WO2007091560A1 - Photosensitive resin composition and photoresist film using the same - Google Patents

Photosensitive resin composition and photoresist film using the same Download PDF

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Publication number
WO2007091560A1
WO2007091560A1 PCT/JP2007/052029 JP2007052029W WO2007091560A1 WO 2007091560 A1 WO2007091560 A1 WO 2007091560A1 JP 2007052029 W JP2007052029 W JP 2007052029W WO 2007091560 A1 WO2007091560 A1 WO 2007091560A1
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WO
WIPO (PCT)
Prior art keywords
photosensitive resin
resin composition
group
weight
meth
Prior art date
Application number
PCT/JP2007/052029
Other languages
French (fr)
Japanese (ja)
Inventor
Shigeru Murakami
Yasuhiro Hamada
Takatoshi Yamamoto
Atsuyoshi Hinata
Original Assignee
Nichigo-Morton Co., Ltd.
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Application filed by Nichigo-Morton Co., Ltd. filed Critical Nichigo-Morton Co., Ltd.
Publication of WO2007091560A1 publication Critical patent/WO2007091560A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
    • H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask

Definitions

  • the present invention relates to a photosensitive resin composition for a photoresist film used for manufacturing a printed wiring board, lead frame processing, a semiconductor package, a display and the like, and a photoresist film using the same.
  • the present invention relates to a photosensitive resin composition excellent in sensitivity, resolving power, adhesion stability, and resist peelability, and a photoresist film using the same.
  • a photoresist method using a photosensitive resin composition is used for manufacturing printed circuit board circuit formation, semiconductor package circuit formation, lead frame processing, and the like.
  • this photoresist method for example, First, a photosensitive resin composition is applied onto a support such as a transparent film to form a photosensitive resin composition layer, and then the photosensitive resin composition layer is formed to form a desired pattern. Then, the photosensitive resin composition layer is exposed to light through a pattern mask, and the unexposed portion is removed by a development process using a solvent or an alkaline aqueous solution.
  • a method of manufacturing a printed circuit board by performing resist etching and performing a known etching process or pattern plating process is generally performed.
  • the semi-additive method is often used in the circuit formation of semiconductor packages.
  • a resist pattern is formed by a known method as described above, and a conductor contact is formed between the formed resist patterns. After application, the hardened resist is peeled off and then a conductor circuit is formed by flash etching.
  • the photosensitive resin composition for improving resist stripping include photopolymerization, which includes, for example, a thermoplastic polymer, an addition polymerizable compound that is liquid or solid at normal temperature and pressure, and a photopolymerization initiator.
  • thermoplastic polymer polymerizable monomer 15 to 40 weight 0/0 having a carboxyl group, styrene monomer 1-35 weight 0/0, acrylic acid ester ⁇ beauty methacrylic acid ester 84 to A photopolymerizable composition composed of 25% by weight (for example, see Patent Document 1) and a binder polymer having a specific unsaturated compound and an OC, ⁇ unsaturated carboxyl group-containing monomer as essential copolymerization components
  • a photosensitive resin composition mainly composed of a photopolymerizable monomer having two or more ethylenically unsaturated groups in one molecule and a photopolymerization initiator (see, for example, Patent Document 2).
  • a photosensitive resin composition mainly composed of a photopolymerizable monomer having two or more ethylenically unsaturated groups in one molecule and a photopolymerization initiator
  • Patent Document 1 Japanese Patent Laid-Open No. 2-161442
  • Patent Document 2 JP-A-9-325487
  • Patent Document 1 has a problem that the adhesion is not stable and the yield decreases during mass production, and the disclosed technique of Patent Document 2 requires further improvement in terms of resolution. It was.
  • the present invention provides a photosensitive resin composition that is excellent in resolving power, adhesion stability, and resist releasability, and a photoresist film using the same, in such a background. It is intended.
  • a photosensitive resin composition comprising a carboxyl group-containing monomer more than a conventional carboxyl group-containing polymer ( ⁇ ), and other phenol group-containing bulle monomers and the following formula (1) Copolymerized with a long-chain acrylate compound represented by As a result, it has been found that the photosensitive resin composition is excellent in resolving power, adhesion stability, and resist releasability.
  • the gist of the present invention is shown below.
  • the photosensitive resin is characterized in that the content of all methacrylic acid (al) is 22 to 35% by weight and the content of the vinyl group-containing vinyl monomer (a2) is 20 to 35% by weight. Fat composition.
  • R 1 is hydrogen or a methyl group
  • R 2 is an ethylene group or a propylene group
  • R 3 is an alkyl group having 8 to 22 carbon atoms
  • n is an integer of 1 to 4.
  • V deviation is characterized in that the carboxyl group-containing polymer (A) has a weight average molecular weight of 30,000 to 100,000 and a polymer acid value of 175 to 250 mgKOHZg Or a photosensitive resin composition.
  • R 1 is a hydrogen atom or a methyl group
  • R 4 is a propylene group or a butylene group
  • 1 km is an integer
  • the average value of k + m is 2 6 1 and the average value is 10 25.
  • a photoresist film comprising a layer of the photosensitive resin composition according to any one of (1) to (6) above and a support film having a haze value of 1.5 or less.
  • the photosensitive resin composition of the present invention and a photoresist film using the same contain a carboxyl group-containing polymer (A), an ethylenically unsaturated compound (B), and a photopolymerization initiator (C).
  • a photosensitive resin composition comprising a carboxyl group-containing polymer (A), a metataric acid (al), a phenyl group-containing vinyl monomer (a2), and a compound represented by the following formula (1) ( a3), and a copolymer that contains other copolymerizable monomer (a4) as a copolymerization component as necessary, so that it has excellent resolution and adhesion stability, as well as excellent resist releasability.
  • it is useful in the semi-additive construction method.
  • Examples of the carboxyl group-containing polymer (A) used in the present invention include methacrylic acid (al), a phenyl group-containing vinyl monomer (a2), and a compound (a3) represented by the above formula (1). It is necessary that the copolymer contains other copolymerizable monomer (a4) as a copolymer component, and the content ratio of each copolymer component is based on the weight of all copolymer components.
  • the content of methacrylic acid (al) is 22 to 35% by weight, preferably 25 to 32% by weight, more preferably 27 to 30% by weight, and the content of the phenyl group-containing bur monomer (a2) is 20%.
  • the content of the compound (a3) represented by the above formula (1) is not particularly limited, but 3 to 20 wt% More preferred is 5 to 15% by weight, and particularly preferred is 5 to 10% by weight.
  • the content of the other copolymerizable monomer (a4) contained if necessary is not particularly limited, but is preferably 10 to 55% by weight, more preferably 10 to 47% by weight, and particularly preferably 20 to 42% by weight. Is a range
  • Examples of the vinyl group-containing vinyl monomer (a2) include styrene, methylstyrene, vinyl benzyl, vinyl biphenyl, and benzoic acid butyl. Among them, styrene is preferable. Used.
  • R 1 is a monovalent organic group selected from hydrogen or a methyl group.
  • R 2 is a divalent alkylene group selected from an ethylene group or a propylene group, and when R 2 is an ethylene group, n is preferably an integer of 1 to 3, and R 3 has 8 to 8 carbon atoms. It is preferably an alkyl group having 22 to 16 carbon atoms.
  • n is preferably an integer of 2 to 4
  • R 3 is preferably an alkyl group having 8 to 12 carbon atoms! /.
  • the compound (a3) represented by the above formula (1) is not particularly limited. , 2-ethylhexyl carbitol metatalylate, alkyl carbitol (meth) acrylate, such as lauryl carbitol (meth) acrylate, lauryl oxytetraethylene glycol (meth) acrylate, stear oxytetraethylene glycol ( Meta) Atallate etc.
  • alkyl carbitol (meth) acrylate such as lauryl carbitol (meth) acrylate, lauryl oxytetraethylene glycol (meth) acrylate, stear oxytetraethylene glycol ( Meta) Atallate etc.
  • 2-ethylhexyl carbitol (meth) acrylate is preferred from the viewpoint of resist adhesion, and 2-ethyl hexyl carbitol acrylate is more preferred.
  • the other copolymerizable monomer (a4) is not particularly limited as long as it is a copolymerizable monomer other than the above (al) to (a3), and examples thereof include methyl (meth) acrylate and ethyl.
  • Aliphatics such as (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, lauryl (meth) acrylate Alkyl (meth) acrylates, alicyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, aromatic substituted alkyl (meth) acrylates such as benzyl (meth) acrylate, Amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate, jetylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, Hydroxyl-containing (meth) acrylates such as hydroxypropyl (meth) acrylate and glycidyl (meth) acrylate, monocarboxylic
  • 175 ⁇ 250mgKOHZg force s preferred instrument More preferably 180 ⁇ 230MgKOHZg, particularly preferably 195 ⁇ 220mgKO HZg. If the acid value is less than the lower limit, the developability is lowered, resulting in a decrease in resolving power, and the resist peelability after tacking tends to be insufficient. If the acid value exceeds the upper limit, the cured resist Of the developer tends to be reduced, and the fine wire adhesion tends to be reduced.
  • the weight average molecular weight of the carboxyl group-containing polymer (A) is preferably 30,000 to 100,000,000, more preferably 40,000-60,000, and the weight average molecular weight S is the lower limit. If it is less than 1, the resist adhesion is unstable and defects such as chipping of the resist also increase, and if the upper limit is exceeded, the resolution tends to decrease.
  • the blending ratio of the carboxyl group-containing polymer ( ⁇ ) is particularly preferably 10 to 95 parts by weight with respect to the total weight of the carboxyl group-containing polymer ( ⁇ ) and the ethylenically unsaturated compound ( ⁇ ). 20 to 80 parts by weight, more preferably 40 to 60 parts by weight. Carbo If the amount of the xyl group-containing polymer (A) is too small, film formation tends to be difficult, and if the amount of the carboxyl group-containing polymer (A) is too large, the resolution and fine line adhesion tend to be lowered.
  • the ethylenically unsaturated compound (B) used in the present invention is not particularly limited as long as it has two or more polymerizable unsaturated groups.
  • the bifunctional monomer may be ethylene glycol di (meta).
  • Atalylate Diethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, Alkylene oxide di (meth) acrylates such as butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A Type di (meta) Alkylene oxide-modified di (meth) acrylates, such as talylate, propylene oxide-modified bisphenol A-type di (meth) acrylate, ethylene oxide 'propion oxide-modified bisphenol A-type di (meth) acrylate, 1, 6 —Hexanediol di (meth) atarylate, 1,10-decane
  • Examples of other bifunctional monomers such as xoxybivalic acid-modified neopentyldalycol di (meth) atalylate include trimethylolpropane tri (meth) atalylate and pentaerythritol. Examples include tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) tertyloxyethoxytrimethylol propane, dariserine polyglycidyl ether poly (meth) acrylate, and the like. Furthermore, it is possible to use any urethane (meta) ata relay toy compound.
  • Two or more types of these bifunctional or more functional monomers can be used, and an appropriate amount of the following monofunctional monomers can be used in combination.
  • Examples of the monofunctional monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polyethylene glycol Recall (meth) acrylate, polypropylene glycol (meth) acrylate, 2-phenoxy —2-hydroxypropyl (meth) acrylate, 2- (meth) tert-yloxy 2-hydroxypropyl phthalate, 3 — black mouth 1-Hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) tarolooxychetyl acid phosphate, half (meth) acrylate of phthalic acid derivatives, poly strength prolatathone mono Examples include (meth) acrylate, N-methylol (meth) acrylamide, and jetylaminoethyl (meth) acrylate.
  • the compound (bl) represented by the following formula (2) is contained as the ethylenically unsaturated compound (B).
  • R 1 is a hydrogen atom or a methyl group
  • R 4 is a propylene group or a butylene group
  • 1, k, m are integers
  • the average value of k + m is 2 to 6
  • the average value of 1 is 10 to 25.
  • k + m is preferably 2 to 6 as an average value, and if it is less than the lower limit, the photocurability is insufficient and the resolution tends to decrease. Resolving power tends to decrease due to a decrease in resistance to the developer and the plating solution.
  • the average value of 1 is preferably 10 to 25, and if it is less than the lower limit, the effect of adhesion stability tends to be insufficient, and if it exceeds the upper limit, the resolution tends to decrease.
  • Specific examples of the compound (bl) represented by the formula (2) are “Blemmer 30 PDC-600B”, “Blemmer 30PDC-800BJ” and the like manufactured by NOF Corporation.
  • the blending ratio of the ethylenically unsaturated compound (B) is preferably 5 to 90 parts by weight with respect to the total weight of the carboxyl group-containing polymer (A) and the ethylenically unsaturated compound (B). Particularly preferred is 20 to 80 parts by weight, still more preferred is 40 to 60 parts by weight.
  • Ethylenic Too little unsaturated compound (B) leads to poor curing, poor flexibility, and slow development speed, too much ethylenically unsaturated compound (B) increases tackiness, cold flow, and removal rate of cured resist. There is a tendency to lead to a decline.
  • the compounding ratio of the compound (bl) represented by the above formula (2) is 5 to 80% with respect to the total ethylenically unsaturated compounds (B). %, More preferably 10 to 70% by weight, especially 20 to 60% by weight.
  • the compounding ratio of the compound (bl) is less than the lower limit, the adhesion of the resist tends to be unstable, and when it exceeds the upper limit, the resist peelability tends to decrease and cold flow tends to occur.
  • the photopolymerization initiator (C) used in the present invention is not particularly limited, and a known photopolymerization initiator can be used.
  • a known photopolymerization initiator can be used.
  • At least an oral fin dimer is contained as the photopolymerization initiator (C) in view of improving resolution, and a dialkylaminobenzophenone is used in combination. Is preferred in terms of obtaining good sensitivity.
  • the content of the powerful fin fin dimer is 2 to 6 parts by weight based on a total of 100 parts by weight of the carboxyl group-containing polymer (A) and the ethylenically unsaturated compound (B), and 3 ⁇ 5 parts by weight, particularly 3.5 to 4.5 parts by weight is preferred. If the mouth fin dimer is less than the lower limit, the resolution is insufficient, and if the upper limit is exceeded, the resist becomes brittle and sludge tends to be generated in the developer.
  • the content of the powerful dialkylaminobenzophenone is 0.05 to 1 part by weight based on 100 parts by weight of the total of the carboxyl group-containing polymer (A) and the ethylenically unsaturated compound (B), and Is preferably 0.1 to 0.5 parts by weight, particularly preferably 0.12 to 0.2 parts by weight. If the dialkylaminobenzophenone is less than the lower limit, sufficient sensitivity and resolving power cannot be obtained, and if it exceeds the upper limit, the adhesion tends to decrease.
  • the content of the photopolymerization initiator (C) includes the carboxyl group-containing polymer (A) and It is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, particularly preferably 1 to 6 parts by weight, based on 100 parts by weight of the total amount of the ethylenically unsaturated compound (B). It is. If the content is less than the lower limit, the sensitivity tends to be significantly reduced and good workability tends not to be obtained. Conversely, if the content exceeds the upper limit, the storage stability of the photoresist film tends to decrease. is there.
  • the specific carboxyl group-containing polymer (A) and the ethylenically unsaturated compound) (preferably including at least the compound (bl) represented by the above formula (2)), photopolymerization.
  • a photosensitive resin composition containing the initiator (C) can be obtained, but as necessary, other components such as thermal polymerization inhibitors, plasticizers, dyes (pigments, discoloring agents), antioxidants, solvents.
