化樹脂膜を製造することができる。 [Resin film with pattern and its manufacturing method]
The method for producing a resin film having a pattern (patterned resin film) of the present invention is a step of forming a coating film of the composition of the present invention on a substrate (1) and a step of selectively exposing the coating film (a step of selectively exposing the coating film). It has 2) and a step (3) of developing the coating film after the exposure. By using the composition of the present invention, the occurrence of ion migration is suppressed, and a patterned resin film having high chemical resistance and crack resistance and high resolution can be produced.
　＜工程（１）＞
　工程（１）では、例えば、最終的に得られるパターン化樹脂膜の厚さが通常０．１～１００μｍとなるように、本発明の組成物を基板上に塗布する。前記組成物塗布後の基板をオーブンやホットプレートを用いて、通常、５０～１４０℃で１０～３６０秒間加熱する。このようにして基板上に本発明の組成物からなる塗膜を形成する。 <Process (1)>
In the step (1), for example, the composition of the present invention is applied onto the substrate so that the thickness of the finally obtained patterned resin film is usually 0.1 to 100 μm. The substrate after applying the composition is usually heated at 50 to 140 ° C. for 10 to 360 seconds using an oven or a hot plate. In this way, a coating film made of the composition of the present invention is formed on the substrate.
　基板としては、例えば、シリコンウエハ、化合物半導体ウエハ、金属薄膜付きウエハ、ガラス基板、石英基板、セラミックス基板、アルミ基板、およびこれらの基板の表面に電極、配線、半導体チップなどを有する基板が挙げられる。電極および配線は、例えば、銅、ニッケル、アルミニウム、および金などの金属からなる。 Examples of the substrate include silicon wafers, compound semiconductor wafers, wafers with metal thin films, glass substrates, quartz substrates, ceramic substrates, aluminum substrates, and substrates having electrodes, wirings, semiconductor chips, etc. on the surface of these substrates. .. The electrodes and wiring consist of metals such as copper, nickel, aluminum, and gold, for example.
　塗布方法としては、例えば、ディッピング法、スプレー法、バーコート法、ロールコート法、スピンコート法、カーテンコート法、グラビア印刷法、シルクスクリーン法、インクジェット法が挙げられる。 Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, and an inkjet method.
　＜工程（２）＞
　工程（２）では、例えばコンタクトアライナー、ステッパーまたはスキャナーを用いて、前記塗膜に対して選択的に露光を行う。「選択的に」とは、具体的には、所定のマスクパターンが形成されたフォトマスクを介して、という意味である。 <Process (2)>
In step (2), for example, a contact aligner, a stepper, or a scanner is used to selectively expose the coating film. "Selectively" specifically means through a photomask in which a predetermined mask pattern is formed.
　露光光としては、例えば、紫外線、可視光線が挙げられ、通常、ｉ線（３６５ｎｍ）などの波長２００～５００ｎｍの光を用いる。露光による照射量は、本発明の組成物中の各成分の種類、含有割合および塗膜の厚さなどによって異なるが、通常１００～１００００ｍＪ／ｃｍ2である。 Examples of the exposure light include ultraviolet rays and visible light, and usually, light having a wavelength of 200 to 500 nm such as i-line (365 nm) is used. The irradiation amount by exposure varies depending on the type and content ratio of each component in the composition of the present invention, the thickness of the coating film, and the like, but is usually 100 to 10000 mJ / cm 2 .
　また、架橋反応を充分に進行させるため、露光後に加熱処理（露光後ベーク）を行うことが好ましい。露光後の加熱処理の条件は、本発明の組成物中の各成分の種類、含有割合および塗膜の厚さなどによって異なるが、通常７０～２５０℃、好ましくは８０～２００℃で、通常１～６０分間である。 Further, in order to allow the cross-linking reaction to proceed sufficiently, it is preferable to perform heat treatment (baking after exposure) after exposure. The conditions for heat treatment after exposure vary depending on the type and content ratio of each component in the composition of the present invention, the thickness of the coating film, and the like, but are usually 70 to 250 ° C., preferably 80 to 200 ° C., and usually 1 ~ 60 minutes.
