WO2010016258A1 - Composition de résine photodurcissable ignifuge, film sec et produit durci obtenus à partir de celle-ci, et carte de câblage imprimé utilisant la composition, le film sec ou le produit durci - Google Patents

Composition de résine photodurcissable ignifuge, film sec et produit durci obtenus à partir de celle-ci, et carte de câblage imprimé utilisant la composition, le film sec ou le produit durci Download PDF

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Publication number
WO2010016258A1
WO2010016258A1 PCT/JP2009/003770 JP2009003770W WO2010016258A1 WO 2010016258 A1 WO2010016258 A1 WO 2010016258A1 JP 2009003770 W JP2009003770 W JP 2009003770W WO 2010016258 A1 WO2010016258 A1 WO 2010016258A1
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Prior art keywords
flame
resin composition
composition
group
photocurable resin
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PCT/JP2009/003770
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English (en)
Japanese (ja)
Inventor
米田一善
横山裕
有馬聖夫
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太陽インキ製造株式会社
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Priority to CN2009801305593A priority Critical patent/CN102112921B/zh
Publication of WO2010016258A1 publication Critical patent/WO2010016258A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/05—Forming flame retardant coatings or fire resistant coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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
    • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2400/00—Characterised by the use of unspecified polymers
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/012—Flame-retardant; Preventing of inflammation

Definitions

  • the present invention relates to a flame retardant photocurable resin composition that can be developed with a dilute alkaline aqueous solution, in particular, a solder resist composition that is photocured by ultraviolet exposure or laser exposure, its dry film and cured product, and using them.
  • the present invention relates to a printed wiring board having a formed flame-retardant cured film.
  • FPC printed wiring boards and flexible wiring boards
  • solder resist which is a part of these, also requires flame resistance.
  • the FPC is usually made of a polyimide substrate, it is a thin film unlike a printed wiring board of a glass epoxy substrate.
  • the solder resist to be applied has the same film thickness on both the printed wiring board and the FPC, in the case of a thin-film FPC, the burden on the solder resist is relatively increased.
  • Patent Document 1 discloses (a) a binder polymer, (b) a halogenated aromatic ring such as a bromophenyl group, and a polymerizable ethylenic group such as a (meth) acryloyl group.
  • JP-A-2001-75270 Patent Document 2 describes (a) epoxy acrylate resin, (b) epoxy resin, (c) diluent, (d) curing agent, and (e) curing acceleration.
  • the photosensitive resin composition characterized by containing, Unexamined-Japanese-Patent No.
  • the present invention has been made in view of the prior art as described above, has a non-halogen composition, has a low environmental load, is excellent in both flame retardancy and storage stability, is rich in flexibility of a cured film, and is suitable for various substrates.
  • a flame retardant photocurable resin composition that can form a cured film with a fine pattern that is excellent in adhesion, solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, etc., and is particularly suitable for FPC It is intended to provide.
  • the object of the present invention is to provide a flame retardant dry film and cured product excellent in the above-mentioned various characteristics obtained by using such a photocurable resin composition, and a solder with the dry film or cured product.
  • An object of the present invention is to provide a printed wiring board on which a flame-retardant cured film such as a resist is formed.
  • a flame retardant comprising (A) a phosphazene compound that is liquid at room temperature, (B) a carboxyl group-containing resin, and (C) a photopolymerization initiator.
  • a photocurable resin composition is provided.
  • the carboxyl group-containing resin (B) is a carboxyl group-containing polyurethane resin.
  • room temperature means the working room temperature, generally 20 to 30 ° C., usually 25 ° C.
  • it further contains (D) a photopolymerizable monomer, or further contains (E) a thermosetting resin.
  • the thermosetting resin (E) preferably contains an epoxy resin having a biphenyl skeleton.
  • a flame retardant photocurable dry film obtained by applying and drying the flame retardant photocurable resin composition on a carrier film, or the flame retardant photocurable resin.
  • a flame retardant cured product obtained by curing the composition or the dry film is also provided.
  • curing the said flame-retardant photocurable resin composition or a dry film is also provided.