  • components such as a surface tension modifier, a stabilizer, a chain transfer agent, an antifoaming agent, a flame retardant, and a copolymer having an ethylenically unsaturated bond can be appropriately added.
  • a thermal polymerization inhibitor is added to prevent thermal polymerization or temporal polymerization of the photosensitive resin composition, and includes p-methoxyphenol, hydroquinone, t-butylcatechol. , Pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, 4-methoxy1-2hydroxybenzophenone, thiourea, phenothiazine, chloranil, naphthylamine, 13 naphthol, 2,6 di-tert-butylcresole, ditro Examples include benzene, picric acid, and p-toluidine.
  • Plasticizers are added to control film physical properties.
  • phthalate esters such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diallyl phthalate; triethylene glycol diacetate, Glycol esters such as tetraethylene glycol diacetate; Phosphate esters such as tricresyl phosphate and triphenyl phosphate; Amides such as p-toluenesulfonamide and N n-butylacetamide; Diisobutyl adipate and dio Aliphatic dibasic acid esters such as octyl adipate, dimethyl sebacate, dioctyl azelate, dibutyl malate; triethyl taenoate, tributyl tamate, glycerin triacetyl ester, butyl laurate, 4,5-diepoxy cyclohexane
  • Examples of the pigment include brilliant green, eosin, ethyl violet, and Ellis mouth.
  • Thin B methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3 diphenyltriazine, alizarin red S, thymolphthalein, methyl violet 2B, quinanoresin red, rose benganole, methanole yellow, chi Monores Norehof Tarain, Xylenol Blue, Methyl Orange, Orange 4, Diphenylthiocarbazone, 2, 7 Diclonal Fluorescein, Paramethyl Red, Congo Red, Benzopurpurin 4B, a Naphthyl Red, Nile Blue A, Phenacetalin, Methyl violet, malachite green, parafuchsin, oil blue # 613 [manufactured by Orient Chemical Industry Co., Ltd.], Vitaria Pure Blue BOH, spiron blue GN [manufactured by Hodogaya I
  • the color changing agent is added to the photosensitive resin composition so that a visible image can be formed by exposure.
  • Specific examples include leuco crystal violet, leucomalachite green and the like in addition to the dye. It is done.
  • the photosensitive resin composition obtained in the present invention is usually used as a photoresist film having a laminated structure.
  • the photoresist film is formed by laminating a photosensitive resin composition on a support film and, if necessary, further laminating a protective film on the photosensitive resin composition layer side. .
  • the support film used in the present invention has heat resistance and solvent resistance when forming the photosensitive resin composition layer.
  • Specific examples of the support film include, for example, Usually, a polyester film, a polyolefin film, a polybutyl alcohol film, a polystyrene film, a polyimide film, a polylactic acid film, and the like can be mentioned.
  • the present invention is not limited to only powerful examples. It should be noted that the thickness of the support film varies depending on the material of the film, and thus cannot be determined unconditionally, and is usually a force that is appropriately adjusted according to the mechanical strength of the film. m.
  • the haze value of the support film is preferably 1.5% or less, and more preferably in the range of 0.1 to 1.0%.
  • the photosensitive resin composition layer has a thickness of 3 to 300 ⁇ m, preferably 5 to 50 ⁇ m. If it is less than 3 / zm, the coating becomes non-uniform or pinholes are likely to occur during coating and drying, and if it is more than 300 m, the exposure sensitivity decreases and the development speed is reduced. Is slow and is not preferable.
  • the protective film used in the present invention when a photoresist film is used in the form of a roll, is transferred to a support film or a photosensitive resin composition layer having adhesive properties. In order to prevent dust and the like from adhering to the physical layer, it is used by being stacked on the photosensitive resin composition layer.
  • strong protective films include polyester film, polyvinyl alcohol film, polyethylene film, polypropylene film, polylactic acid film, and Teflon (registered trademark) film.
  • the present invention is limited only to powerful examples. It is not something.
  • the thickness of the protective film is not particularly limited and is usually 10 to 50 ⁇ m, and the thickness may be 10 to 30 ⁇ m.
  • the photosensitive resin composition described above is used as a solution, and this is applied to a support film such as a polyester film, polyvinyl alcohol film, polypropylene film, polystyrene film, etc., dried with hot air, and then as necessary.
  • a support film such as a polyester film, polyvinyl alcohol film, polypropylene film, polystyrene film, etc.
  • the coating surface is also coated with a protective film such as a polyethylene film or polybulal alcohol film to form a photoresist film.
  • the photosensitive resin composition of the present invention is directly applied on a (copper) substrate to be processed by a conventional method such as a date coating method, a flow coating method, or a screen printing method.
  • a photosensitive layer having a thickness of 1 to 150 m can be easily formed.
  • solvents can also be added.
  • a support film and a photosensitive resin Compare the adhesive strength with the composition layer and the adhesive strength between the protective film and the photosensitive resin composition layer. After peeling off the film with the lower adhesive strength, the photosensitive resin composition layer side is copper-clad. After being attached to a metal surface such as a copper surface of the substrate, the pattern mask is brought into close contact with the other film and exposed. When the photosensitive resin composition does not have adhesiveness, the pattern mask can be directly brought into contact with the photosensitive resin composition layer after the other film is peeled off for exposure. If the coating is applied directly to the metal surface, the pattern mask is brought into contact with the coated surface directly or via a polyester film, etc., and then subjected to exposure.
  • the exposure is usually performed by ultraviolet irradiation, and as a light source at that time, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a short arc lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, a YAG laser, an Ar laser, A semiconductor laser or the like is used. After UV irradiation, heating can be performed as necessary to complete the curing.
  • the film on the resist is peeled and removed to perform development.
  • the photosensitive resin composition of the present invention is of a dilute alkali development type, development after exposure is performed using a dilute aqueous solution of about 0.3 to 2% by weight of alkali such as sodium carbonate or potassium carbonate.
  • alkali such as sodium carbonate or potassium carbonate.
  • a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.
  • Etching is usually performed according to a conventional method using an acidic etching solution such as an aqueous solution of cupric chloride monohydrochloride or an aqueous solution of ferric chloride monohydrochloride. In rare cases, an ammonia-based Al-reetching solution is also used.
  • pretreatment is performed using a pretreatment such as a degreasing agent and a soft etching agent, and then plating is performed using a plating solution.
  • plating solutions copper plating solution, nickel plating solution, iron plating solution, silver plating solution, gold plating solution, tin plating solution, cobalt plating solution, zinc plating solution, nickel cobalt plating solution, solder plating
  • a dipping solution In particular, a copper plating solution is used in the semi-additive method.
  • the remaining cured resist is peeled off.
  • the cured resist is peeled and removed with about 0.5 to 5% by weight of sodium hydroxide, potassium hydroxide, etc. It is carried out using an alkaline stripping solution that also has a strength of alkaline aqueous solution.
  • the circuit pattern is formed by removing the cured resist after the plating step and performing flash etching with an acidic etching solution.
  • the photosensitive resin composition of the present invention and a photoresist film using the composition are an etching resist or a film used for the production of printed wiring boards, precision metal processing, lead film production, semiconductor packages, and the like. It is a photosensitive resin composition containing a carboxyl group-containing polymer (A), an ethylenically unsaturated compound (B), and a photopolymerization initiator (C).
  • A carboxyl group-containing polymer
  • B ethylenically unsaturated compound
  • C photopolymerization initiator
  • Methyl metatalylate ⁇ Styrene ⁇ 2-Ethylhexyl carbitol acrylate (Toago Seikagaku Kogyo Co., Ltd., “Aguchi-tas ⁇ —120”)
  • Methyl metatalylate ⁇ Styrene ⁇ 2-Ethylhexyl carbitol acrylate manufactured by Toagosei Kagaku Kogyo Co., Ltd., “Aguchi-tas 120—120”
  • the numerical value in () in the table is the blending amount (part) as solid content.
  • the photosensitive resin composition layer was laminated on a copper clad substrate preheated to 60 ° C. in an oven at a laminating roll temperature of 100. C, same mouth Lamination was performed at a roll pressure of 0.3 MPa and a laminating speed of 1.2 mZmin. After that, a hold time of 15 minutes was taken.
  • the copper-clad substrate used here is 1.6 mm thick and is a 200 mm x 125 mm substrate with 35 ⁇ m copper foil laminated on both sides of a glass fiber epoxy base. The surface is flattened through.
  • the substrate was vacuum-contacted with a 5 kW mercury short arc lamp (parallel light source) and exposed at an exposure amount of 90 mjZcm 2 .
  • the polyester film is peeled off, and a 1% sodium carbonate aqueous solution at 30 ° C is developed at 0.15 MPa, twice the breakpoint (time when the unexposed area is completely dissolved).
  • a 1% sodium carbonate aqueous solution at 30 ° C is developed at 0.15 MPa, twice the breakpoint (time when the unexposed area is completely dissolved).
  • the line width force of the parallel line pattern in which the width of the exposed portion Z unexposed portion is 1Z1 is 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, A negative image of 18 and 20 m, and a ring width with an inner diameter of ⁇ 50 / ⁇ ⁇ 5, 6, 7, 8, 9, 10, 12.5, 15, 17.5, 20 / zm
  • This is a synthetic quartz chrome mask having a negative image.
  • Pattern copper plating was performed on the substrate after the development process.
  • LAC-41 Rohm and Haas Electronic Materials 20% aqueous solution, treated at 40 ° C for 5 minutes, and then plated with copper sulfate in a bath of copper sulfate 1. 45 AZdm 2 Partial pattern plating was performed to form a 22 m thick copper plating pattern.
  • the substrate after the plating process was sprayed for 120 seconds at 50 ° C and 0.2 MPa using a 2% aqueous solution of caustic soda to remove the resist and form a plating pattern.
  • the substrate after the resist was peeled off was observed with a metallographic microscope, and the presence or absence of a resist peeling residue in the parallel line pattern portion where the exposed portion Z unexposed portion was 18 ⁇ m 18 ⁇ m was confirmed.
  • the evaluation criteria are as follows.
  • Table 3 shows the evaluation results of Examples and Comparative Examples. Struggle
  • the photosensitive resin composition of the present invention and a photoresist film using the composition are used as an etching resist or adhesive resist used in the production of printed wiring boards, precision metal processing, lead film production, semiconductor packages, and the like.
  • a photosensitive resin composition containing a carboxyl group-containing polymer (A), an ethylenically unsaturated compound (B), and a photopolymerization initiator (C), comprising a carboxyl group-containing polymer ( A) is methacrylic acid ( al ), A phenyl group-containing vinyl monomer (a2), and a compound (a3) represented by the above formula (1) at a specific ratio as a copolymerization component, the resolution, adhesion stability, It exhibits an excellent effect on resist peelability, and is particularly useful as a photoresist film used in a semi-additive process employed in circuit formation of semiconductor packages.

Abstract

Disclosed are: a photosensitive resin composition having excellent resolving power, contact stability and resist stripping properties; and a photoresist film. The photosensitive resin composition comprises a polymer having a carboxyl group (A), an ethylenically unsaturated compound (B) and a photopolymerization initiator (C). The polymer having a carboxyl group (A) is a copolymer having methacrylic acid (a1), a vinyl monomer having a phenyl group (a2) and a compound represented by the formula (1) (a3) as the copolymerization components, wherein the content of the component (a1) is 22 to 35% by weight and the content of the component (a2) is 20 to 35% by weight, both relative to the total amount of the copolymerization components.

Description

明 細 書  Specification
感光性樹脂組成物及びそれを用いたフォトレジストフィルム  Photosensitive resin composition and photoresist film using the same
技術分野  Technical field
[0001] 本発明は、プリント配線基板及びリードフレーム加工、半導体パッケージ、ディスプ レイ等の製造に用いられるフォトレジストフィルム用の感光性榭脂組成物およびそれ を用いたフォトレジストフィルムに関し、更に詳しくは、感度、解像力、密着安定性、レ ジスト剥離性に優れた感光性榭脂組成物およびこれを用いたフォトレジストフィルム に関するものである。  TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition for a photoresist film used for manufacturing a printed wiring board, lead frame processing, a semiconductor package, a display and the like, and a photoresist film using the same. The present invention relates to a photosensitive resin composition excellent in sensitivity, resolving power, adhesion stability, and resist peelability, and a photoresist film using the same.
背景技術  Background art
[0002] プリント配線板回路形成、半導体パッケージ回路形成、リードフレーム加工等の製 造には感光性榭脂組成物を用いたフォトレジスト法が用いられており、このフォトレジ スト法においては、例えば、まず透明なフィルム等の支持体上に感光性榭脂組成物 を塗布して感光性榭脂組成物層を形成した後、この感光性榭脂組成物層を所望の ノ ターンを形成しょうとする基板表面に積層し、次 、で該感光性榭脂組成物層にパ ターンマスクを介して露光した後、未露光部分を溶剤又はアルカリ水溶液による現像 処理により除去して、レジスト画像を保護マスクとし、公知のエッチング処理又はパタ ーンめっき処理を行った後、レジスト剥離して印刷回路基板を製造する方法が通常 行われる。中でも特に、半導体パッケージの回路形成においては、セミアディティブ 工法が採用されることも多い。  [0002] A photoresist method using a photosensitive resin composition is used for manufacturing printed circuit board circuit formation, semiconductor package circuit formation, lead frame processing, and the like. In this photoresist method, for example, First, a photosensitive resin composition is applied onto a support such as a transparent film to form a photosensitive resin composition layer, and then the photosensitive resin composition layer is formed to form a desired pattern. Then, the photosensitive resin composition layer is exposed to light through a pattern mask, and the unexposed portion is removed by a development process using a solvent or an alkaline aqueous solution. In general, a method of manufacturing a printed circuit board by performing resist etching and performing a known etching process or pattern plating process is generally performed. In particular, the semi-additive method is often used in the circuit formation of semiconductor packages.
[0003] 力かるセミアディティブ工法では、基板上に薄層の導体層を形成した後、上記の如 き公知の方法によりレジストパターンを形成し、そして、形成されたレジストパターン間 に導体めつきを施した後、硬化レジストを剥離除去し、その後、フラッシュエッチング により導体回路を形成するのである。  [0003] In the powerful semi-additive method, after forming a thin conductor layer on a substrate, a resist pattern is formed by a known method as described above, and a conductor contact is formed between the formed resist patterns. After application, the hardened resist is peeled off and then a conductor circuit is formed by flash etching.
[0004] このようなセミアディティブ工法においては、めっきパターンのアスペクト比が 1を超 えるような高精細パターンを形成する時には導体めつきのパターンの間にレジストパ ターンが挟まれた状態となって、レジスト剥離が困難となるため、レジスト剥離性に優 れた感光性榭脂組成物が求められている。 [0005] レジスト剥離性を改善する感光性榭脂組成物としては、例えば、熱可塑性高分子と 、常温常圧で液体または固体の付加重合性化合物と、光重合開始剤とを含有する 光重合性組成物であって、該熱可塑性高分子が、カルボキシル基を有する重合性 モノマー 15〜40重量0 /0、スチレン系モノマー 1〜35重量0 /0、アクリル酸エステル及 びメタクリル酸エステル 84〜25重量％で構成されて ヽる光重合性組成物（例えば、 特許文献 1参照。）や、特定の不飽和化合物と OC , β 不飽和カルボキシル基含有 モノマーを必須の共重合成分とするバインダーポリマーと、 1分子中に 2個以上のェ チレン性不飽和基を有する光重合性モノマーと、光重合開始剤を主成分とする感光 性榭脂組成物 (例えば、特許文献 2参照。）が提案されている。 [0004] In such a semi-additive method, when forming a high-definition pattern in which the aspect ratio of the plating pattern exceeds 1, the resist pattern is sandwiched between conductive patterns, and the resist pattern Since peeling becomes difficult, a photosensitive resin composition excellent in resist peelability is desired. [0005] Examples of the photosensitive resin composition for improving resist stripping include photopolymerization, which includes, for example, a thermoplastic polymer, an addition polymerizable compound that is liquid or solid at normal temperature and pressure, and a photopolymerization initiator. a sex compositions, thermoplastic polymer, polymerizable monomer 15 to 40 weight 0/0 having a carboxyl group, styrene monomer 1-35 weight 0/0, acrylic acid ester及beauty methacrylic acid ester 84 to A photopolymerizable composition composed of 25% by weight (for example, see Patent Document 1) and a binder polymer having a specific unsaturated compound and an OC, β unsaturated carboxyl group-containing monomer as essential copolymerization components And a photosensitive resin composition mainly composed of a photopolymerizable monomer having two or more ethylenically unsaturated groups in one molecule and a photopolymerization initiator (see, for example, Patent Document 2). Has been.