　＜工程（３）＞
　工程（３）では、例えば、アルカリ性現像液を用いて前記露光後の塗膜を現像して非露光部を溶解・除去することにより、基板上に所望のパターン化樹脂膜を形成する。 <Process (3)>
In the step (3), for example, a desired patterned resin film is formed on the substrate by developing the coating film after exposure with an alkaline developer to dissolve and remove the non-exposed portion.
　現像方法としては、例えば、シャワー現像法、スプレー現像法、浸漬現像法、パドル現像法が挙げられる。現像条件は、例えば、５～４０℃で１～１０分間である。
　アルカリ性現像液としては、例えば、水酸化ナトリウム、水酸化カリウム、アンモニア水、テトラメチルアンモニウムハイドロキサイド、コリン等のアルカリ性化合物を、１～１０質量％濃度となるように水に溶解させたアルカリ性水溶液が挙げられる。前記アルカリ性水溶液には、例えば、メタノール、エタノール等の水溶性の有機溶剤および界面活性剤などを適量添加することもできる。なお、アルカリ性現像液で前記露光後の塗膜を現像した後は、水で洗浄し、乾燥してもよい。 Examples of the developing method include a shower developing method, a spray developing method, a dipping developing method, and a paddle developing method. The developing conditions are, for example, 5 to 40 ° C. for 1 to 10 minutes.
The alkaline developer is, for example, an alkaline aqueous solution prepared by dissolving an alkaline compound such as sodium hydroxide, potassium hydroxide, aqueous ammonia, tetramethylammonium hydroxide, or choline in water so as to have a concentration of 1 to 10% by mass. Can be mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution. After developing the exposed coating film with an alkaline developer, it may be washed with water and dried.
　パターン化樹脂膜におけるパターンの形状としては、凹凸構造を有する形状であれば特に限定されないが、例えば、ライン・アンド・スペースパターン、ドットパターン、ホールパターン、格子パターンが挙げられる。 The shape of the pattern in the patterned resin film is not particularly limited as long as it has a concavo-convex structure, and examples thereof include a line and space pattern, a dot pattern, a hole pattern, and a lattice pattern.
　＜工程（４）＞
　本発明のパターン化樹脂膜の製造方法は、工程（３）後、絶縁膜としての特性を充分に発現させるため、必要に応じて、加熱処理（ポストベーク）により前記パターン化樹脂膜を充分に硬化させる工程（４）を有することができる。硬化条件は特に限定されないが、パターン化樹脂膜の用途に応じて、通常１００～２５０℃、好ましくは１５０～２５０℃で、通常３０分間～１０時間加熱する。 <Process (4)>
In the method for producing a patterned resin film of the present invention, after the step (3), the patterned resin film is sufficiently subjected to heat treatment (post-baking) as necessary in order to sufficiently exhibit the characteristics as an insulating film. It can have a step (4) of curing. The curing conditions are not particularly limited, but it is usually heated at 100 to 250 ° C., preferably 150 to 250 ° C. for 30 minutes to 10 hours depending on the use of the patterned resin film.
　本発明の製造方法で得られるパターン化樹脂膜は、半導体回路基板が有する絶縁膜として好適に用いることができる。前記絶縁膜は、例えば、表面保護膜、層間絶縁膜、平坦化膜である。 The patterned resin film obtained by the production method of the present invention can be suitably used as an insulating film contained in a semiconductor circuit board. The insulating film is, for example, a surface protective film, an interlayer insulating film, and a flattening film.
　［半導体回路基板］
　本発明の組成物を用いることにより、上述のパターンを有する樹脂膜（パターン化樹脂膜）を含む半導体回路基板を製造することができる。前記半導体回路基板は、上述した本発明の組成物から形成されたパターン化樹脂膜、好ましくは表面保護膜、層間絶縁膜および平坦化膜等のパターン化絶縁膜を有することから、高周波回路基板として有用である。
特に、本発明の半導体回路基板は、ＳｉＣやＧａＮなどのワイドギャップ半導体を用いた半導体回路基板として好適である。 [Semiconductor circuit board]
By using the composition of the present invention, a semiconductor circuit board including a resin film (patterned resin film) having the above-mentioned pattern can be manufactured. Since the semiconductor circuit board has a patterned resin film formed from the composition of the present invention described above, preferably a patterned insulating film such as a surface protective film, an interlayer insulating film and a flattening film, the semiconductor circuit board can be used as a high frequency circuit board. It is useful.