  • the flame-retardant photocurable resin composition of the present invention uses a phosphazene derivative that is liquid at room temperature together with a carboxyl group-containing resin, once dissolved in a photosensitive composition as in the past, it is re-used during storage. There is no phenomenon of crystallization or precipitation of crystals with time after coating and drying, so that a relatively large amount of the phosphazene compound can be added, the flame retardancy effect becomes very large, and the liquid composition And it is excellent in stability as a dry film. Therefore, non-halogen composition with low environmental impact and excellent flame retardancy, rich cured film flexibility, adhesion to various substrates, solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, etc.
  • the flame-retardant photocurable resin composition of the present invention can be advantageously applied to the formation of a flame-retardant cured film such as a printed wiring board, particularly an FPC solder resist.
  • the flame-retardant photocurable resin composition of the present invention is characterized in that the phosphazene compound (A) that is liquid at room temperature is used together with the carboxyl group-containing resin (B).
  • the phosphazene compound (A) that is liquid at room temperature is used together with the carboxyl group-containing resin (B).
  • the phosphazene compound (A) that is liquid at room temperature contained in the flame-retardant photocurable resin composition of the present invention is a viscous liquid or liquid at 25 ° C., and is preferably subjected to the following conditions. Those having characteristics are preferred. -Halogen free (other than ionic impurities). -5% weight loss is 260 ° C or higher.
  • the phosphazene compound represented by the general formula (I) may be linear or cyclic, and may have a molecular weight distribution in a plurality of mixtures.
  • R 1 and R 2 are preferably independently asymmetric or independently different substituents. From the viewpoint of heat resistance, it is more preferable that R 1 and R 2 have at least one organic group-substituted or unsubstituted phenoxy structure.
  • the smaller the number of m the stronger the crystallization, but the easier it is to dissolve in the diluent used in the photosensitive composition, and the composition often recrystallizes over time in the cooled or dried state. . Therefore, liquefaction is achieved by controlling the molecular weight distribution of the ring or linear material, the types of R 1 and R 2 , etc. in the production stage.
  • Specific examples of the phosphazene compound (A) which is liquid at room temperature include FP-366 and FP-390 manufactured by Fushimi Pharmaceutical Co., Ltd.
  • the blending amount of the phosphazene compound (A) which is liquid at room temperature is 0.5 to 30% by mass, preferably 1 to 20% by mass in the total composition.
  • the amount is more than the above range, the tack-free performance of the coating film is lowered or the viscosity of the composition is increased, which is not preferable.
  • the carboxyl group-containing resin (B) contained in the flame retardant photocurable resin composition of the present invention a known and commonly used resin compound containing a carboxyl group in the molecule can be used. Furthermore, it is preferable to use a carboxyl group-containing photosensitive resin (B ′) having an ethylenically unsaturated double bond in the molecule because photocurability can be imparted and an alkali developable composition is obtained.
  • the unsaturated double bond is preferably derived from (meth) acrylic acid or a (meth) acrylic acid derivative.
  • the carboxyl group-containing resin which does not have an ethylenically unsaturated double bond
  • it has two or more ethylenically unsaturated groups in the molecule
  • the carboxyl group-containing resin (B) compounds listed below (any of oligomers and polymers) can be suitably used.
  • Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers
  • a carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
  • Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its modified partial anhydride, carboxyl group-containing dialcohol compound and diol compound.
  • a compound having one hydroxyl group and one or more (meth) acryl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing urethane resin.
  • one isocyanate group and one or more (meth) acryl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.
  • the carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.
  • a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
  • Functional carboxyl group-containing resin is
  • a carboxyl group-containing polyester resin obtained by reacting a difunctional oxetane resin as described later with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
  • a photosensitive carboxyl group-containing resin obtained by adding a compound having one epoxy group and one or more (meth) acryl groups in one molecule to the resins (1) to (8).
  • carboxyl group-containing resins preferred are (X) carboxy group-containing polyurethane resins, particularly those in which the isocyanate groups of the urethane resin containing isocyanate groups (including diisocyanates) are not directly bonded to the benzene ring.
  • (Y) the polyfunctional epoxy resin used in the synthesis of the resins of (6) and (7) above is bisphenol A structure, bisphenol F structure, biphenol structure, bisxylenol. In the case of a compound having a structure and its hydrogenated compound, it is preferable from the viewpoints of heat resistance and flame retardancy.