[0006] 特許文献 1 :特開平 2— 161442号公報  [0006] Patent Document 1: Japanese Patent Laid-Open No. 2-161442
特許文献 2：特開平 9— 325487号公報  Patent Document 2: JP-A-9-325487
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0007] し力しながら、上記特許文献 1及び 2の開示技術では、レジスト剥離性の改善はみ られるもののまだまだ充分ではなぐ特に高精細パターンめっき後に水酸ィ匕ナトリウム 水溶液を剥離液とする場合においてはレジスト剥離が困難なものであった。 [0007] However, in the techniques disclosed in Patent Documents 1 and 2 above, although the resist strippability is improved, it is still not sufficient. In particular, when using a sodium hydroxide aqueous solution as a stripper after high-definition pattern plating, In this case, it was difficult to remove the resist.
また、特許文献 1の開示技術においては、密着性が安定せず量産時に歩留まりが 低下する問題があったり、特許文献 2の開示技術においては、解像力の点で更なる 改良が求められるものであつた。  In addition, the disclosed technique of Patent Document 1 has a problem that the adhesion is not stable and the yield decreases during mass production, and the disclosed technique of Patent Document 2 requires further improvement in terms of resolution. It was.
[0008] そこで、本発明ではこのような背景下において、解像力、密着安定性に優れ、且つ レジスト剥離性にも優れた感光性榭脂組成物及びそれを用いたフォトレジストフィル ムを提供することを目的とするものである。 Accordingly, the present invention provides a photosensitive resin composition that is excellent in resolving power, adhesion stability, and resist releasability, and a photoresist film using the same, in such a background. It is intended.
課題を解決するための手段  Means for solving the problem
[0009] しかるに、本発明者等は力かる事情に鑑み鋭意研究を重ねた結果、カルボキシル 基含有ポリマー (Α)、エチレン性不飽和化合物 (Β)、及び光重合開始剤 (C)を含有 する感光性榭脂組成物であって、カルボキシル基含有ポリマー (Α)として、カルボキ シル基含有モノマーを従来よりも多く用い、他のフエ-ル基含有ビュル系単量体及 び下記（1)式で示される長鎖のアクリル酸エステルの化合物と組み合わせて共重合 してなること〖こより、解像力、密着安定性に優れ、且つレジスト剥離性にも優れた感光 性榭脂組成物となることを見出した。 [0009] However, as a result of intensive studies in light of the circumstances, the present inventors, as a result, contain a carboxyl group-containing polymer (ポ リ マ ー), an ethylenically unsaturated compound (Β), and a photopolymerization initiator (C). A photosensitive resin composition comprising a carboxyl group-containing monomer more than a conventional carboxyl group-containing polymer (Α), and other phenol group-containing bulle monomers and the following formula (1) Copolymerized with a long-chain acrylate compound represented by As a result, it has been found that the photosensitive resin composition is excellent in resolving power, adhesion stability, and resist releasability.
即ち、本発明の要旨を以下に示す。  That is, the gist of the present invention is shown below.
(1) カルボキシル基含有ポリマー (A)、エチレン性不飽和化合物（B)、及び光重合 開始剤 (C)を含有する感光性榭脂組成物であって、カルボキシル基含有ポリマー（ A)力 メタクリル酸 (al)、フエニル基含有ビニル系単量体 (a2)、及び下記（1)式で 示される化合物 (a3)を、共重合成分として含む共重合体であり、全共重合成分に対 してのメタクリル酸（al)の含有量が 22〜35重量％で、フエ-ル基含有ビニル系単量 体 (a2)の含有量が 20〜35重量％であることを特徴とする感光性榭脂組成物。  (1) A photosensitive resin composition containing a carboxyl group-containing polymer (A), an ethylenically unsaturated compound (B), and a photopolymerization initiator (C), wherein the carboxyl group-containing polymer (A) A copolymer containing an acid (al), a phenyl group-containing vinyl monomer (a2), and a compound (a3) represented by the following formula (1) as a copolymerization component. The photosensitive resin is characterized in that the content of all methacrylic acid (al) is 22 to 35% by weight and the content of the vinyl group-containing vinyl monomer (a2) is 20 to 35% by weight. Fat composition.
[化 1] [Chemical 1]
CH2-CR1— COO— (R20) n— R3 · · ' ( 1 ) CH2-CR 1 — COO— (R 2 0) n — R3 · · '(1)
ここで、 R1は水素又はメチル基、 R2はエチレン基又はプロピレン基、 R3は炭素数 8〜 22個のアルキル基、 nは 1〜4の整数である。 Here, R 1 is hydrogen or a methyl group, R 2 is an ethylene group or a propylene group, R 3 is an alkyl group having 8 to 22 carbon atoms, and n is an integer of 1 to 4.
(2) フエ-ル基含有ビニル系単量体 (a2)がスチレンであることを特徴とする上記（1 )に記載の感光性榭脂組成物。  (2) The photosensitive resin composition as described in (1) above, wherein the vinyl group-containing vinyl monomer (a2) is styrene.
(3) (1)式で示される化合物（a3)力 2—ェチルへキシルカルビトール (メタ）アタリ レートであることを特徴とする上記（1)又は（2)記載の感光性榭脂組成物。  (3) The photosensitive resin composition according to the above (1) or (2), which is a compound represented by the formula (1) (a3) force 2-ethylhexyl carbitol (meth) atalylate .
(4) カルボキシル基含有ポリマー（A)の重量平均分子量が 30, 000〜100, 000 であり、ポリマー酸価が 175〜250mgKOHZgであることを特徴とする上記（1)〜（3 ) Vヽずれか記載の感光性榭脂組成物。  (4) The above-mentioned (1) to (3) V deviation is characterized in that the carboxyl group-containing polymer (A) has a weight average molecular weight of 30,000 to 100,000 and a polymer acid value of 175 to 250 mgKOHZg Or a photosensitive resin composition.
(5) エチレン性不飽和化合物（B)として、下記（2)式で示される化合物 (bl)を含有 してなることを特徴とする上記（1)〜 (4) V、ずれか記載の感光性榭脂組成物。 [化 2] (5) The photosensitivity as described in any one of (1) to (4) above, wherein the ethylenically unsaturated compound (B) contains a compound (bl) represented by the following formula (2): Rosin composition. [Chemical 2]
Figure imgf000005_0001
(C2H4O) k- (IK)) (C2H4O) m-CO— . · ' ( 2 )
Figure imgf000005_0001
(C2H4O) k- (IK)) (C2H4O) m -CO—. · '(2)
ここで、 R1は水素原子又はメチル基、 R4はプロピレン基又はブチレン基、 1 k mは整 数であり、 k+mの平均値が 2 6 1の平均値が 10 25である。 Here, R 1 is a hydrogen atom or a methyl group, R 4 is a propylene group or a butylene group, 1 km is an integer, and the average value of k + m is 2 6 1 and the average value is 10 25.
(6) 光重合開始剤 (C)として、口フィン二量体を含有してなることを特徴とする上記（ 1) （5) ずれか記載の感光性榭脂組成物。  (6) The photosensitive resin composition as described in any one of (1) and (5) above, wherein the photopolymerization initiator (C) comprises an oral fin dimer.
(7) 上記（1)〜（6)いずれか記載の感光性榭脂組成物の層と、ヘーズ値 1. 5以下 の支持体フィルムとを含むことを特徴とするフォトレジストフィルム。  (7) A photoresist film comprising a layer of the photosensitive resin composition according to any one of (1) to (6) above and a support film having a haze value of 1.5 or less.
(8) 更に、保護フィルムを感光性榭脂組成物層側に有することを特徴とする上記 (7 )記載のフォトレジストフィルム。  (8) The photoresist film as described in (7) above, further comprising a protective film on the photosensitive resin composition layer side.
発明の効果  The invention's effect
[0011] 本発明の感光性榭脂組成物及びそれを用いたフォトレジストフィルムは、カルボキ シル基含有ポリマー (A)、エチレン性不飽和化合物 (B)、及び光重合開始剤 (C)を 含有する感光性榭脂組成物であって、カルボキシル基含有ポリマー (A)力 メタタリ ル酸 (al)、フエニル基含有ビニル系単量体 (a2)、及び下記（1)式で示される化合 物（a3)、必要によりその他の共重合性モノマー（a4)を、共重合成分として含む共重 合体であるため、解像力、密着安定性に優れ、且つレジスト剥離性にも優れた効果 を奏するものであり、特にセミアディティブ工法において有用である。  The photosensitive resin composition of the present invention and a photoresist film using the same contain a carboxyl group-containing polymer (A), an ethylenically unsaturated compound (B), and a photopolymerization initiator (C). A photosensitive resin composition comprising a carboxyl group-containing polymer (A), a metataric acid (al), a phenyl group-containing vinyl monomer (a2), and a compound represented by the following formula (1) ( a3), and a copolymer that contains other copolymerizable monomer (a4) as a copolymerization component as necessary, so that it has excellent resolution and adhesion stability, as well as excellent resist releasability. In particular, it is useful in the semi-additive construction method.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0012] 以下に、本発明を詳細に説明する。 [0012] The present invention is described in detail below.
本発明で用いるカルボキシル基含有ポリマー (A)としては、メタクリル酸 (al)、フエ ニル基含有ビニル系単量体 (a2)、及び上記（1)式で示される化合物（a3)、必要に よりその他の共重合性モノマー（a4)を、共重合成分として含む共重合体であることが 必要であり、各共重合成分の含有割合としては、全共重合成分の重量を基準として、 メタクリル酸 (al)の含有量は 22〜35重量％、好ましくは 25〜32重量％、更に好まし くは 27〜30重量％、フエニル基含有ビュル系単量体（a2)の含有量は 20〜35重量 %、好ましくは 23〜32重量％、更に好ましくは 26〜30重量％、上記（1)式で示され る化合物（a3)の含有量は特に限定されないが、 3〜20重量％が好ましぐ更には 5 〜15重量％が好ましぐ特には 5〜10重量％が好ましい。必要により含まれるその他 の共重合性モノマー（a4)の含有量も特に限定されないが、好ましくは 10〜55重量 %、更には 10〜47重量％が好ましぐ特には 20〜42重量％が好ましい範囲である Examples of the carboxyl group-containing polymer (A) used in the present invention include methacrylic acid (al), a phenyl group-containing vinyl monomer (a2), and a compound (a3) represented by the above formula (1). It is necessary that the copolymer contains other copolymerizable monomer (a4) as a copolymer component, and the content ratio of each copolymer component is based on the weight of all copolymer components. The content of methacrylic acid (al) is 22 to 35% by weight, preferably 25 to 32% by weight, more preferably 27 to 30% by weight, and the content of the phenyl group-containing bur monomer (a2) is 20%. To 35 wt%, preferably 23 to 32 wt%, more preferably 26 to 30 wt%, and the content of the compound (a3) represented by the above formula (1) is not particularly limited, but 3 to 20 wt% More preferred is 5 to 15% by weight, and particularly preferred is 5 to 10% by weight. The content of the other copolymerizable monomer (a4) contained if necessary is not particularly limited, but is preferably 10 to 55% by weight, more preferably 10 to 47% by weight, and particularly preferably 20 to 42% by weight. Is a range
[0013] メタクリル酸 (al)が下限値未満ではめつき後のレジスト剥離性が不充分であり、上 限値を超えるとレジストの密着性が低下することとなる。フエ-ル基含有ビニル系単量 体 (a2)が下限値未満では解像力が充分得られず、上限値を超えるとめつき後のレジ スト剥離が困難となり、レジストの欠け等の欠損も増加することとなる。上記（1)式で示 される化合物 (a3)の化合物が下限値未満ではレジストの密着が不安定となる傾向と なり、上限値を超えると解像力が低下する傾向となる。 [0013] When the methacrylic acid (al) is less than the lower limit value, the resist peelability after fitting is insufficient, and when the methacrylic acid (al) exceeds the upper limit value, the adhesion of the resist is lowered. If the vinyl group-containing monomer (a2) is less than the lower limit, sufficient resolving power cannot be obtained, and if it exceeds the upper limit, resist peeling after staking becomes difficult, and defects such as resist chipping increase. It becomes. If the compound of the compound (a3) represented by the above formula (1) is less than the lower limit value, the adhesion of the resist tends to be unstable, and if it exceeds the upper limit value, the resolution tends to decrease.
[0014] 上記フエ-ル基含有ビニル系単量体（a2)としては、例えば、スチレン、メチルスチ レン、ビニルベンジル、ビニルビフエ-ル、安息香酸ビュルなどが挙げられるが、中で もスチレンが好適に用いられる。  [0014] Examples of the vinyl group-containing vinyl monomer (a2) include styrene, methylstyrene, vinyl benzyl, vinyl biphenyl, and benzoic acid butyl. Among them, styrene is preferable. Used.
[0015] 上記（1)式で示される化合物（a3)において、 R1は水素又はメチル基より選択される 一価の有機基である。また、 R2はエチレン基又はプロピレン基より選択される二価の アルキレン基であり、 R2がエチレン基である場合、 nは 1〜3の整数が好適であり、 R3 は炭素数 8〜22のアルキル基であり、炭素数 8〜16のアルキル基であることが好まし い。 R2がプロピレン基である場合、 nは 2〜4の整数が好適であり、 R3は炭素数 8〜12 のアルキル基であることが好まし!/、。 In the compound (a3) represented by the above formula (1), R 1 is a monovalent organic group selected from hydrogen or a methyl group. R 2 is a divalent alkylene group selected from an ethylene group or a propylene group, and when R 2 is an ethylene group, n is preferably an integer of 1 to 3, and R 3 has 8 to 8 carbon atoms. It is preferably an alkyl group having 22 to 16 carbon atoms. When R 2 is a propylene group, n is preferably an integer of 2 to 4, and R 3 is preferably an alkyl group having 8 to 12 carbon atoms! /.
[0016] 上記（1)式で示される化合物（a3)としては、特に限定されず、例えば 2 ェチルへ キシルカルビトールアタリレート (東亞合成化学工業社製、「ァ口-タス M— 120」）、 2 ェチルへキシルカルビトールメタタリレート、ラウリルカルビトール（メタ）アタリレート などのアルキルカルビトール (メタ）アタリレート、ラウ口キシテトラエチレングリコール (メ タ）アタリレート、ステア口キシテトラエチレングリコール (メタ）アタリレート等が挙げられ るが、中でも、レジスト密着性の点で、 2—ェチルへキシルカルビトール (メタ）アタリレ ートが好ましぐより好ましくは 2—ェチルへキシルカルビトールアタリレートである。 [0016] The compound (a3) represented by the above formula (1) is not particularly limited. , 2-ethylhexyl carbitol metatalylate, alkyl carbitol (meth) acrylate, such as lauryl carbitol (meth) acrylate, lauryl oxytetraethylene glycol (meth) acrylate, stear oxytetraethylene glycol ( Meta) Atallate etc. Of these, 2-ethylhexyl carbitol (meth) acrylate is preferred from the viewpoint of resist adhesion, and 2-ethyl hexyl carbitol acrylate is more preferred.