In particular, the semiconductor circuit board of the present invention is suitable as a semiconductor circuit board using a wide-gap semiconductor such as SiC or GaN.
　半導体回路基板における電極および／または配線は、例えば、銅、ニッケル、アルミニウム、および金などの金属からなる。これらの電極および／または配線間にある絶縁膜として本発明のパターン化樹脂膜を用いることにより、前述したイオンマイグレーションの発生を良好に抑制することができる。 Electrodes and / or wiring in semiconductor circuit boards are made of metals such as copper, nickel, aluminum, and gold, for example. By using the patterned resin film of the present invention as the insulating film between these electrodes and / or wiring, the occurrence of the above-mentioned ion migration can be satisfactorily suppressed.
　以下、本発明を実施例に基づいてさらに具体的に説明するが、本発明はこれら実施例に限定されない。以下の実施例等の記載において、特に言及しない限り、「部」は「質量部」の意味で用いる。 Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. In the following examples and the like, unless otherwise specified, "part" is used to mean "part by mass".
　＜物性の測定方法＞
　（樹脂の重量平均分子量（Ｍｗ）の測定方法）
　下記条件下でゲルパーミエーションクロマトグラフィー（ＧＰＣ）法にてフェノール性水酸基を有する樹脂の重量平均分子量（Ｍｗ）を測定した。
・カラム：東ソー社製カラムのＴＳＫ－ＭおよびＴＳＫ２５００を直列に接続
・溶媒：テトラヒドロフラン
・流速：０．３５ｍＬ／分
・温度：４０℃
・検出方法：屈折率法
・標準物質：ポリスチレン
・ＧＰＣ装置：東ソー製、装置名「ＨＬＣ－８２２０－ＧＰＣ」 <Measurement method of physical properties>
(Measuring method of weight average molecular weight (Mw) of resin)
Under the following conditions, the weight average molecular weight (Mw) of the resin having a phenolic hydroxyl group was measured by a gel permeation chromatography (GPC) method.
-Column: Tosoh columns TSK-M and TSK2500 are connected in series.-Solvent: Tetrahydrofuran-Flow velocity: 0.35 mL / min-Temperature: 40 ° C
-Detection method: Refractive index method-Standard substance: Polystyrene-GPC device: Tosoh, device name "HLC-8220-GPC"
　＜感光性樹脂組成物の製造＞
　［実施例１Ａ～実施例１８Ａ、比較例１Ａ～比較例３Ａ］
　下記表１に示す種類および量の各成分を均一に混合することにより、実施例１Ａ～実施例１８Ａ、および比較例１Ａ～比較例３Ａの感光性樹脂組成物を製造した。表１に示す各成分の詳細は以下のとおりである。なお、表１中の各成分の数値の単位は質量部である。 <Manufacturing of photosensitive resin composition>
[Example 1A to Example 18A, Comparative Example 1A to Comparative Example 3A]
The photosensitive resin compositions of Examples 1A to 18A and Comparative Examples 1A to 3A were produced by uniformly mixing each component of the type and amount shown in Table 1 below. Details of each component shown in Table 1 are as follows. The unit of the numerical value of each component in Table 1 is the mass part.