  • the carboxylic group-containing polyurethane resins (1), (2), (3) and (4) and the modified products such as (9) have a urethane bond in the main chain. And preferred for warping. Furthermore, in order to achieve both properties such as flexibility and solder heat resistance, the carboxyl group-containing urethane resins (1), (2), (3), (4) and modified products such as those (9) And, it is most preferable to use the carboxyl group-containing resins (5), (6), (7) and (8) and modified products such as (9) in combination.
  • (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
  • the acid value of the carboxyl group-containing resin (B) is desirably in the range of 40 to 200 mgKOH / gg, more preferably in the range of 45 to 120 mgKOH / g.
  • the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult.
  • the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary.
  • the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.
  • the weight average molecular weight of the carboxyl group-containing resin (B) varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000.
  • the weight average molecular weight is less than 2,000, the tack-free performance of the coating film may be inferior, the moisture resistance of the coating film after exposure may be poor, the film may be reduced during development, and the resolution may be greatly inferior.
  • the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.
  • the blending amount of the carboxyl group-containing resin (B) as described above is 10 to 60% by mass, preferably 20 to 50% by mass in the entire composition.
  • the amount is less than the above range, the coating strength is lowered, which is not preferable.
  • the amount is larger than the above range, the viscosity of the composition is increased or the coating property is lowered, which is not preferable.
  • photopolymerization initiator (C) used in the present invention known and commonly used compounds can be used.
  • a particularly preferred photopolymerization initiator there is a phosphorus element-containing photopolymerization initiator, which has an effect of improving flame retardancy while being a photopolymerization initiator.
  • an acylphosphine oxide photopolymerization initiator having a group represented by the following general formula (II-1) can be preferably used.
  • each of R 3 and R 4 independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a cyclohexyl group, or cyclopentyl.
  • Examples of the acylphosphine oxide photopolymerization initiator having a group represented by the general formula (II-1) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl)- Examples thereof include phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide.
  • Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure (registered trademark) 819 manufactured by Ciba Specialty Chemicals.
  • R 3 has the same meaning as described above, and R 5 is, independently of R 3 , a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group. Or an aryl group substituted with a halogen atom or an alkyl group, and an R—C ( ⁇ O) — group (where R is a hydrocarbon group having 1 to 20 carbon atoms).
  • the blending amount of such a phosphorus element-containing photopolymerization initiator can be selected from the range of 1 to 80 parts by mass, preferably 2 to 50 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (B). .
  • the photopolymerization initiator that can be added in addition to the phosphorus element-containing photopolymerization initiator includes an oxime ester photopolymerization initiator having a group represented by the following general formula (III), represented by the following general formula (IV): There are ⁇ -aminoacetophenone photopolymerization initiators having the following groups.
  • R 6 represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), R 7 is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups).
  • a cycloalkyl group having 5 to 8 carbon atoms an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 6 carbon atoms)
  • R 8 and R 9 each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group
  • R 10 and R 11 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded.
  • the oxime ester photopolymerization initiator having a group represented by the general formula (III) is preferably 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (V):
  • the compound represented by the following general formula (VI) and the compound represented by the following general formula (VII) are mentioned.
  • R 12 is a hydrogen atom, halogen atom, alkyl group having 1 to 12 carbon atoms, cyclopentyl group, cyclohexyl group, phenyl group, benzyl group, benzoyl group, alkanoyl group having 2 to 12 carbon atoms, or 2 to 2 carbon atoms. 12 alkoxycarbonyl groups (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and one or more oxygen atoms are placed in the middle of the alkyl chain.
  • R 13 and R 15 are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), R 14 is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms
  • a cycloalkyl group having 5 to 8 carbon atoms may have one or more oxygen atoms in the middle of the alkyl chain
  • a cycloalkyl group having 5 to 8 carbon atoms may have one or more oxygen atoms in the middle of the alkyl chain
  • an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having a carbon number).
  • R 16 , R 17 and R 22 each independently represents an alkyl group having 1 to 12 carbon atoms
  • R 18 , R 19 , R 20 and R 21 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • M represents O, S or NH
  • n and p each independently represents an integer of 0 to 5.
  • oxime ester photopolymerization initiators 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the formula (V) and a compound represented by the formula (VI) are more preferable.
  • Examples of commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Specialty Chemicals, and N-1919 manufactured by ADEKA Corporation. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.
  • Examples of the ⁇ -aminoacetophenone photopolymerization initiator having a group represented by the general formula (IV) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like.
  • Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.
  • the blending amount of the photopolymerization initiator (C) as described above is in the range of 0.01 to 50 parts by mass, preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (B). You can choose from. If it is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off or the coating film properties such as chemical resistance are deteriorated. On the other hand, if it exceeds 50 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator (C) becomes violent and the deep curability tends to decrease, which is not preferable.
  • the blending amount is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (B). It is desirable to select from the range of 20 parts by mass, more preferably from 0.01 to 5 parts by mass.
  • photopolymerization initiators, photoinitiator assistants and sensitizers that can be suitably used in the photocurable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenones.
  • a compound, a xanthone compound, a tertiary amine compound, etc. can be mentioned.
  • benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
  • acetophenone compound examples include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone.
  • anthraquinone compound examples include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.
  • thioxanthone compound examples include, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.
  • ketal compound examples include acetophenone dimethyl ketal and benzyl dimethyl ketal.
  • benzophenone compound include, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyldiphenyl. Sulfide.
  • tertiary amine compound examples include, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylamino.
  • an ethanolamine compound a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylamino.
  • Dialkylamino benzophenones such as benzophenone (EAB manufactured by Hodogaya Chemical Co.), and dialkylamino groups such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin) Contained coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA, Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB, International Bio-Synthetics), 4-dimethylaminobenzoic acid n-butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhe
  • the composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep curable properties. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone A thioxanthone compound such as
  • the amount of such a thioxanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the carboxyl group-containing resin (B). If the amount of the thioxanthone compound is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.
  • a compound having a dialkylaminobenzene structure is preferable, among which a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable.
  • a dialkylaminobenzophenone compound 4,4'-diethylaminobenzophenone is preferable because of its low toxicity.
  • a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has a maximum absorption wavelength in the ultraviolet region, so that it is less colored and uses a color pigment as well as a colorless and transparent photosensitive composition.
  • a colored solder resist film reflecting the color can be provided.
  • 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.
  • the amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (B). It is. When the amount of the tertiary amine compound is 0.1 parts by mass or less, there is a tendency that a sufficient sensitizing effect cannot be obtained. When the amount exceeds 20 parts by mass, light absorption on the surface of the dried solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease.
  • photopolymerization initiators can be used alone or as a mixture of two or more.
  • the total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably in the range of 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin (B). When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.
  • a conventionally known (meth) acrylate monomer can be used as the photopolymerizable monomer (D) blended in the composition of the present invention to form an image with light.
  • Conventionally known (meth) acrylate monomers include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl
  • Polyhydric alcohols such as isocyanurates or polyhydric acrylates such as these ethylene oxide adducts, propylene oxide adducts or caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene of these phenols
  • Polyhydric acrylates such as oxide adducts; and urethane acrylates of the above polyal
  • a phosphorus element-containing acrylate is preferable from the viewpoint of flame retardancy.
  • phosphate polyfunctional acrylates typified by trisacryloyloxyethyl phosphate, or specifically phosphorus-containing compound-modified acrylates represented by the following general formula (VIII) can be mentioned.
  • R 23 is an acrylate residue
  • R 24 and R 25 are acrylate derivatives which are organic groups other than hydrogen or halogen.
  • Such phosphorus-containing compound-modified acrylates can generally be synthesized by a Michael addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with a conventionally known polyfunctional acrylate. .
  • thermosetting resin (E) can be added as a thermosetting component.
  • a thermosetting component (E) having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.
  • cyclic (thio) ether groups cyclic (thio) ether groups
  • a bifunctional epoxy resin is preferable, and diisocyanate or its polyfunctional blocked isocyanate can also be used.
  • thermosetting component (E) having two or more cyclic (thio) ether groups in such a molecule is either a three-, four- or five-membered cyclic ether group or a cyclic thioether group in the molecule.
  • a compound having two or more of two types of groups for example, a compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound (E-1), at least two oxetanyl in the molecule
  • Examples of the polyfunctional epoxy compound (E-1) include jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 1050, and Epitome 2055 manufactured by Dainippon Ink and Chemicals, Inc. Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Kasei Chemical Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R.
  • Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Japan Epoxy Resin Co., Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd. D. Chemicals manufactured by Dow Chemical Company.
  • E. R. 542 Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R.