[0017] 上記のその他の共重合性モノマー（a4)としては、上記 (al)〜（a3)以外の共重合 可能なモノマーであれば特に限定されず、例えば、メチル (メタ)アタリレート、ェチル (メタ）アタリレート、プロピル (メタ）アタリレート、ブチル (メタ）アタリレート、へキシル (メ タ）アタリレート、 2—ェチルへキシル (メタ）アタリレート、ラウリル (メタ）アタリレート等の 脂肪族アルキル (メタ)アタリレート類、シクロへキシル (メタ)アタリレート等の脂環式ァ ルキル (メタ)アタリレート類、ベンジル (メタ)アタリレート等の芳香族置換アルキル (メ タ）アタリレート類、ジメチルアミノエチル (メタ）アタリレート、ジェチルアミノエチル (メタ )アタリレート等のアミノ基含有 (メタ)アタリレート類、ヒドロキシェチル (メタ)アタリレー ト、ヒドロキシプロピル (メタ)アタリレート、グリジシル (メタ)アタリレート等の水酸基含有 (メタ）アタリレート類、アクリル酸、クロトン酸等のモノカルボン酸、マレイン酸、フマー ル酸、ィタコン酸等のジカルボン酸あるいはそれらの無水物やハーフエステル等のェ チレン性不飽和カルボン酸類、（メタ)アクリルアミド、（メタ)アクリロニトリル、酢酸ビ- ル、アルキルビュルエーテル等のその他のエチレン性不飽和モノマー等が挙げられ る。 [0017] The other copolymerizable monomer (a4) is not particularly limited as long as it is a copolymerizable monomer other than the above (al) to (a3), and examples thereof include methyl (meth) acrylate and ethyl. Aliphatics such as (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, lauryl (meth) acrylate Alkyl (meth) acrylates, alicyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, aromatic substituted alkyl (meth) acrylates such as benzyl (meth) acrylate, Amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate, jetylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, Hydroxyl-containing (meth) acrylates such as hydroxypropyl (meth) acrylate and glycidyl (meth) acrylate, monocarboxylic acids such as acrylic acid and crotonic acid, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid or Examples thereof include ethylenically unsaturated carboxylic acids such as anhydrides and half esters, and other ethylenically unsaturated monomers such as (meth) acrylamide, (meth) acrylonitrile, acetic acid vinyl, and alkyl butyl ether.
[0018] カルボキシル基含有ポリマー（A)の酸価については、 175〜250mgKOHZg力 s 好ましぐ更に好ましくは 180〜230mgKOHZg、特に好ましくは 195〜220mgKO HZgである。カゝかる酸価が下限値未満では現像性が低下し、解像力の低下を招くこ ととなりめつき後のレジスト剥離性が不充分となる傾向があり、酸価が上限値を超える と硬化レジストの耐現像液性が低下し、細線密着性の低下を招く傾向がある。 [0018] For the acid value of the carboxyl group-containing polymer (A), 175~250mgKOHZg force s preferred instrument More preferably 180～230MgKOHZg, particularly preferably 195~220mgKO HZg. If the acid value is less than the lower limit, the developability is lowered, resulting in a decrease in resolving power, and the resist peelability after tacking tends to be insufficient. If the acid value exceeds the upper limit, the cured resist Of the developer tends to be reduced, and the fine wire adhesion tends to be reduced.
[0019] 更に、カルボキシル基含有ポリマー（A)の重量平均分子量は 30, 000〜100, 00 0力 S好ましく、更に好ましく ίま 40, 000-60, 000であり、重量平均分子量力 S下限値 未満では、レジスト密着が不安定でレジストの欠け等の欠損も増加することとなり、上 限値を超えると解像力が低下する傾向がある。  [0019] Further, the weight average molecular weight of the carboxyl group-containing polymer (A) is preferably 30,000 to 100,000,000, more preferably 40,000-60,000, and the weight average molecular weight S is the lower limit. If it is less than 1, the resist adhesion is unstable and defects such as chipping of the resist also increase, and if the upper limit is exceeded, the resolution tends to decrease.
カルボキシル基含有ポリマー (Α)の配合割合は、カルボキシル基含有ポリマー (Α) とエチレン性不飽和化合物（Β)の総重量に対して、 10〜95重量部であることが好ま しぐ特に好ましくは 20〜80重量部、更に好ましくは 40〜60重量部である。カルボ キシル基含有ポリマー（A)の過少はフィルム形成が困難となる傾向があり、カルボキ シル基含有ポリマー (A)の過多は解像力や細線密着性の低下を招く傾向がある。 The blending ratio of the carboxyl group-containing polymer (Α) is particularly preferably 10 to 95 parts by weight with respect to the total weight of the carboxyl group-containing polymer (Α) and the ethylenically unsaturated compound (Β). 20 to 80 parts by weight, more preferably 40 to 60 parts by weight. Carbo If the amount of the xyl group-containing polymer (A) is too small, film formation tends to be difficult, and if the amount of the carboxyl group-containing polymer (A) is too large, the resolution and fine line adhesion tend to be lowered.
[0020] 本発明で用いるエチレン性不飽和化合物（B)としては、重合性不飽和基を 2個以 上有するものであれば特に限定されず、例えば、 2官能モノマーとしては、エチレング リコールジ (メタ）アタリレート、ジエチレングリコールジ (メタ）アタリレート、テトラエチレ ングリコールジ (メタ）アタリレート、ポリエチレングリコールジ (メタ）アタリレート、プロピ レングリコールジ（メタ）アタリレート、ポリプロピレングリコールジ (メタ）アタリレート、ブ チレングリコールジ (メタ）アタリレート、ネオペンチルグリコールジ (メタ）アタリレート、 プロピレンオキサイド変性ネオペンチルグリコールジ (メタ）アタリレート等のアルキレン オキサイドジ (メタ)アタリレート類、エチレンオキサイド変性ビスフエノール A型ジ (メタ )アタリレート、プロピレンオキサイド変性ビスフエノール A型ジ (メタ）アタリレート、ェチ レンオキサイド 'プロピオンオキサイド変性ビスフエノール A型ジ (メタ）アタリレート等の アルキレンオキサイド変性ジ (メタ）アタリレート類、 1, 6—へキサンジオールジ (メタ） アタリレート、 1, 10—デカンジオールジ (メタ）アタリレート等のアルキレンジオールジ (メタ）アタリレート類、グリセリンジ (メタ）アタリレート、ペンタエリスリトールジ (メタ）ァク リレート、エチレングリコールジグリシジルエーテルジ (メタ）アタリレート、ジエチレング リコールジグリシジルエーテルジ (メタ）アタリレート、フタル酸ジグリシジルエステルジ（ メタ）アタリレート等のポリオールジ (メタ）アタリレート類、ビュルアタリレート、ヒドロキシ ビバリン酸変性ネオペンチルダリコールジ (メタ）アタリレート等のその他の 2官能モノ マー類が挙げられ、又、 3官能以上のモノマーとしては、トリメチロールプロパントリ（メ タ）アタリレート、ペンタエリスリトールトリ（メタ）アタリレート、ジペンタエリスリトールペン タ (メタ）アタリレート、トリ（メタ）アタリロイルォキシエトキシトリメチロールプロパン、ダリ セリンポリグリシジルエーテルポリ（メタ）アタリレート等が挙げられる。さらに任意のウレ タン (メタ)アタリレートイ匕合物を使用することも可能である。  [0020] The ethylenically unsaturated compound (B) used in the present invention is not particularly limited as long as it has two or more polymerizable unsaturated groups. For example, the bifunctional monomer may be ethylene glycol di (meta). ) Atalylate, Diethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, Alkylene oxide di (meth) acrylates such as butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A Type di (meta) Alkylene oxide-modified di (meth) acrylates, such as talylate, propylene oxide-modified bisphenol A-type di (meth) acrylate, ethylene oxide 'propion oxide-modified bisphenol A-type di (meth) acrylate, 1, 6 —Hexanediol di (meth) atarylate, 1,10-decanedioldi (meth) atalylate and other alkylene dioldi (meth) atalylates, glycerindi (meth) atalylate, pentaerythritoldi (meth) a Polyol di (meth) acrylates such as chlorate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, etc. Atarirate, Hide Examples of other bifunctional monomers such as xoxybivalic acid-modified neopentyldalycol di (meth) atalylate include trimethylolpropane tri (meth) atalylate and pentaerythritol. Examples include tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) tertyloxyethoxytrimethylol propane, dariserine polyglycidyl ether poly (meth) acrylate, and the like. Furthermore, it is possible to use any urethane (meta) ata relay toy compound.
[0021] これらの 2官能以上のモノマーは 2種類以上使用することも可能であると共に、下記 の単官能モノマーを適当量併用することもできる。  [0021] Two or more types of these bifunctional or more functional monomers can be used, and an appropriate amount of the following monofunctional monomers can be used in combination.
[0022] 単官能モノマーの例としては、 2—ヒドロキシェチル (メタ）アタリレート、 2—ヒドロキ シプロピル (メタ）アタリレート、 2—ヒドロキシブチル (メタ）アタリレート、ポリエチレング リコール (メタ）アタリレート、ポリプロピレングリコール (メタ）アタリレート、 2—フエノキシ —2—ヒドロキシプロピル (メタ）アタリレート、 2- (メタ）アタリロイルォキシ一 2—ヒドロ キシプロピルフタレート、 3—クロ口一 2—ヒドロキシプロピル（メタ）アタリレート、グリセリ ンモノ（メタ）アタリレート、 2- (メタ）アタリロイルォキシェチルアシッドホスフェート、フ タル酸誘導体のハーフ（メタ）アタリレート、ポリ力プロラタトンモノ (メタ）アタリレート、 N —メチロール (メタ）アクリルアミド、ジェチルアミノエチル (メタ）アタリレート等が挙げら れる。 [0022] Examples of the monofunctional monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polyethylene glycol Recall (meth) acrylate, polypropylene glycol (meth) acrylate, 2-phenoxy —2-hydroxypropyl (meth) acrylate, 2- (meth) tert-yloxy 2-hydroxypropyl phthalate, 3 — black mouth 1-Hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) tarolooxychetyl acid phosphate, half (meth) acrylate of phthalic acid derivatives, poly strength prolatathone mono Examples include (meth) acrylate, N-methylol (meth) acrylamide, and jetylaminoethyl (meth) acrylate.
[0023] 本発明においては、特にエチレン性不飽和化合物（B)として、少なくとも下記（2) 式で示される化合物 (bl)を含有することが解像力及びレジストの密着安定性の点で 好ましい。  In the present invention, it is particularly preferable from the viewpoint of resolving power and resist adhesion stability that at least the compound (bl) represented by the following formula (2) is contained as the ethylenically unsaturated compound (B).
[0024] [化 3]  [0024] [Chemical 3]
CHFCR1— COO— (C2H40) k - ( ） 1一 (C2H40) . - CO- CR^CHs - ■ · ( 2 ) CHFCR 1 — COO— (C2H40) k-() 1 1 (C 2 H 4 0).-CO- CR ^ CHs-■ · (2)
ここで、 R1は水素原子又はメチル基、 R4はプロピレン基又はブチレン基、 1、 k、 mは整 数であり、 k+mの平均値が 2〜6、 1の平均値が 10〜25である。 Here, R 1 is a hydrogen atom or a methyl group, R 4 is a propylene group or a butylene group, 1, k, m are integers, the average value of k + m is 2 to 6, and the average value of 1 is 10 to 25.
[0025] 上記（2)式において、 k+mは平均値として 2〜6が好適であり、下限値未満では光 硬化性が不充分なため解像力が低下する傾向があり、上限値を超えると現像液やめ つき液に対する耐性が低下するため解像力が低下する傾向がある。 1は平均値として 10〜25が好適であり、下限値未満では密着安定ィ匕の効果が不充分となる傾向があ り、上限値を超えると解像力が低下する傾向がある。  [0025] In the above formula (2), k + m is preferably 2 to 6 as an average value, and if it is less than the lower limit, the photocurability is insufficient and the resolution tends to decrease. Resolving power tends to decrease due to a decrease in resistance to the developer and the plating solution. The average value of 1 is preferably 10 to 25, and if it is less than the lower limit, the effect of adhesion stability tends to be insufficient, and if it exceeds the upper limit, the resolution tends to decrease.
[0026] 力かる（2)式で示される化合物 (bl)の具体例としては 日本油脂製「ブレンマー 30 PDC - 600B」、「ブレンマー 30PDC - 800BJ等が挙げられる。  Specific examples of the compound (bl) represented by the formula (2) are “Blemmer 30 PDC-600B”, “Blemmer 30PDC-800BJ” and the like manufactured by NOF Corporation.
[0027] エチレン性不飽和化合物（B)の配合割合は、カルボキシル基含有ポリマー (A)と エチレン性不飽和化合物（B)の総重量に対して、 5〜90重量部であることが好ましく 、特に好ましくは 20〜80重量部、更に好ましくは 40〜60重量部である。エチレン性 不飽和化合物（B)の過少は硬化不良、可撓性の低下、現像速度の遅延を招き、ェ チレン性不飽和化合物（B)の過多は粘着性の増大、コールドフロー、硬化レジストの 剥離速度の低下を招く傾向がある。 [0027] The blending ratio of the ethylenically unsaturated compound (B) is preferably 5 to 90 parts by weight with respect to the total weight of the carboxyl group-containing polymer (A) and the ethylenically unsaturated compound (B). Particularly preferred is 20 to 80 parts by weight, still more preferred is 40 to 60 parts by weight. Ethylenic Too little unsaturated compound (B) leads to poor curing, poor flexibility, and slow development speed, too much ethylenically unsaturated compound (B) increases tackiness, cold flow, and removal rate of cured resist. There is a tendency to lead to a decline.
[0028] また、エチレン性不飽和化合物（B)の中でも上記（2)式で示される化合物 (bl)の 配合割合としては、エチレン性不飽和化合物（B)全体に対して、 5〜80重量％であ ることが好ましぐ更には 10〜70重量％、特には 20〜60重量％であることが好まし い。化合物 (bl)の配合割合が下限値未満ではレジストの密着が安定しない傾向が あり、上限値を超えるとレジスト剥離性が低下すると共にコールドフローが発生しやす くなる傾向がある。 [0028] Among the ethylenically unsaturated compounds (B), the compounding ratio of the compound (bl) represented by the above formula (2) is 5 to 80% with respect to the total ethylenically unsaturated compounds (B). %, More preferably 10 to 70% by weight, especially 20 to 60% by weight. When the compounding ratio of the compound (bl) is less than the lower limit, the adhesion of the resist tends to be unstable, and when it exceeds the upper limit, the resist peelability tends to decrease and cold flow tends to occur.