　Ａ－１：クレゾールノボラック樹脂（ｍ－クレゾール：ｐ－クレゾール＝６：４（モル比）、ポリスチレン換算重量平均分子量＝６，０００）
　Ａ－２：ヒドロキシスチレン／スチレン共重合体（ヒドロキシスチレン：スチレン＝８：２（モル比）、ポリスチレン換算重量平均分子量＝１０，０００）
　Ｂ－１：１，３，４，６－テトラキス（メトキシメチル）グリコールウリル
　Ｃ１－１：下記式（Ｃ１－１）に示す化合物
　Ｃ－１　：下記式（Ｃ－１）に示す化合物
　Ｃ１－２：下記式（Ｃ１－２）に示す化合物
　Ｃ１－３：下記式（Ｃ１－３）に示す化合物
　Ｃ１－４：下記式（Ｃ１－４）に示す化合物
　Ｃ１－５：下記式（Ｃ１－５）に示す化合物 A-1: Cresol novolak resin (m-cresol: p-cresol = 6: 4 (molar ratio), polystyrene-equivalent weight average molecular weight = 6,000)
A-2: Hydroxystyrene / styrene copolymer (hydroxystyrene: styrene = 8: 2 (molar ratio), polystyrene-equivalent weight average molecular weight = 10,000)
B-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluryl C1-1: Compound represented by the following formula (C1-1) C-1: Compound represented by the following formula (C-1) C1-2 : Compound represented by the following formula (C1-2) C1-3: Compound represented by the following formula (C1-3) C1-4: Compound represented by the following formula (C1-4) C1-5: The following formula (C1-5) Compound shown in
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　Ｄ－１：１，１－ビス（４－ヒドロキシ－２，５－ジメチルフェニル）プロパン－２－オン
　Ｅ－１：トリス（トリメトキシシリルプロピル）イソシアヌレート
　Ｅ－２：フッ素系界面活性剤（商品名「ＮＢＸ－１５」、ネオス（株）製）
　Ｆ－１：乳酸エチル
　Ｆ－２：２－ヘプタノン D-1: 1,1-bis (4-hydroxy-2,5-dimethylphenyl) propan-2-one E-1: tris (trimethoxysilylpropyl) isocyanurate E-2: fluorine-based surfactant (commodity) Name "NBX-15", manufactured by Neos Co., Ltd.)
F-1: Ethyl lactate F-2: 2-Heptanone
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　＜パターンを有する樹脂膜の製造＞
　［実施例１Ｂ］
　東京エレクトロン社製コーター・デベロッパー（製品名「ＭＡＲＫ－８」）にて、シリコンウエハ基板上に表２に示す実施例１Ａの感光性樹脂組成物をスピンコートし、次いで１１０℃で１８０秒間加熱し塗膜を形成した。前記塗膜を、ステッパー（ニコン社製、型式「ＮＳＲ－ｉ１０Ｄ」）を用い、パターンマスクを介して、波長３６５ｎｍで露光した。露光後の塗膜を、１２５℃で１８０秒間加熱し、次いで、２．３８質量％のテトラメチルアンモニウムハイドロオキサイド水溶液に１２０秒間浸漬して現像した。その後、流水洗浄し、窒素ブローして、シリコンウエハ基板上に実施例１Ｂのパターンを有する樹脂膜（ライン幅＝２０μｍ、スペース幅＝１０μｍ、樹脂膜の厚さ＝１０μｍ）を形成した。
　パターンを有する樹脂膜を電子顕微鏡で観察し、パターンを有する樹脂膜のスペース幅が１０μｍとなる露光量を感度として評価した。評価結果を表２に示す。 <Manufacturing of resin film with pattern>
[Example 1B]
The photosensitive resin composition of Example 1A shown in Table 2 was spin-coated on a silicon wafer substrate by a coater developer (product name "MARK-8") manufactured by Tokyo Electron Limited, and then heated at 110 ° C. for 180 seconds. A coating film was formed. The coating film was exposed to a wavelength of 365 nm using a stepper (manufactured by Nikon Corporation, model “NSR-i10D”) via a pattern mask. The exposed coating film was heated at 125 ° C. for 180 seconds and then immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 120 seconds for development. Then, it was washed with running water and blown with nitrogen to form a resin film having the pattern of Example 1B (line width = 20 μm, space width = 10 μm, resin film thickness = 10 μm) on a silicon wafer substrate.
The resin film having the pattern was observed with an electron microscope, and the exposure amount at which the space width of the resin film having the pattern was 10 μm was evaluated as the sensitivity. The evaluation results are shown in Table 2.