  • E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink & Chemicals, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170 manufactured by Toto Kasei Co., YDF- 175, YDF-2004, Araldide XPY306 manufactured by Ciba Specialty Chemicals (both trade names), bisphenol F type epoxy resins; Epototo ST-2004, ST-2007, ST-3000 (trade names, manufactured by Tohto Kasei) Hydrogenated bisphenol A type epoxy resin such as: jER604 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumi-Epoxy ELM manufactured by Sumitom
  • Xylenol type or biphenol type epoxy resins or mixtures thereof bisphenol S type such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin; YL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals, etc.
  • bisphenol S type such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin
  • bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin
  • Tetraphenylolethane type epoxy resin Tetraphenylolethane type epoxy resin
  • Heterocyclic epoxy resins such as Araldide PT810 manufactured by BA Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries (both trade names); biphenyl novolac resins such as NC-3000 and NC-3100 manufactured by Nippon Kayaku Co., Ltd.
  • Diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats
  • tetraglycidyl xylenoyl ethane resin such as ZX-1063 manufactured by Tohto Kasei
  • Naphthalene group-containing epoxy resins such as HP-4032, EXA-4750 and EXA-4700; Epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink and Chemicals, Inc. CP- manufactured by Nippon Oil & Fats Co., Ltd.
  • glycidyl methacrylate such as 50S and CP-50M Compound epoxy resin; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industries), CTBN-modified epoxy resin (for example, YR-102 manufactured by Tohto Kasei Co., Ltd.) , YR-450 and the like), but are not limited thereto.
  • These epoxy resins can be used alone or in combination of two or more.
  • an epoxy resin having a biphenyl skeleton such as a biphenyl novolac type epoxy resin is particularly preferable.
  • Examples of the polyfunctional oxetane compound (E-2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3- In addition to polyfunctional oxetanes such as ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane Alcohol and novolak resin, poly (p-
  • Examples of the compound (E-3) having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resins. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
  • the amount of the thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule is preferably 0.6 relative to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (B). It is in the range of ⁇ 2.5 equivalents, more preferably 0.8 ⁇ 2.0 equivalents.
  • the blending amount of the thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule is less than 0.6 equivalents, carboxyl groups remain in the solder resist film, heat resistance, alkali resistance, This is not preferable because the electrical insulation property is lowered.
  • the amount exceeds 2.5 equivalents the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.
  • the photocurable resin composition of the present invention can further contain a phosphorus-containing compound as a flame retardant auxiliary.
  • a phosphorus-containing compound those conventionally known as organic phosphorus flame retardants may be used, and examples include phosphoric acid esters and condensed phosphoric acid esters, cyclic phosphazene compounds, phosphazene oligomers, and compounds represented by the following general formula (IX).
  • R26, R27 and R28 each independently represent a substituent other than a halogen atom.
  • Commercially available products of the compound represented by the general formula (IX) include HCA, SANKO-220, M-ESTER, HCA-HQ and the like.
  • thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule it is preferable to contain a thermosetting catalyst.
  • thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole.
  • Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide; benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine.
  • Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like.
  • thermosetting catalyst for epoxy resins or oxetane compounds or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used.
  • thermosetting component (E) having a carboxyl group-containing resin (B) or two or more cyclic (thio) ether groups in the molecule.
  • the amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass with respect to 100 parts by mass.
  • the photocurable resin composition of the present invention can contain a colorant.
  • a colorant conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.
  • Blue colorant include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds classified as Pigment, specifically, the following color index (CI; The Society of Dyers and Colorists) (Issued by The Society of Dyers and Colorists) can be listed with numbers: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4 , Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.
  • CI The Society of Dyers and Colorists
  • the dye systems include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used.
  • a metal-substituted or unsubstituted phthalocyanine compound can also be used.
  • Green colorant examples include phthalocyanine, anthraquinone, and perylene. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
  • Yellow colorant examples include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
  • Anthraquinone series Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
  • Isoindolinone type Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
  • Condensed azo series Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.
  • Benzimidazolone series Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.
  • Monoazo Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183.
  • Disazo Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.
  • Red colorant examples include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. It is done.
  • Monoazo Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
  • Disazo Pigment Red 37, 38, 41.
  • Monoazo lakes Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1,68.
  • Benzimidazolone series Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.
  • Perylene series Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.
  • Diketopyrrolopyrrole series Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
  • Condensed azo series Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242.