[0029] 本発明で用いる光重合開始剤 (C)としては、特に限定されず、公知の光重合開始 剤を用いることができ、例えば、 p, v' —ビス（ジメチルァミノ）ベンゾフエノン、 p, p' -ビス（ジェチルァミノ）ベンゾフエノン、 p, p' -ビス（ジブチルァミノ）ベンゾフエノン 、ベンゾイン、ベンゾインメチルエーテル、ベンゾインェチルエーテル、ベンゾインイソ プロピノレエーテノレ、ベンゾイン n—ブチノレエーテノレ、ベンゾインフエニノレエーテノレ、ベ ンゾインイソブチルエーテル、ベンゾィル安息香酸、ベンゾィル安息香酸メチル、ベ ンジルジフエ-ルジスルフイド、ベンジルジメチルケタール、ジベンジル、ジァセチル 、アントラキノン、ナフトキノン、 3, 3' —ジメチルー 4ーメトキシベンゾフエノン、ベンゾ フエノン、ジクロロアセトフエノン、 2—クロ口チォキサントン、 2—メチルチオキサントン 、 2, 4 ジェチルチオキサントン、 2, 2 ジエトキシァセトフエノン、 2, 2 ジクロロー 4—フエノキシァセトフエノン、フエ-ルグリオキシレート、 a—ヒドロキシイソブチルフエ ノン、ジベンゾスパロン、 1— (4—イソプロピルフエ-ル） 2 ヒドロキシ一 2—メチル — 1 プロパノン、 2 メチル [4 (メチルチオ）フエ-ル] 2 モルフオリノー 1 プロパノン、トリブロモフエ-ルスルホン、トリブロモメチルフエ-ルスルホン、更には 2 , 4, 6— [トリス（トリクロロメチル） ] 1, 3, 5 トリァジン、 2, 4— [ビス（トリクロロメチ ル）]—6— (4' —メトキシフエ-ル）一 1, 3, 5 トリァジン、 2, 4— [ビス（トリクロロメ チル） ]—6— (4' —メトキシナフチル） 1, 3, 5 トリアジン、 2, 4— [ビス（トリクロ口 メチル）]—6— (ピぺ口-ル）一 1, 3, 5 トリアジン、 2, 4— [ビス（トリクロロメチル）] —6— (4' —メトキシスチリル）— 1, 3, 5 トリァジン等のトリァジン誘導体、アタリジ ン及び 9 フエ-ルァクリジン等のアタリジン誘導体、 2, 2' —ビス（o クロ口フエ- ル） 4, 5, 4' , 5' —テトラフエ-ルー 1, 2' —ビイミダゾール、 2, 2' —ビス（o— クロ口フエ-ル）一 4, 5, 4' , 5' —テトラフエ-ルー 1, \' —ビイミダゾール、 2, 2 ' —ビス（o フルオロフェ-ル）一4, 5, 4' , 5' —テトラフエ-ルー 1, 1' —ビイミ ダゾール、 2, 2' —ビス（o—メトキシフエ-ル）一 4, 5, 4' , 5' —テトラフエ-ル一 1, \' ービイミダゾール、 2, 2' —ビス（p—メトキシフエ-ル）一 4, 5, 4' , 5' —テ トラフエ-ルー 1, \' —ビイミダゾール、 2, 4, 2' , 4' —ビス [ビ（p—メトキシフエ- ル）]—5, 5' —ジフエ-ル— 1, 1' —ビイミダゾール、 2, 2' —ビス（2, 4 ジメトキ シフエ-ル）一 4, 5, 4' , 5' —ジフエ-ルー 1, \' ービイミダゾール、 2, 2' —ビ ス（p—メチルチオフエ-ル）一 4, 5, 4' , 5' —ジフエ-ル 1, / —ビイミダゾー ル、ビス（2, 4, 5 トリフエ-ル）— 1, \' —ビイミダゾール、 1, 2' —、 1, 4' —、 2 , 4' 一で共有結合している互変異性体等の口フィン二量体、トリフエニルフォスフィ ン、 2 ベンゾィル 2 ジメチルァミノ一 1— [4 モルフォリノフエ-ル]—ブタン等 が挙げられる。 [0029] The photopolymerization initiator (C) used in the present invention is not particularly limited, and a known photopolymerization initiator can be used. For example, p, v'-bis (dimethylamino) benzophenone, p, p '-Bis (jetylamino) benzophenone, p, p'-Bis (dibutylamino) benzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropinoreethenole, benzoin n-butinoleethenore, benzoinphenenoleethenore , Benzoin isobutyl ether, benzoyl benzoic acid, methyl benzoyl benzoate, benzyl diphenyl disulfide, benzyl dimethyl ketal, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3, 3'-dimethyl-4-methoxybenzophenone, benzophenone, Dichloroace Phenone, 2-chlorothioxanthone, 2-Methylthioxanthone, 2, 4 Jetylthioxanthone, 2, 2 Diethoxyacetophenone, 2, 2 Dichloro-4-phenoxyacetophenone, phenol glyoxylate, a-hydroxy Isobutyl phenone, dibenzosperone, 1— (4-Isopropylphenol) 2 Hydroxy 2-methyl — 1 Propanone, 2 Methyl [4 (Methylthio) phenol] 2 Morpholinol 1 Propanone, Tribromophenol sulfone, Tribromomethyl Phenolsulfone, and 2, 4, 6- [tris (trichloromethyl)] 1, 3,5 triazine, 2, 4- [bis (trichloromethyl)]-6- (4'-methoxyphenol) 1, 3, 5 Triazine, 2, 4— [Bis (trichloromethyl)] —6— (4 ′ —methoxynaphthyl) 1, 3, 5 Triazine, 2, 4— [Bis (Trichloro Methyl)]-6- (Pipe Methyl) 1, 3, 5 Triazine, 2, 4— [Bis (trichloromethyl)] —6— (4 '—Methoxystyryl) — 1, 3, 5 Triazine Triazine derivatives such as Atariji , 9 Aphalidine derivatives such as phthalacridine, 2, 2 '-bis (o black mouth phenol) 4, 5, 4', 5 '-tetraphenyl 1,2' -biimidazole, 2, 2 ' —One bis (o—black-mouthed) 4, 5, 4 ', 5' —Tetraferroic 1, \ '—Biimidazole, 2, 2' —One bis (o-fluorophenol) 4, 5, 4 ', 5' —tetraphenol 1, 1 '—biimidazole, 2, 2' —bis (o-methoxyphenol) 1, 4, 5, 4 ', 5' —tetraphenol 1, 1, \ '-biimidazole , 2, 2 '— Bis (p-methoxyphenol) 4, 5, 4', 5 '— Tetraflulu 1, \' — Biimidazole, 2, 4, 2 ', 4' — Bis [bi (P-methoxyphenyl)]-5,5'-diphenyl-1,1,1'-biimidazole, 2,2'-bis (2,4 dimethyoxyphenyl) 4, 5, 4 ', 5 '—Diferro- 1, 2,' -biimidazole, 2, 2 '— Bis (p-methylthiophenol) 1, 4, 5, 4' , 5 '— Diphenyl 1, / — Biimidazole, Bis (2, 4, 5 Triphenyl) — 1, \' — Biimidazole, 1, 2 '—, 1, 4' —, 2, 4 ' Mouth fin dimers such as tautomers that are covalently bonded to each other, triphenylphosphine, 2 benzoyl 2 dimethylamino 1- [4 morpholinophenol] -butane, and the like.
[0030] 本発明にお ヽては、光重合開始剤 (C)として、少なくとも口フィン二量体を含有する ことが解像力が向上する点で好ましぐ更に、ジアルキルァミノべンゾフエノンを併用 することが良好な感度を得る点で好ま ヽ。  [0030] In the present invention, it is preferable that at least an oral fin dimer is contained as the photopolymerization initiator (C) in view of improving resolution, and a dialkylaminobenzophenone is used in combination. Is preferred in terms of obtaining good sensitivity.
[0031] 力かる口フィン二量体の含有量としては、カルボキシル基含有ポリマー（A)とェチレ ン性不飽和化合物（B)の合計 100重量部に対して 2〜6重量部、更には 3〜5重量 部、特には 3. 5〜4. 5重量部が好ましい。口フィン二量体が下限値未満では解像力 が不充分であり、上限値を超えるとレジストが脆くなるうえ現像液中にスラッジが発生 する傾向がある。  [0031] The content of the powerful fin fin dimer is 2 to 6 parts by weight based on a total of 100 parts by weight of the carboxyl group-containing polymer (A) and the ethylenically unsaturated compound (B), and 3 ~ 5 parts by weight, particularly 3.5 to 4.5 parts by weight is preferred. If the mouth fin dimer is less than the lower limit, the resolution is insufficient, and if the upper limit is exceeded, the resist becomes brittle and sludge tends to be generated in the developer.
[0032] 力かるジアルキルァミノべンゾフエノンの含有量としては、カルボキシル基含有ポリ マー (A)とエチレン性不飽和化合物（B)の合計 100重量部に対して 0. 05〜1重量 部、更には 0. 1〜0. 5重量部、特には 0. 12〜0. 2重量部が好ましい。ジアルキル ァミノべンゾフエノンが下限値未満では充分な感度と解像力が得られず、上限値を超 えると密着性が低下する傾向がある。  [0032] The content of the powerful dialkylaminobenzophenone is 0.05 to 1 part by weight based on 100 parts by weight of the total of the carboxyl group-containing polymer (A) and the ethylenically unsaturated compound (B), and Is preferably 0.1 to 0.5 parts by weight, particularly preferably 0.12 to 0.2 parts by weight. If the dialkylaminobenzophenone is less than the lower limit, sufficient sensitivity and resolving power cannot be obtained, and if it exceeds the upper limit, the adhesion tends to decrease.
[0033] また、光重合開始剤 (C)の含有量としては、カルボキシル基含有ポリマー (A)及び エチレン性不飽和化合物（B)の合計 100重量部に対して、 0. 01〜10重量部である ことが好ましぐ更に好ましくは 0. 1〜8重量部、特に好ましくは 1〜6重量部である。 力かる含有量が下限値未満では感度が著しく低下して良好な作業性が得られない 傾向があり、逆に上限値を超えるとフォトレジストフィルムとしたときの保存安定性が低 下する傾向がある。 [0033] The content of the photopolymerization initiator (C) includes the carboxyl group-containing polymer (A) and It is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, particularly preferably 1 to 6 parts by weight, based on 100 parts by weight of the total amount of the ethylenically unsaturated compound (B). It is. If the content is less than the lower limit, the sensitivity tends to be significantly reduced and good workability tends not to be obtained. Conversely, if the content exceeds the upper limit, the storage stability of the photoresist film tends to decrease. is there.
[0034] 力べして本発明では、上記特定のカルボキシル基含有ポリマー (A)、エチレン性不 飽和化合物 ）（好ましくは少なくとも上記 (2)式で示される化合物 (bl)を含む。）、 光重合開始剤 (C)を含有する感光性榭脂組成物が得られるが、必要に応じてその 他の成分として、熱重合禁止剤、可塑剤、染料 (色素、変色剤)、酸化防止剤、溶剤 、表面張力改質剤、安定剤、連鎖移動剤、消泡剤、難燃剤、エチレン性不飽和結合 を有する共重合体等の成分を適宜添加することができる。  [0034] In the present invention, the specific carboxyl group-containing polymer (A) and the ethylenically unsaturated compound) (preferably including at least the compound (bl) represented by the above formula (2)), photopolymerization. A photosensitive resin composition containing the initiator (C) can be obtained, but as necessary, other components such as thermal polymerization inhibitors, plasticizers, dyes (pigments, discoloring agents), antioxidants, solvents In addition, components such as a surface tension modifier, a stabilizer, a chain transfer agent, an antifoaming agent, a flame retardant, and a copolymer having an ethylenically unsaturated bond can be appropriately added.
[0035] 例えば、熱重合禁止剤は感光性榭脂組成物の熱的な重合又は経時的な重合を防 止するために添カ卩するもので、 p—メトキシフエノール、ヒドロキノン、 tーブチルカテコ ール、ピロガロール、 2 ヒドロキシベンゾフエノン、 4ーメトキシ 2 ヒドロキシベンゾ フエノン、 4—メトキシ一 2 ヒドロキシベンゾフエノン、チォ尿素、フエノチアジン、クロ ラニル、ナフチルァミン、 13 ナフトール、 2, 6 ジ tーブチルー p クレゾール、二 トロベンゼン、ピクリン酸、 p トルイジン等が挙げられる。  [0035] For example, a thermal polymerization inhibitor is added to prevent thermal polymerization or temporal polymerization of the photosensitive resin composition, and includes p-methoxyphenol, hydroquinone, t-butylcatechol. , Pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, 4-methoxy1-2hydroxybenzophenone, thiourea, phenothiazine, chloranil, naphthylamine, 13 naphthol, 2,6 di-tert-butylcresole, ditro Examples include benzene, picric acid, and p-toluidine.
[0036] 可塑剤は膜物性をコントロールするために添加するもので、例えばジブチルフタレ ート、ジヘプチルフタレート、ジォクチルフタレート、ジァリルフタレート等のフタル酸ェ ステル類；トリエチレングリコールジアセテート、テトラエチレングリコールジアセテート 等のグリコールエステル類；トリクレジルホスフェート、トリフエ-ルホスフェート等のリン 酸エステル類； p -トルエンスルホンアミド、 N n—ブチルァセトアミド等のアミド類； ジイソブチルアジペート、ジォクチルアジペート、ジメチルセバケート、ジォクチルァゼ レート、ジブチルマレート等の脂肪族二塩基酸エステル類;タエン酸トリエチル、タエ ン酸トリブチル、グリセリントリァセチルエステル、ラウリン酸ブチル、 4, 5—ジエポキシ シクロへキサン 1, 2—ジカルボン酸ジォクチル、ポリエチレングリコール、ポリプロピ レンダリコール等のグリコール類等が挙げられる。  [0036] Plasticizers are added to control film physical properties. For example, phthalate esters such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diallyl phthalate; triethylene glycol diacetate, Glycol esters such as tetraethylene glycol diacetate; Phosphate esters such as tricresyl phosphate and triphenyl phosphate; Amides such as p-toluenesulfonamide and N n-butylacetamide; Diisobutyl adipate and dio Aliphatic dibasic acid esters such as octyl adipate, dimethyl sebacate, dioctyl azelate, dibutyl malate; triethyl taenoate, tributyl tamate, glycerin triacetyl ester, butyl laurate, 4,5-diepoxy cyclohexane 1 , 2— Carboxylic acid Jiokuchiru, polyethylene glycol, glycols, etc. Poripuropi render recalls like.
[0037] 色素としては、例えば、ブリリアントグリーン、ェォシン、ェチルバイオレット、エリス口 シン B、メチルグリーン、クリスタルバイオレット、べィシックフクシン、フエノールフタレ イン、 1 , 3 ジフエニルトリアジン、ァリザリンレッド S、チモールフタレイン、メチルバィ ォレット 2B、キナノレジンレッド、ローズべンガノレ、メタニノレイエロー、チモーノレスノレホフ タレイン、キシレノールブルー、メチルオレンジ、オレンジ 4、ジフエ二ルチオカルバゾ ン、 2, 7 ジクロ口フルォレセイン、パラメチルレッド、コンゴ一レッド、ベンゾプルプリ ン 4B、 a ナフチルレッド、ナイルブルー A、フエナセタリン、メチルバイオレット、マ ラカイトグリーン、パラフクシン、オイルブルー # 613 [オリエント化学工業 (株)製]、ビ タトリアピュアブルー BOH、スピロンブルー GN [保土ケ谷ィ匕学工業 (株)製]、ローダ ミン 6G等が挙げられる。 [0037] Examples of the pigment include brilliant green, eosin, ethyl violet, and Ellis mouth. Thin B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3 diphenyltriazine, alizarin red S, thymolphthalein, methyl violet 2B, quinanoresin red, rose benganole, methanole yellow, chi Monores Norehof Tarain, Xylenol Blue, Methyl Orange, Orange 4, Diphenylthiocarbazone, 2, 7 Diclonal Fluorescein, Paramethyl Red, Congo Red, Benzopurpurin 4B, a Naphthyl Red, Nile Blue A, Phenacetalin, Methyl violet, malachite green, parafuchsin, oil blue # 613 [manufactured by Orient Chemical Industry Co., Ltd.], Vitaria Pure Blue BOH, spiron blue GN [manufactured by Hodogaya Igaku Kogyo Co., Ltd.], rhodamine 6G, etc. Mentioned That.