　［実施例２Ｂ～実施例１８Ｂ、および比較例１Ｂ～比較例３Ｂ］
　実施例１Ｂにおいて、表２に示す感光性樹脂組成物を用いた以外は実施例１Ｂと同様にパターンを有する樹脂膜を製造し、感度を評価した。評価結果を表２に示す。 [Example 2B to Example 18B, and Comparative Example 1B to Comparative Example 3B]
In Example 1B, a resin film having a pattern was produced in the same manner as in Example 1B except that the photosensitive resin composition shown in Table 2 was used, and the sensitivity was evaluated. The evaluation results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　＜イオンマイグレーション耐性の評価＞
　［実験例１Ａ］
　図１に示すように、シリコンウエハをカットして作成した基板１上に銅からなる櫛形電極２（電極の厚さ＝６μｍ、電極の幅＝２０μｍ、電極間の距離＝２０μｍ）を有する基材３に、実施例１Ａの感放射線性組成物をスピンコートし、次いで１１０℃で１８０秒間加熱し、櫛形電極２上での厚さが１０μｍになるよう塗膜形成した。前記塗膜を、ステッパー（ニコン社製、型式「ＮＳＲ－ｉ１０Ｄ」）で実施例１Ｂでの表２の「感度」で示した露光量で全面露光し、露光後の塗膜を１２５℃で１８０秒間加熱し、２．３８質量％のテトラメチルアンモニウムハイドロオキサイド水溶液に１２０秒間浸漬し、次いで、２００℃で１時間加熱し、イオンマイグレーション耐性評価用基板を作成した。 <Evaluation of ion migration resistance>
[Experimental Example 1A]
As shown in FIG. 1, a base material having a comb-shaped electrode 2 made of copper (electrode thickness = 6 μm, electrode width = 20 μm, distance between electrodes = 20 μm) on a substrate 1 made by cutting a silicon wafer. In No. 3, the radiation-sensitive composition of Example 1A was spin-coated, and then heated at 110 ° C. for 180 seconds to form a coating film so that the thickness on the comb-shaped electrode 2 was 10 μm. The coating film is entirely exposed with a stepper (manufactured by Nikon Corporation, model "NSR-i10D") at the exposure amount shown in "Sensitivity" of Table 2 in Example 1B, and the coating film after exposure is 180 at 125 ° C. It was heated for 1 second, immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 120 seconds, and then heated at 200 ° C. for 1 hour to prepare a substrate for ion migration resistance evaluation.
　前記イオンマイグレーション耐性評価用基板をタバイエスペック社製型式「ＡＥＩ，ＥＨＳ－２２１ＭＤ」で、温度１３０℃、湿度８５％、印加電圧１５Ｖの条件にて、高速加速寿命試験（ＨＡＳＴ試験）を行い、抵抗値が１０11Ω以下となる時間をイオンマイグレーションの発生時間としてイオンマイグレーション耐性を評価した。評価結果を表３に示す。 The substrate for ion migration resistance evaluation was subjected to a high-speed accelerated life test (HAST test) under the conditions of a temperature of 130 ° C., a humidity of 85%, and an applied voltage of 15 V with a model "AEI, EHS-221MD" manufactured by Tabei Espec Co., Ltd. Ion migration resistance was evaluated with the time when the value was 10 11 Ω or less as the occurrence time of ion migration. The evaluation results are shown in Table 3.
　［実験例２Ａ～１８Ａ、比較実験例１Ａ～３Ａ］
　実験例１Ａにおいて、表３に示す感光性樹脂組成物を用いた以外は実験例１Ａと同様にイオンマイグレーション耐性評価用基板を作成し、イオンマイグレーション耐性を評価した。評価結果を表３に示す。図２は、実験例２Ａのイオンマイグレーション耐性評価後の基板の光学顕微鏡の写真を示す。図３は、比較実験例２Ａのイオンマイグレーション耐性評価後の基板の光学顕微鏡の写真を示す。 [Experimental Examples 2A to 18A, Comparative Experimental Examples 1A to 3A]
In Experimental Example 1A, a substrate for evaluating ion migration resistance was prepared in the same manner as in Experimental Example 1A except that the photosensitive resin composition shown in Table 3 was used, and the ion migration resistance was evaluated. The evaluation results are shown in Table 3. FIG. 2 shows a photograph of an optical microscope of the substrate after the ion migration resistance evaluation of Experimental Example 2A. FIG. 3 shows a photograph of an optical microscope of the substrate after the ion migration resistance evaluation of Comparative Experimental Example 2A.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
１：基板
２：櫛形電極
３：基材 1: Substrate 2: Comb electrode 3: Substrate

Claims (8)

  1. 　フェノール性水酸基を有する樹脂（Ａ）、架橋剤（Ｂ）、および下記式（Ｃ１）に示す光カチオン発生剤（Ｃ１）を含有する感光性樹脂組成物であり、
    　前記感光性樹脂組成物の固形分中に含まれる前記光カチオン発生剤（Ｃ１）の含有割合が、０．０１～０．９質量％である、
    感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     ［式（Ｃ１）中、Ｒ1は非置換または置換の炭化水素基を示し、Ｒ2～Ｒ7はそれぞれ独立に水素原子、または非置換もしくは置換のアルキル基を示し、Ｒ2～Ｒ7のうち少なくとも一つは非置換または置換のアルキル基を示す。］     A photosensitive resin composition containing a resin (A) having a phenolic hydroxyl group, a cross-linking agent (B), and a photocation generator (C1) represented by the following formula (C1).