  • Anthraquinone series Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.
  • Kinacridone series Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.
  • a colorant such as purple, orange, brown, or black may be added.
  • the blending ratio of the colorant as described above is not particularly limited, but is preferably 0 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (B). Is sufficient.
  • a filler can be blended as necessary in order to increase the physical strength of the coating film.
  • a filler at least one selected from the group consisting of known and commonly used inorganic fillers and organic fillers can be used, but inorganic fillers, particularly barium sulfate, spherical silica and talc are preferably used.
  • inorganic fillers particularly barium sulfate, spherical silica and talc are preferably used.
  • metal oxide fine particles may be added, and specific examples include aluminum hydroxide, magnesium hydroxide, boehmite and the like.
  • the blending amount of these fillers is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, and particularly preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (B). Part.
  • the blending amount of the filler exceeds 300 parts by mass, it is not preferable because the viscosity of the photocurable resin composition becomes high and the printability is lowered or the cured product becomes brittle.
  • the photocurable resin composition of the present invention uses an organic solvent for the synthesis of the carboxyl group-containing resin (B), the preparation of the composition, or the viscosity adjustment for application to a substrate or a carrier film.
  • organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like.
  • ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane
  • the photo-curable resin composition of the present invention further contains, as necessary, known and commonly used thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, and phenothiazine, finely divided silica, organic bentonite, and montmorillonite.
  • thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, and phenothiazine, finely divided silica, organic bentonite, and montmorillonite.
  • Known and commonly used thickeners silicone-based, fluorine-based and polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, rust inhibitors, etc.
  • the known and conventional additives such as can be blended.
  • the photocurable resin composition of the present invention can also be in the form of a dry film comprising a carrier film (support) and a layer made of the photocurable resin composition formed on the carrier film.
  • the photocurable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and is applied to a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll.
  • a film can be obtained by applying a uniform thickness on a carrier film with a coater, gravure coater, spray coater or the like, and drying usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes.
  • the coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 10 to 150 ⁇ m, preferably 20 to 60 ⁇ m.
  • a plastic film As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used.
  • the thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 ⁇ m.
  • a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film.
  • a peelable cover film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used, and when the cover film is peeled off, the adhesive strength between the film and the carrier film is exceeded. What is necessary is just to have a smaller adhesive force between the membrane and the cover film.
  • the photocurable resin composition according to the present invention or this dry film becomes a cured product by being photocured on copper.
  • Photocuring can be performed by an ultraviolet exposure apparatus, but it can also be cured by laser light having a wavelength of 350 to 410 nm.
  • a dry film, a cured product, and a printed wiring board are formed as follows. That is, the photocurable resin composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and is applied on the substrate by a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen.
  • a tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100.degree.
  • the photocurable resin composition layer is laminated on the substrate so that the carrier film is in contact with the carrier film.
  • a resin insulating layer By peeling off, a resin insulating layer can be formed.
  • the contact type (or non-contact type) is selectively exposed with active energy rays through a photomask having a pattern formed, and the unexposed portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution).
  • a dilute alkaline aqueous solution for example, 0.3 to 3% sodium carbonate aqueous solution.
  • a resist pattern is formed.
  • a composition containing a thermosetting component (E) for example, by heating to a temperature of about 140 to 180 ° C.
  • thermosetting component (E) having two or more cyclic ether groups and / or cyclic thioether groups reacted with each other, and was excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.
  • a cured coating film can be formed.
  • thermosetting component (E) is not contained, by performing heat treatment, the ethylenically unsaturated bond remaining in an unreacted state at the time of exposure undergoes thermal radical polymerization, and the coating film characteristics are improved.
  • heat treatment thermosetting
  • the base material examples include printed circuit boards and flexible printed circuit boards that are pre-formed with a circuit, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin. , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminates of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET A film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.
  • the volatile drying performed after the photocurable resin composition of the present invention is applied is a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (with a heat source of an air heating method using steam, Can be carried out using a method in which the hot air is brought into countercurrent contact, or a method in which the hot air is blown onto the support from a nozzle.
  • the exposure equipment used for the active energy ray irradiation includes a laser direct lithography system (laser direct imaging system), an exposure machine equipped with a metal halide lamp, an exposure machine equipped with a (super) high-pressure mercury lamp, and a mercury short arc lamp. Or a direct drawing apparatus using an ultraviolet lamp such as a (super) high-pressure mercury lamp can be used.