[0038] 変色剤は、露光により可視像を与えることができるように感光性榭脂組成物中に添 加され、具体例として前記色素の他にロイコクリスタルバイオレット、ロイコマラカイトグ リーン等が挙げられる。 [0038] The color changing agent is added to the photosensitive resin composition so that a visible image can be formed by exposure. Specific examples include leuco crystal violet, leucomalachite green and the like in addition to the dye. It is done.
[0039] 本発明で得られる感光性榭脂組成物は、普通、積層構造のフォトレジストフィルムと して用いられる。該フォトレジストフィルムは、支持体フィルムに感光性榭脂組成物を 積層してなるものであり、必要に応じて更に、感光性榭脂組成物層側に保護フィルム を積層してなるものである。  [0039] The photosensitive resin composition obtained in the present invention is usually used as a photoresist film having a laminated structure. The photoresist film is formed by laminating a photosensitive resin composition on a support film and, if necessary, further laminating a protective film on the photosensitive resin composition layer side. .
[0040] 本発明に用いられる支持体フィルムは、感光性榭脂組成物層を形成する際の耐熱 性及び耐溶剤性を有するものが用いられ、前記支持体フィルムの具体例としては、 例えば、通常、ポリエステルフィルム、ポリオレフインフィルム、ポリビュルアルコールフ イルム、ポリスチレンフィルム、ポリイミドフィルム、ポリ乳酸フィルム等が挙げられるが、 本発明は力かる例示のみに限定されるものではない。尚、前記支持体フィルムの厚さ は、該フィルムの材質によって異なるので一概には決定することができず、通常該フ イルムの機械的強度等に応じて適宜調整される力 通常は 3〜50 m程度である。  [0040] The support film used in the present invention has heat resistance and solvent resistance when forming the photosensitive resin composition layer. Specific examples of the support film include, for example, Usually, a polyester film, a polyolefin film, a polybutyl alcohol film, a polystyrene film, a polyimide film, a polylactic acid film, and the like can be mentioned. However, the present invention is not limited to only powerful examples. It should be noted that the thickness of the support film varies depending on the material of the film, and thus cannot be determined unconditionally, and is usually a force that is appropriately adjusted according to the mechanical strength of the film. m.
[0041] また、支持体フィルムのヘーズとしては、低!、程レジストパターン側壁が平滑となる ため、めっき後のレジスト剥離時にレジストの引つ力かりが無くなり、レジスト剥離が確 実となる。支持体フィルムのヘーズ値としては、 1. 5%以下が好適であり、さらに好ま しくは 0. 1〜1. 0%の範囲であることが望ましい。  [0041] Further, since the haze of the support film is low and the resist pattern side wall becomes smoother, the resist pulling force is eliminated at the time of resist peeling after plating, and the resist peeling is ensured. The haze value of the support film is preferably 1.5% or less, and more preferably in the range of 0.1 to 1.0%.
[0042] 前記感光性榭脂組成物層の厚さは、 3〜300 μ m、好ましくは 5〜50 μ mであるこ と力望ましく、 3 /z m未満では塗工、乾燥する際に、被膜が不均一になったり、ピンホ ールが生じやすくなり、また 300 mより大きい場合には、露光感度が低下し、現像 速度が遅くなり好ましくない。 [0042] The photosensitive resin composition layer has a thickness of 3 to 300 µm, preferably 5 to 50 µm. If it is less than 3 / zm, the coating becomes non-uniform or pinholes are likely to occur during coating and drying, and if it is more than 300 m, the exposure sensitivity decreases and the development speed is reduced. Is slow and is not preferable.
[0043] 本発明に用いられる保護フィルムは、フォトレジストフィルムをロール状にして用いる 場合に、粘着性を有する感光性榭脂組成物層が支持体フィルムに転着したり、感光 性榭脂組成物層に埃などが付着するのを防止する目的で感光性榭脂組成物層に積 層して用いられる。力かる保護フィルムとしては、例えばポリエステルフィルム、ポリビ -ルアルコール系フィルム、ポリエチレンフィルム、ポリプロピレンフィルム、ポリ乳酸フ イルム、テフロン (登録商標）フィルム等が挙げられる力 本発明は力かる例示のみに 限定されるものではない。尚、該保護フィルムの厚さについては特に限定はなぐ通 常 10〜50 μ m、な力んづく 10〜30 μ mであればよい。  [0043] The protective film used in the present invention, when a photoresist film is used in the form of a roll, is transferred to a support film or a photosensitive resin composition layer having adhesive properties. In order to prevent dust and the like from adhering to the physical layer, it is used by being stacked on the photosensitive resin composition layer. Examples of strong protective films include polyester film, polyvinyl alcohol film, polyethylene film, polypropylene film, polylactic acid film, and Teflon (registered trademark) film. The present invention is limited only to powerful examples. It is not something. In addition, the thickness of the protective film is not particularly limited and is usually 10 to 50 μm, and the thickness may be 10 to 30 μm.
[0044] 次に、本発明の感光性榭脂組成物を用いたフォトレジストフィルムの製造及びそれ を用いる印刷配線基板の製法について説明する。  [0044] Next, the production of a photoresist film using the photosensitive resin composition of the present invention and the method for producing a printed wiring board using the same will be described.
[0045] (成層方法）  [0045] (stratification method)
上記の感光性榭脂組成物を溶液とし、これをポリエステルフィルム、ポリビニルアル コール系フィルム、ポリプロピレンフィルム、ポリスチレンフィルム等の支持体フィルム 面に塗工し、熱風にて乾燥した後、必要に応じてその塗工面の上力もポリエチレンフ イルム、ポリビュルアルコール系フィルム等の保護フィルムを被覆してフォトレジストフ イルムとする。  The photosensitive resin composition described above is used as a solution, and this is applied to a support film such as a polyester film, polyvinyl alcohol film, polypropylene film, polystyrene film, etc., dried with hot air, and then as necessary. The coating surface is also coated with a protective film such as a polyethylene film or polybulal alcohol film to form a photoresist film.
[0046] フォトレジストフィルム以外の用途としては、本発明の感光性榭脂組成物を、デイツ プコート法、フローコート法、スクリーン印刷法等の常法により、加工すべき (銅)基板 上に直接塗工し、厚さ 1〜 150 mの感光層を容易に形成することもできる。塗工時 に、メタノール、エタノール、イソプロパノール、アセトン、メチルェチルケトン、メチル セロソルブアセテート、ェチルセ口ソルブアセテート、酢酸ェチル、酢酸ブチル、シク 口へキサン、ヘプタン、メチルセ口ソルブ、テトラヒドロフラン、トルエン、キシレン等の 溶剤を添加することもできる。  [0046] As an application other than the photoresist film, the photosensitive resin composition of the present invention is directly applied on a (copper) substrate to be processed by a conventional method such as a date coating method, a flow coating method, or a screen printing method. By coating, a photosensitive layer having a thickness of 1 to 150 m can be easily formed. During coating, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl cellosolve acetate, ethyl acetate sorb acetate, ethyl acetate, butyl acetate, cyclohexane, heptane, methyl acetate solvate, tetrahydrofuran, toluene, xylene, etc. These solvents can also be added.
[0047] (露光）  [0047] (Exposure)
フォトレジストフィルムによって画像を形成させるには支持体フィルムと感光性榭脂 組成物層との接着力及び保護フィルムと感光性榭脂組成物層との接着力を比較し、 接着力の低い方のフィルムを剥離してから感光性榭脂組成物層の側を銅張基板の 銅面等の金属面に貼り付けた後、他方のフィルム上にパターンマスクを密着させて露 光する。感光性榭脂組成物が粘着性を有しないときは、前記他方のフィルムを剥離し てからパターンマスクを感光性榭脂組成物層に直接接触させて露光することもできる 。金属面に直接塗工した場合は、その塗工面に直接またはポリエステルフィルム等を 介してパターンマスクを接触させ、露光に供する。 To form an image with a photoresist film, a support film and a photosensitive resin Compare the adhesive strength with the composition layer and the adhesive strength between the protective film and the photosensitive resin composition layer. After peeling off the film with the lower adhesive strength, the photosensitive resin composition layer side is copper-clad. After being attached to a metal surface such as a copper surface of the substrate, the pattern mask is brought into close contact with the other film and exposed. When the photosensitive resin composition does not have adhesiveness, the pattern mask can be directly brought into contact with the photosensitive resin composition layer after the other film is peeled off for exposure. If the coating is applied directly to the metal surface, the pattern mask is brought into contact with the coated surface directly or via a polyester film, etc., and then subjected to exposure.
[0048] 露光は通常紫外線照射により行い、その際の光源としては、高圧水銀灯、超高圧 水銀灯、ショートアーク灯、カーボンアーク灯、キセノン灯、メタルノヽライドランプ、ケミ カルランプ、 YAGレーザー、 Arレーザー、半導体レーザー等が用いられる。紫外線 照射後は、必要に応じ加熱を行って、硬化の完全を図ることもできる。  [0048] The exposure is usually performed by ultraviolet irradiation, and as a light source at that time, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a short arc lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, a YAG laser, an Ar laser, A semiconductor laser or the like is used. After UV irradiation, heating can be performed as necessary to complete the curing.
[0049] (現像）  [0049] (Development)
露光後は、レジスト上のフィルムを剥離除去してカゝら現像を行う。本発明の感光性 榭脂組成物は稀アルカリ現像型であるので、露光後の現像は、炭酸ソーダ、炭酸カリ ゥム等のアルカリ 0. 3〜2重量％程度の稀薄水溶液を用いて行う。該アルカリ水溶液 中には、表面活性剤、消泡剤、現像を促進させるための少量の有機溶剤等を混入さ せてもよい。  After the exposure, the film on the resist is peeled and removed to perform development. Since the photosensitive resin composition of the present invention is of a dilute alkali development type, development after exposure is performed using a dilute aqueous solution of about 0.3 to 2% by weight of alkali such as sodium carbonate or potassium carbonate. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.
[0050] (エッチング、めっき） [0050] (Etching, plating)
エッチングは、通常塩化第二銅一塩酸水溶液や塩化第二鉄一塩酸水溶液等の酸 性エッチング液を用いて常法に従ってエッチングを行う。稀にアンモニア系のアル力 リエッチング液も用いられる。めっき法は、脱脂剤、ソフトエッチング剤等のめっき前処 理を用いて前処理を行った後、めっき液を用いてめっきを行う。めっき液としては銅め つき液、ニッケルめっき液、鉄めつき液、銀めつき液、金めつき液、スズめっき液、コバ ルトめっき液、亜鉛めつき液、ニッケル コバルトめっき液、はんだめつき液等が挙げ られる。殊にセミアディティブ工法においては銅めつき液が使用される。  Etching is usually performed according to a conventional method using an acidic etching solution such as an aqueous solution of cupric chloride monohydrochloride or an aqueous solution of ferric chloride monohydrochloride. In rare cases, an ammonia-based Al-reetching solution is also used. In the plating method, pretreatment is performed using a pretreatment such as a degreasing agent and a soft etching agent, and then plating is performed using a plating solution. As plating solutions, copper plating solution, nickel plating solution, iron plating solution, silver plating solution, gold plating solution, tin plating solution, cobalt plating solution, zinc plating solution, nickel cobalt plating solution, solder plating For example, a dipping solution. In particular, a copper plating solution is used in the semi-additive method.
[0051] (硬化レジストの剥離除去） [0051] (Removal removal of cured resist)
エッチング工程又はめつき工程の後、残っている硬化レジストの剥離を行う。硬化レ ジストの剥離除去は、水酸化ナトリウム、水酸ィ匕カリウム等の 0. 5〜5重量％程度の 濃度のアルカリ水溶液力もなるアルカリ剥離液を用いて行う。 After the etching process or the mating process, the remaining cured resist is peeled off. The cured resist is peeled and removed with about 0.5 to 5% by weight of sodium hydroxide, potassium hydroxide, etc. It is carried out using an alkaline stripping solution that also has a strength of alkaline aqueous solution.
[0052] また、セミアディティブ工法においては、上記のめっき工程後に、硬化レジストの剥 離を行い、酸性エッチング液によりフラッシュエッチングすることにより、回路パターン が形成される。  [0052] In the semi-additive method, the circuit pattern is formed by removing the cured resist after the plating step and performing flash etching with an acidic etching solution.
[0053] 本発明の感光性榭脂組成物及び該組成物を用いたフォトレジストフィルムは、印刷 配線板の製造、金属の精密加工、リードフィルム製造、半導体パッケージ等に用いら れるエッチングレジスト又はめつきレジストとして非常に有用であり、カルボキシル基 含有ポリマー (A)、エチレン性不飽和化合物 (B)、光重合開始剤 (C)を含有する感 光性榭脂組成物であって、カルボキシル基含有ポリマー (A)力 メタクリル酸 (al)、 フ ニル基含有ビニル系単量体 (a2)、上記（1)式で示される化合物（a3)、その他の 共重合性モノマー (a4)を特定割合で共重合してなる共重合体であるため、解像力、 密着安定性、レジスト剥離性に優れた効果を示すものであり、とりわけ半導体パッケ ージの回路形成等で採用されるセミアディティブ工法に用いるフォトレジストフィルム として非常に有用である。  [0053] The photosensitive resin composition of the present invention and a photoresist film using the composition are an etching resist or a film used for the production of printed wiring boards, precision metal processing, lead film production, semiconductor packages, and the like. It is a photosensitive resin composition containing a carboxyl group-containing polymer (A), an ethylenically unsaturated compound (B), and a photopolymerization initiator (C). Polymer (A) Strength Methacrylic acid (al), vinyl group-containing vinyl monomer (a2), compound (a3) represented by the above formula (1), and other copolymerizable monomer (a4) in specific proportions Since it is a copolymer formed by copolymerization, it exhibits excellent effects in resolving power, adhesion stability, and resist releasability. In particular, it is a photoreactive material used in semi-additive construction methods used in circuit formation of semiconductor packages. It is very useful as a strike film.
実施例  Example
[0054] 以下、実施例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を超 えない限り以下の実施例に限定されるものではな 、。  [0054] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless the gist thereof is exceeded.
尚、例中「部」、「％」とあるのは、断りのない限り重量基準を意味する。  In the examples, “parts” and “%” mean weight basis unless otherwise specified.
[0055] 下記の通り、カルボキシル基含有ポリマー (A)、エチレン性不飽和化合物（B)、光 重合開始剤 (C)及びその他の添加剤を用意した。 [0055] As described below, a carboxyl group-containing polymer (A), an ethylenically unsaturated compound (B), a photopolymerization initiator (C), and other additives were prepared.