    The content ratio of the photocation generator (C1) contained in the solid content of the photosensitive resin composition is 0.01 to 0.9% by mass.
    Photosensitive resin composition.
    Figure JPOXMLDOC01-appb-C000001
     [In formula (C1), R 1 represents an unsubstituted or substituted hydrocarbon group, R 2 to R 7 each independently represent a hydrogen atom or an unsubstituted or substituted alkyl group, and R 2 to R 7 At least one of them represents an unsubstituted or substituted alkyl group. ]
  2. 　前記架橋剤（Ｂ）１００質量部に対する前記光カチオン発生剤（Ｃ１）の含有量が、１～１５質量部である、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the content of the photocation generator (C1) with respect to 100 parts by mass of the cross-linking agent (B) is 1 to 15 parts by mass.
  3. 　前記架橋剤（Ｂ）が、－ＲB1－Ｏ－ＲB2で表される基を少なくとも２個有する架橋剤（ｂ１）（式中、ＲB1はアルカンジイル基であり、ＲB2は水素原子またはアルキル基である）である、請求項１または２に記載の感光性樹脂組成物。 Wherein the crosslinking agent is (B), -R B1 -O- R B2 a group having at least two crosslinking agents represented (b1) (wherein, R B1 is an alkane diyl group, R B2 is a hydrogen atom or The photosensitive resin composition according to claim 1 or 2, which is an alkyl group).
  4. 　前記感光性樹脂組成物が光カチオン発生剤（Ｃ）を含有し、全光カチオン発生剤（Ｃ）中に含まれる前記光カチオン発生剤（Ｃ１）の含有割合が９０質量％以上である、請求項１～３のいずれか１項に記載の感光性樹脂組成物。 Claimed that the photosensitive resin composition contains a photocation generator (C) and the content ratio of the photocation generator (C1) contained in the total photocation generator (C) is 90% by mass or more. Item 2. The photosensitive resin composition according to any one of Items 1 to 3.
  5. 　さらに、低分子フェノール化合物（Ｄ）を含有する、請求項１～４のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 4, further containing a low molecular weight phenol compound (D).
  6. 　請求項１～５のいずれか１項に記載の感光性樹脂組成物の塗膜を基板上に形成する工程（１）、前記塗膜を選択的に露光する工程（２）、および前記露光後の塗膜を現像する工程（３）を有する、パターンを有する樹脂膜の製造方法。 A step of forming a coating film of the photosensitive resin composition according to any one of claims 1 to 5 on a substrate (1), a step of selectively exposing the coating film (2), and after the exposure. A method for producing a resin film having a pattern, which comprises the step (3) of developing the coating film of.
  7. 　請求項６に記載の製造方法により形成された、パターンを有する樹脂膜。 A resin film having a pattern formed by the production method according to claim 6.
  8. 　請求項７に記載のパターンを有する樹脂膜を含む半導体回路基板。 A semiconductor circuit board including a resin film having the pattern according to claim 7.
PCT/JP2020/022677 2019-06-25 2020-06-09 Photosensitive resin composition, patterned resin film and method for manufacturing same, and semiconductor circuit board WO2020261979A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015001804A1 (en) * 2013-07-05 2015-01-08 サンアプロ株式会社 Photoacid generator, and resin composition for photolithography
JP2018091939A (en) * 2016-11-30 2018-06-14 株式会社Adeka Negative photosensitive composition, cured product thereof and method for curing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015001804A1 (en) * 2013-07-05 2015-01-08 サンアプロ株式会社 Photoacid generator, and resin composition for photolithography
JP2018091939A (en) * 2016-11-30 2018-06-14 株式会社Adeka Negative photosensitive composition, cured product thereof and method for curing the same

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