[0056] <カルボキシル基含有ポリマー（A) > [0056] <Carboxyl group-containing polymer (A)>
[カルボキシル基含有ポリマー (A— 1) ]  [Carboxyl group-containing polymer (A-1)]
メチルメタタリレート Zスチレン Z2—ェチルへキシルカルビトールアタリレート（東亞 合成化学工業社製、「ァ口-タス M— 120」）Zメタクリル酸 =32Z30Z10Z28 (重 量比）の共重合体で、重量平均分子量は 52, 000、酸価は 182mgKOHZgである 。 〔榭脂分 40%、溶媒:メチルェチルケトン Zイソプロピルアルコール =80Z20 (重 量比)〕  Methyl metatalylate Z Styrene Z2—Ethylhexyl carbitol acrylate (Toagosei Kagaku Kogyo Co., Ltd., “Aguchi-Tas M-120”) Z copolymer of methacrylic acid = 32Z30Z10Z28 (weight ratio), weight The average molecular weight is 52,000 and the acid value is 182mgKOHZg. (40% fat, solvent: methyl ethyl ketone Z isopropyl alcohol = 80Z20 (weight ratio))
[0057] [カルボキシル基含有ポリマー (Α— 2) ] メチルメタタリレート Zスチレン Z2—ェチルへキシルカルビトールアタリレート（東亞 合成化学工業社製、「ァ口-タス M— 120」） Zメタクリル酸 = 35/30/5/30 (重量 比）の共重合体で、重量平均分子量は 60, 000、酸価は 195mgKOHZgである。〔 榭脂分 40%、溶媒:メチルェチルケトン Zイソプロピルアルコール =80Z20 (重量比 ) ] [0057] [Carboxyl group-containing polymer (Α-2)] Methyl metatalylate Z Styrene Z2—Ethylhexyl carbitol atarylate (manufactured by Toagosei Kagaku Kogyo Co., Ltd., “Aguchi-Tas M-120”) Z The polymer has a weight average molecular weight of 60,000 and an acid value of 195 mg KOHZg. [40% rosin content, solvent: methyl ethyl ketone Z isopropyl alcohol = 80Z20 (weight ratio)]
[0058] [カルボキシル基含有ポリマー（Α— 3) ]  [0058] [Carboxyl group-containing polymer (Α-3)]
メチノレメタタリレート Ζスチレン Ζラウ口キシテトラエチレングリコーノレメタタリレート Ζ メタクリル酸 =35Ζ30Ζ5Ζ30(重量比）の共重合体で、重量平均分子量は 50, 00 0、酸価は 195mgKOH/gである。〔榭脂分 40%、溶媒:メチルェチルケトン Zイソ プロピノレアノレコーノレ =80Z20 (重量比）〕  Methinoremetatalylate ΖStyrene ΖLautoxytetraethyleneglycolole methanolate ΖMethacrylic acid = 35Ζ30Ζ5Ζ30 (weight ratio) copolymer, weight average molecular weight 50,000, acid value 195mgKOH / g . [Rubber content 40%, Solvent: Methyl ethyl ketone Z Isopropino rareno reconole = 80Z20 (weight ratio)]
[0059] [カルボキシル基含有ポリマー（Α，一 1) ]  [0059] [Carboxyl group-containing polymer (Α, 1)]
メチルメタタリレート Ζスチレン Ζ2—ェチルへキシルカルビトールアタリレート（東亞 合成化学工業社製、「ァ口-タス Μ— 120」）Ζアクリル酸 =32Ζ30Ζ10Ζ28 (重量 比）の共重合体で、重量平均分子量は 55, 000、酸価は 218mgKOHZgである。〔 榭脂分 40%、溶媒:メチルェチルケトン Zイソプロピルアルコール =80Z20 (重量比 ) ]  Methyl metatalylate ΖStyrene Ζ2-Ethylhexyl carbitol acrylate (Toago Seikagaku Kogyo Co., Ltd., “Aguchi-tas Μ—120”) ΖAcrylic acid = 32Ζ30Ζ10Ζ28 (weight ratio) copolymer, weight average The molecular weight is 55,000 and the acid value is 218mgKOHZg. [40% rosin content, solvent: methyl ethyl ketone Z isopropyl alcohol = 80Z20 (weight ratio)]
[0060] [カルボキシル基含有ポリマー（Α，一 2) ]  [0060] [Carboxyl group-containing polymer (Α, 1 2)]
メチルメタタリレート Ζスチレン Ζ2—ェチルへキシルカルビトールアタリレート（東亞 合成化学工業社製、「ァ口-タス Μ— 120」）Ζメタクリル酸 =40Ζ30Ζ10Ζ20(重 量比）の共重合体で、重量平均分子量は 50, 000、酸価は 142mgKOHZgである 。 〔榭脂分 40%、溶媒:メチルェチルケトン Zイソプロピルアルコール =80Z20 (重 量比)〕  Methyl metatalylate ΖStyrene Ζ2-Ethylhexyl carbitol acrylate (manufactured by Toagosei Kagaku Kogyo Co., Ltd., “Aguchi-tas 120—120”) Ζ Methacrylic acid = 40-30 Ζ 10-20 (weight ratio) copolymer, weight The average molecular weight is 50,000 and the acid value is 142mgKOHZg. (40% fat, solvent: methyl ethyl ketone Z isopropyl alcohol = 80Z20 (weight ratio))
[0061] [カルボキシル基含有ポリマー (Α， - 3) ]  [0061] [Carboxyl group-containing polymer (Α,-3)]
メチルメタタリレート Ζスチレン Ζ2—ェチルへキシルカルビトールアタリレート（東亞 合成化学工業社製、「ァ口-タス Μ— 120」）Ζメタクリル酸 =23Ζ30Ζ10Ζ37(重 量比）の共重合体で、重量平均分子量は 59, 000、酸価は 241mgKOHZgである 。 〔榭脂分 37%、溶媒:メチルェチルケトン Zイソプロピルアルコール =80Z20 (重 量比)〕 [0062] [カルボキシル基含有ポリマー（A，—4) ] Methyl metatalylate ΖStyrene Ζ2-Ethylhexyl carbitol acrylate (manufactured by Toagosei Kagaku Kogyo Co., Ltd., “Aguchi-tas Μ—120”) The average molecular weight is 59,000, and the acid value is 241mgKOHZg. (37% rosin, solvent: methyl ethyl ketone Z isopropyl alcohol = 80Z20 (weight ratio)) [0062] [Carboxyl group-containing polymer (A, -4)]
メチルメタタリレート Z2—ェチルへキシルカルビトールアタリレート（東亞合成化学 工業社製、「ァ口-タス M— 120」） Zメタクリル酸 = 52/20/28 (重量比）の共重合 体で、重量平均分子量は 60, 000、酸価は 182mgKOHZg、である。〔榭脂分 40 %、溶媒:メチルェチルケトン Zイソプロピルアルコール =80Z20 (重量比）〕  Methyl metatalylate Z2—Ethylhexyl carbitol atarylate (manufactured by Toagosei Kagaku Kogyo Co., Ltd., “Aguchi-tas M-120”) Z The weight average molecular weight is 60,000, and the acid value is 182 mgKOHZg. [40% fat, solvent: methyl ethyl ketone Z isopropyl alcohol = 80Z20 (weight ratio)]
[0063] [カルボキシル基含有ポリマー（Α，一 5) ]  [0063] [Carboxyl group-containing polymer (Α, 1-5)]
メチルメタタリレート Ζスチレン Ζ2—ェチルへキシルカルビトールアタリレート（東亞 合成化学工業社製、「ァ口-タス Μ— 120」）Ζメタクリル酸 =22Ζ40Ζ10Ζ28 (重 量比）の共重合体で、重量平均分子量は 45, 000、酸価は 182mgKOHZgである 。 〔榭脂分 40%、溶媒:メチルェチルケトン Zイソプロピルアルコール =80Z20 (重 量比)〕  Methylmetatalylate ΖStyrene Ζ2-Ethylhexyl carbitol acrylate (Toagosei Chemical Industry Co., Ltd., “Aguchi-tas Μ—120”) Ζ Methacrylic acid = 22Ζ40Ζ10Ζ28 (weight ratio) copolymer, weight The average molecular weight is 45,000 and the acid value is 182mgKOHZg. (40% fat, solvent: methyl ethyl ketone Z isopropyl alcohol = 80Z20 (weight ratio))
[0064] [カルボキシル基含有ポリマー（Α，一 6) ]  [0064] [Carboxyl group-containing polymer (Α, 1-6)]
メチルメタタリレート Ζスチレン Ζメタクリル酸 =42/30/28 (重量比）の共重合体 で、重量平均分子量は 55, 000、酸価は 182mgKOHZgである。〔榭脂分 40%、 溶媒:メチルェチルケトン Zイソプロピルアルコール =80Z20 (重量比）〕  It is a copolymer of methylmethalate, styrene, methacrylic acid = 42/30/28 (weight ratio), and has a weight average molecular weight of 55,000 and an acid value of 182 mgKOHZg. [40% rosin content, solvent: methyl ethyl ketone Z isopropyl alcohol = 80Z20 (weight ratio)]
[0065] <エチレン性不飽和化合物（Β) > [0065] <Ethylenically unsaturated compound (Β)>
(Β— 1)：上記（2)式において、 R1:メチル基、 R4=プロピレン、 k+m= 3、 1=8. 5 の化合物（日本油脂社製、「30PDC— 800BJ ) (Β—1): In the above formula (2), R 1 : methyl group, R 4 = propylene, k + m = 3, 1 = 8.5 (Nippon Yushi Co., Ltd., “30PDC—800BJ”)
(B— 2)：上記（2)式にぉ 、て、 R1:メチル基、 R4 =プロピレン、 k + m= 14、 1= 17 の化合物（日本油脂社製、「40PDC— 1700BJ ) (B-2): In the above formula (2), R 1 : methyl group, R 4 = propylene, k + m = 14, 1 = 17 compound (manufactured by NOF Corporation, “40PDC-1700BJ”)
(B—3)：上記（2)式において、 =水素、 k+m=0、 l= 12の化合物（新中村ィ匕 学工業社製、「APG— 700」）  (B-3): In the above formula (2), = Hydrogen, k + m = 0, l = 12 (Shin-Nakamura Yigaku Kogyo Co., Ltd. “APG-700”)
(B-4)：エチレンオキサイド変性（10モル）ビスフエノール A型ジメタタリレート（新中 村ィ匕学工業社製、 ΓΒΡΕ- 500] )  (B-4): Ethylene oxide-modified (10 mol) bisphenol A type dimetatalylate (manufactured by Shin-Nakamura Yigaku Kogyo Co., Ltd., ΓΒΡΕ-500])
(B- 5)：メタクリロイルォキシェチルフタレート（共栄社ィ匕学工業社製、「HOA— MP Ej )  (B-5): Methacryloyloxetyl phthalate (manufactured by Kyoeisha Co., Ltd., “HOA—MP Ej”)
[0066] <光重合開始剤（C) >  [0066] <Photoinitiator (C)>
(C— 1) : 2, 2—ビス一（o—クロ口フエ-ル）一 4,5,4' 5' —テトラフエ-ルー 1, 2' ービイミダゾール (C-1): 2, 2-bis screw (o-black mouth) 1,4,5,4 '5' -tetra-phenol 1, 2 ' -Biimidazole
(C— 2) : 4, 4，一ビスジェチノレアミノべンゾフエノン  (C—2): 4, 4, 1 Bisjetino Reaminobenzophenone
[0067] <その他の添加剤 > [0067] <Other additives>
• ロイコクリスタルバイオレット（LCV)  • Leuco Crystal Violet (LCV)
• マラカイトグリーン (蓚酸塩）（MG)  • Malachite Green (Salt) (MG)
[0068] 実施例 1〜5及び比較例 1〜7 [0068] Examples 1 to 5 and Comparative Examples 1 to 7
下記表 1及び 2に示す如き配合組成にて配合し、感光性榭脂組成物のドープを調 製した〔榭脂分 50%、溶媒:メチルェチルケトン Zイソプロピルアルコール =86Z 14 Formulated as shown in Tables 1 and 2 below, a dope was prepared for the photosensitive resin composition (50% resin, solvent: methyl ethyl ketone Z isopropyl alcohol = 86Z 14
(重量比)〕。 (Weight ratio)].
[0069] [表 1] [0069] [Table 1]
Figure imgf000019_0001
Figure imgf000019_0001
注） 表中の （ ） 内の数値は、 固形分としての配合量 （部） である。  Note) The numerical value in () in the table is the blending amount (part) as solid content.
[0070] [表 2] 力ルポキシル基 エチレン性 光重合開始剤 その他の添加剤 含有ポリマー 不飽和化合物 (C) [0070] [Table 2] Power Lupoxyl group Ethylene photopolymerization initiator Other additives Containing polymer Unsaturated compound (C)
(A) (Β)  (A) (Β)
比較例 1 Α' 一 1 (50) Β - 1 (25) C一 1 (3. 5) LCV (0. 5)  Comparative Example 1 Α '1 1 (50) Β-1 (25) C 1 1 (3. 5) LCV (0. 5)
Β-4 (20) C- 2 (0. 2) G (0. 03) Β- 5 (5)  Β-4 (20) C- 2 (0. 2) G (0. 03) Β-5 (5)
比較例 2 A' - 2 (50) Β- 1 (25) C一 1 (3. 5) LCV (0. 5)  Comparative Example 2 A '-2 (50) Β-1 (25) C 1 1 (3.5) LCV (0.5)
Β-4 (20) C一 2 (0. 2) MG (0. 03) w Cd w Β - 5 (5)  Β-4 (20) C 1 2 (0. 2) MG (0. 03) w Cd w Β-5 (5)
比較剁 3 A' - 3 (50) Β - 1 (25) C- 1 (3. 5) LCV (0. 5)  Comparison 剁 3 A '-3 (50) Β-1 (25) C- 1 (3. 5) LCV (0. 5)
Β-4 (n (?>N20) C-2 (0. 2) MG (0. 03) Β - 5 (5)  Β-4 (n (?> N20) C-2 (0. 2) MG (0. 03) Β-5 (5)
比較例 4 A' —4 (50) Β- 1 (25) C一 1 (3. 5) LCV (0. 5)  Comparative Example 4 A '—4 (50) Β- 1 (25) C 1 1 (3. 5) LCV (0. 5)
Β-4 (20) C-2 (0. 2) MG (0. 03) Β- 5 (5)  Β-4 (20) C-2 (0. 2) MG (0. 03) Β-5 (5)
比較例 5 A' -5 (50) Β - 1 (25) C一 1 (3. 5) LCV (0. 5)  Comparative Example 5 A '-5 (50) Β-1 (25) C 1 1 (3.5) LCV (0.5)
Β-4 (20) C-2 (0. 2) MG (0. 03) Β- 5 (5)  Β-4 (20) C-2 (0. 2) MG (0. 03) Β-5 (5)
比較例 6 A' -6 (50) C— 1 (3. 5) LCV (0. 5)  Comparative Example 6 A '-6 (50) C— 1 (3. 5) LCV (0. 5)
C一 2 (0. 2) MG (0. 03) 注） 表中の （ ） 内の数値は、 固形分としての配合量 （部） である。  C 1 2 (0. 2) MG (0. 03) Note) The numbers in () in the table are the amount (parts) of solids.
上記ドープを、ギャップ 4ミルのアプリケーターを用いて、厚さ 16 μ m、ヘーズ 0.5 %のポリエステルフィルム上に塗工し、室温で 1分 30秒放置した後、 90。Cのオーブン で 3分間乾燥して、更に、その上に厚さ 21 μ mのポリエチレンフィルムで被覆し、レジ スト厚 25 μ mのフォトレジストフィルムを得た。 90. After applying the dope on a polyester film having a thickness of 16 μm and a haze of 0.5% using an applicator with a gap of 4 mil, and leaving it at room temperature for 1 minute and 30 seconds, 90. It was dried in a C oven for 3 minutes, and further coated with a 21 μm thick polyethylene film to obtain a photoresist film with a resist thickness of 25 μm.
(基板へのラミネート） (Lamination on the substrate)
このフォトレジストフィルムのポリエチレンフィルムを剥離した後、感光性榭脂組成物 層をオーブンで 60°Cに予熱した銅張基板上に、ラミネートロール温度 100。C、同口 ール圧 0. 3MPa、ラミネート速度 1. 2mZminにてラミネートした。その後 15分間の ホールドタイムをとつた。尚、ここで用いた銅張基板は厚さ 1. 6mmであり、ガラス繊 維エポキシ基材の両面に 35 μ mの銅箔を張り合わせた 200mm X 125mmの基板 で、パフ（ # 1000)研磨機に通して整面したものである。 After peeling off the polyethylene film of this photoresist film, the photosensitive resin composition layer was laminated on a copper clad substrate preheated to 60 ° C. in an oven at a laminating roll temperature of 100. C, same mouth Lamination was performed at a roll pressure of 0.3 MPa and a laminating speed of 1.2 mZmin. After that, a hold time of 15 minutes was taken. The copper-clad substrate used here is 1.6 mm thick and is a 200 mm x 125 mm substrate with 35 μm copper foil laminated on both sides of a glass fiber epoxy base. The surface is flattened through.
[0073] (露光、現像）  [0073] (Exposure, development)
次いで得られた基板に、 5kW水銀ショートアーク灯（平行光源）で、ノ ターンマスク を真空密着させて、 90mjZcm2の露光量で露光した。露光後 15分間経過してから ポリエステルフィルムを剥離し、 30°Cで 1%炭酸ナトリウム水溶液を 0. 15MPaの条 件で、ブレークポイント (未露光部分が完全に溶解する時間）の 2倍の現像時間でス プレーすることにより未露光部分を溶解除去してレジストパターンを得た。 Next, the substrate was vacuum-contacted with a 5 kW mercury short arc lamp (parallel light source) and exposed at an exposure amount of 90 mjZcm 2 . After 15 minutes of exposure, the polyester film is peeled off, and a 1% sodium carbonate aqueous solution at 30 ° C is developed at 0.15 MPa, twice the breakpoint (time when the unexposed area is completely dissolved). By spraying with time, unexposed portions were dissolved and removed to obtain a resist pattern.
[0074] 尚、パターンマスクは、露光部 Z未露光部の幅が 1Z1となる平行線パターンの線 幅力 5、 6、 7、 8、 9、 10、 11、 12、 14、 15、 16、 18、 20 mとなるネガ画像と、内 径カ ΐ50 /ζ πιのリング状で線幅力 5、 6、 7、 8、 9、 10、 12. 5、 15、 17. 5、 20 /z mと なるネガ画像が存在する合成石英クロムマスクである。  [0074] It should be noted that the line width force of the parallel line pattern in which the width of the exposed portion Z unexposed portion is 1Z1 is 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, A negative image of 18 and 20 m, and a ring width with an inner diameter of ΐ50 / ζ πι 5, 6, 7, 8, 9, 10, 12.5, 15, 17.5, 20 / zm This is a synthetic quartz chrome mask having a negative image.
[0075] (めっき）  [0075] (Plating)
現像工程後の基板にパターン銅めつきを行った。  Pattern copper plating was performed on the substrate after the development process.
めっき前処理として、 LAC— 41 (ロームアンドハース電子材料製） 20%水溶液で、 4 0°Cで 5分間処理をした後、銅めつきとして硫酸銅めつき浴にて 1. 5AZdm2で 45分 間パターンめっきを行い、 22 m厚の銅めつきパターンを形成した。 As pre-plating treatment, LAC-41 (Rohm and Haas Electronic Materials) 20% aqueous solution, treated at 40 ° C for 5 minutes, and then plated with copper sulfate in a bath of copper sulfate 1. 45 AZdm 2 Partial pattern plating was performed to form a 22 m thick copper plating pattern.
[0076] [硫酸銅めつき液]
Figure imgf000021_0001
[0076] [Copper sulfate plating solution]
Figure imgf000021_0001
98%— H SO : 98ml  98% — H SO: 98ml
2 4  twenty four
カパラシド HL (アトテック製）： 20mlZL  Kaparaside HL (Atotech): 20mlZL
カパラシド GS (アトテック製）： 0. lml/L  Kaparaside GS (Atotech): 0. lml / L
めっき工程後の基板を 2%苛性ソーダ水溶液を用い、 50°C、 0. 2MPaで 120秒ス プレーしレジストを剥離し、めっきのパターンを形成した。  The substrate after the plating process was sprayed for 120 seconds at 50 ° C and 0.2 MPa using a 2% aqueous solution of caustic soda to remove the resist and form a plating pattern.
[0077] 上記工程にぉ 、て、以下の項目を下記の如く評価した。 [0077] During the above process, the following items were evaluated as follows.
(解像力） 上記のライン Zスペース = l Z 1のパターンマスクを用 、て露光した後、ブレークポ イントの 2倍の時間で現像したとき、レジストのライン剥がれや変形がなぐライン間に 榭脂残渣もなく、画像が形成される最小ライン幅（ μ m)を金属顕微鏡で観察して評 価し 7こ。 (Resolution) After exposure using the pattern mask with the above-mentioned line Z space = l Z 1 and developing in a time twice as long as the breakpoint, there is no resin residue between the lines where resist line peeling or deformation does not occur, and the image Evaluate the minimum line width (μm) that can be formed with a metallurgical microscope.
[0078] (密着性） [0078] (Adhesion)
上記の内径力 S 150 mのリング状で線幅力 5、 6、 7、 8、 9、 10、 12. 5、 15、 17. 5 、 20 mとなるパターンを用いて露光した後、ブレークポイントの 2倍の時間で現像し たとき、レジストのライン剥がれや変形がなく画像が形成される最小ライン幅（ m)を 金属顕微鏡で観察して評価した。  Break point after exposure using pattern with inner diameter force S of 150 m and line width force of 5, 6, 7, 8, 9, 10, 12.5, 15, 17.5, 20 m The minimum line width (m) at which an image was formed without peeling or deformation of the resist when developed in twice the time was evaluated by observing with a metallurgical microscope.
[0079] (密着安定性） [0079] (Adhesion stability)
密着性が不安定な場合、現像後パターンの密着が確保されても、めっき工程中に 基材とレジストパターン間にめつき液が浸透し銅面変色が発生する。更に進行すると 銅めつきが析出することにより、 目的とする形状の回路を形成できない不具合が発生 する（めっき潜り）。この現象は、特にリング状パターンにおいて顕著である。  When the adhesion is unstable, even if the adhesion of the post-development pattern is ensured, the plating solution permeates between the base material and the resist pattern during the plating process, resulting in copper surface discoloration. As it progresses further, copper plating will precipitate, causing a problem that the circuit of the desired shape cannot be formed (plating dive). This phenomenon is particularly remarkable in a ring-shaped pattern.
従って、レジスト線幅 20 πι、内径 150 /z m幅のリング状パターンについて、レジス ト下のめっき析出、または基材銅面の変色の有無についても確認した。評価基準は 下記の通りである。  Therefore, with respect to a ring-shaped pattern having a resist line width of 20πι and an inner diameter of 150 / zm, the presence or absence of plating deposition under the resist or discoloration of the base copper surface was also confirmed. The evaluation criteria are as follows.
〇 · · ·めっき析出、銅面変色ともになし  ○ · · · Neither plating deposition nor copper surface discoloration
• · · ·めっき析出なし、銅面変色あり  • · · · No plating deposition, copper surface discoloration
X · · ·めっき析出あり  X ...
[0080] (レジスト剥離性） [0080] (Resist stripping property)
レジストを剥離した後の基板を金属顕微鏡にて観察し、露光部 Z未露光部が 18Z1 8 μ mの平行線パターン部でのレジスト剥離残渣の有無を確認した。  The substrate after the resist was peeled off was observed with a metallographic microscope, and the presence or absence of a resist peeling residue in the parallel line pattern portion where the exposed portion Z unexposed portion was 18 μm 18 μm was confirmed.
評価基準は下記の通りである。  The evaluation criteria are as follows.
• …レジスト剥離残渣なし  •… no resist stripping residue
. . . ·パターンの 50%未満の面積でレジスト剥離残渣あり  .. Resist stripping residue in less than 50% of pattern area
X · · 'パターンの 50%以上の面積でレジスト剥離残渣あり  X · · 'Resist stripping residue over 50% of pattern area
[0081] 実施例及び比較例の評価結果を表 3に示す。 闘 [0081] Table 3 shows the evaluation results of Examples and Comparative Examples. Struggle
Figure imgf000023_0001
Figure imgf000023_0001
比較例 3および比較例 4のレジスト剥離性は、 めっき不着のため評価できなかった。  The resist peelability of Comparative Examples 3 and 4 could not be evaluated due to non-plating.
本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲 を逸脱することなく様々な変更や修正をカ卩えることができることは当業者にとって明ら かである。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. .
本出願は、 2006年 2月 8日出願の日本特許出願 (特願 2006— 030470)、に基づ くものであり、その内容はここに参照として取り込まれる。 This application is based on a Japanese patent application filed on Feb. 8, 2006 (Japanese Patent Application No. 2006-030470) , the contents of which are incorporated herein by reference.
産業上の利用可能性 Industrial applicability
本発明の感光性榭脂組成物及び該組成物を用いたフォトレジストフィルムは、印刷 配線板の製造、金属の精密加工、リードフィルム製造、半導体パッケージ等に用いら れるエッチングレジスト又はめつきレジストとして非常に有用であり、カルボキシル基 含有ポリマー (A)、エチレン性不飽和化合物 (B)、及び光重合開始剤 (C)を含有す る感光性榭脂組成物であって、カルボキシル基含有ポリマー (A)が メタクリル酸 (a l )、フエニル基含有ビニル系単量体 (a2)、及び上記（1)式で示される化合物（a3)を 、共重合成分として特定割合で含む共重合体であるため、解像力、密着安定性、レ ジスト剥離性に優れた効果を示すものであり、とりわけ半導体パッケージの回路形成 等で採用されるセミアディティブ工法に用いるフォトレジストフィルムとして非常に有用 である。 The photosensitive resin composition of the present invention and a photoresist film using the composition are used as an etching resist or adhesive resist used in the production of printed wiring boards, precision metal processing, lead film production, semiconductor packages, and the like. A photosensitive resin composition containing a carboxyl group-containing polymer (A), an ethylenically unsaturated compound (B), and a photopolymerization initiator (C), comprising a carboxyl group-containing polymer ( A) is methacrylic acid ( al ), A phenyl group-containing vinyl monomer (a2), and a compound (a3) represented by the above formula (1) at a specific ratio as a copolymerization component, the resolution, adhesion stability, It exhibits an excellent effect on resist peelability, and is particularly useful as a photoresist film used in a semi-additive process employed in circuit formation of semiconductor packages.

Claims

請求の範囲 カルボキシル基含有ポリマー (A)、エチレン性不飽和化合物（B)、及び光重合開 始剤 (C)を含有する感光性榭脂組成物であって、カルボキシル基含有ポリマー (A) 力 メタクリル酸 (al)、フ ニル基含有ビニル系単量体 (a2)、及び下記（1)式で示さ れる化合物 (a3)を、共重合成分として含む共重合体であり、全共重合成分に対して のメタクリル酸（al)の含有量が 22〜35重量％で、フエ-ル基含有ビニル系単量体 ( a2)の含有量が 20〜35重量％であることを特徴とする感光性榭脂組成物。 A photosensitive resin composition containing a carboxyl group-containing polymer (A), an ethylenically unsaturated compound (B), and a photopolymerization initiator (C), wherein the carboxyl group-containing polymer (A) A copolymer containing methacrylic acid (al), a vinyl group-containing vinyl monomer (a2), and a compound (a3) represented by the following formula (1) as a copolymerization component. The photosensitivity is characterized in that the content of methacrylic acid (al) is 22 to 35% by weight and the content of the vinyl group-containing vinyl monomer (a2) is 20 to 35% by weight. A rosin composition.
[化 1]  [Chemical 1]
Figure imgf000025_0001
Figure imgf000025_0001
ここで、 R1は水素又はメチル基、 R2はエチレン基又はプロピレン基、 R3は炭素数 8〜Here, R 1 is hydrogen or methyl group, R 2 is ethylene group or propylene group, R 3 is carbon number 8 ~
22個のアルキル基、 nは 1〜4の整数である。 22 alkyl groups, n is an integer of 1 to 4.
[2] フエ-ル基含有ビニル系単量体 (a2)がスチレンであることを特徴とする請求項 1記 載の感光性榭脂組成物。 [2] The photosensitive resin composition according to claim 1, wherein the vinyl group-containing vinyl monomer (a2) is styrene.
[3] (1)式で示される化合物（a3)力 ¾ ェチルへキシルカルビトール (メタ）アタリレート であることを特徴とする請求項 1又は 2記載の感光性榭脂組成物。 [3] The photosensitive resin composition according to claim 1 or 2, wherein the compound represented by the formula (1) is (a3) strength hexyl carbitol (meth) acrylate.
[4] カルボキシル基含有ポリマー（A)の重量平均分子量が 30, 000〜100, 000であ り、ポリマー酸価が 175〜250mgKOHZgであることを特徴とする請求項 1〜3いず れか記載の感光性榭脂組成物。 [4] The carboxyl group-containing polymer (A) has a weight average molecular weight of 30,000 to 100,000, and a polymer acid value of 175 to 250 mgKOHZg. Photosensitive resin composition.
[5] エチレン性不飽和化合物（B)として、下記（2)式で示される化合物 (bl)を含有して なることを特徴とする請求項 1〜4いずれか記載の感光性榭脂組成物。 [5] The photosensitive resin composition according to any one of [1] to [4], comprising a compound (bl) represented by the following formula (2) as the ethylenically unsaturated compound (B): .
[化 2] CH^CR!-COO- (C2H4O) k- (RO) 1- (C2H4O) m— CO— CE^CHs · · · ( 2 ) [Chemical 2] CH ^ CR! -COO- (C2H4O) k- (RO) 1- (C2H4O) m — CO— CE ^ CHs · · · · (2)
ここで、 R1は水素原子又はメチル基、 R4はプロピレン基又はブチレン基、 1、 k、 mは整 数であり、 k+mの平均値が 2〜6、 1の平均値が 10〜25である。 Here, R 1 is a hydrogen atom or a methyl group, R 4 is a propylene group or a butylene group, 1, k, m are integers, the average value of k + m is 2 to 6, and the average value of 1 is 10 to 25.
[6] 光重合開始剤 (C)として、口フィン二量体を含有してなることを特徴とする請求項 1[6] The photopolymerization initiator (C) comprises an oral fin dimer.
〜5 ヽずれか記載の感光性榭脂組成物。 -5 Photosensitive resin composition according to any deviation.
[7] 請求項 1〜6いずれか記載の感光性榭脂組成物の層と、ヘーズ値 1. 5以下の支持 体フィルムとを含むことを特徴とするフォトレジストフィルム。 [7] A photoresist film comprising a layer of the photosensitive resin composition according to any one of claims 1 to 6 and a support film having a haze value of 1.5 or less.
[8] 更に、保護フィルムを感光性榭脂組成物層側に有することを特徴とする請求項 7記 載のフォトレジストフィルム。  8. The photoresist film according to claim 7, further comprising a protective film on the photosensitive resin composition layer side.
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