  • a laser beam having a maximum wavelength in the range of 350 to 410 nm is used as the active energy ray
  • either a gas laser or a solid laser may be used.
  • the exposure amount varies depending on the film thickness and the like, but can be generally in the range of 5 to 200 mJ / cm 2 , preferably 5 to 100 mJ / cm 2 , more preferably 5 to 50 mJ / cm 2 .
  • the direct drawing apparatus for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any apparatus may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .
  • the developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.
  • Curing agent formulation examples 1 and 2 Each component shown in Table 2 was blended in the proportions (parts by mass) shown in Table 2, preliminarily mixed with a stirrer, and then kneaded with a three-roll mill to prepare a varnish of a hardener composition for solder resist.
  • ⁇ Electroless gold plating resistance> Using a commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 3 ⁇ m and gold 0.03 ⁇ m, and the presence or absence of peeling of the resist layer or plating penetration is confirmed by tape peeling. After the evaluation, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows. ⁇ : Infiltration and peeling are not seen. ⁇ : Slight penetration is observed after plating, but does not peel off after tape peeling. X: Permeation is observed after plating, and peeling is also observed after tape peeling.
  • thermosetting was performed at 150 ° C. for 60 minutes to obtain an evaluation sample.
  • This flame retardant evaluation sample was subjected to a thin material vertical combustion test based on the UL94 standard. The evaluation was expressed as VTM-0 or VTM-1 based on the UL94 standard.
  • compositions of each Example and Comparative Example were applied to a 25 ⁇ m polyimide film (Kapton 100H) by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature to obtain a single-side coated substrate.
  • the entire surface of the solder resist is exposed to this substrate with an optimum exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. is applied under a spray pressure of 0.2 MPa.
  • Second development was performed, and thermosetting was performed at 150 ° C. for 60 minutes.
  • the solder resist of the obtained sample is turned outside, and 180 ° bending by goat folding is repeated several times, and the crack occurrence state in the coating film at that time is observed visually and with an optical microscope with a magnification of 200, and no crack is generated. The number of times was evaluated.
  • Table 5 shows the results of the evaluation tests.
  • the flame-retardant photocurable resin compositions of Examples 1 to 4 of the present invention not only have excellent storage stability but also solder heat resistance, Excellent electroless gold plating resistance, electrical properties, flame retardancy, and flexibility.
  • Examples 5-8 A flame-retardant photocurable resin composition prepared according to Examples 1 to 4 shown in Table 4 was diluted with methyl ethyl ketone, applied onto a carrier film, and dried by heating to form a photosensitive resin composition layer having a thickness of 20 ⁇ m. Then, a cover film was laminated thereon to obtain a dry film. Thereafter, the cover film was peeled off, and the film was bonded to the patterned polyimide film substrate using a laminator.
  • the substrate is exposed to the solder resist pattern at an optimum exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, the carrier film is peeled off, and then a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. is sprayed. Development was performed for 60 seconds under the condition of 0.2 MPa to obtain a resist pattern. Thereafter, heat curing was performed for 60 minutes in a hot air dryer at 150 ° C. to prepare a test substrate. About the test board
  • the evaluation of the grain stability over time in the dry film state was performed as follows. That is, the flame retardant photocurable resin composition prepared according to Example 1 and Comparative Example 1 shown in Table 4 was diluted with methyl ethyl ketone, applied onto a carrier film, dried by heating, and a photosensitive resin having a thickness of 20 ⁇ m. A composition layer was formed, and a cover film was laminated thereon to create a dry film. The prepared dry film was stored for one week at 5 ° C. in the same manner as in the above-mentioned ⁇ Grade stability over time> evaluation. No grain was confirmed in the dry film obtained from the composition of Example 1, but a comparative example. Grain was confirmed in the dry film prepared from the composition of No. 1.

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Abstract

L'invention porte sur une composition de résine photodurcissable ignifuge sans halogène dont l’impact environnemental est faible. La composition de résine photodurcissable ignifuge présente un caractère ignifuge et une stabilité de stockage excellents et est apte à former un film de revêtement durci qui présente une excellente souplesse. L'invention porte également sur un film sec et sur un produit durci de la composition ainsi que sur une carte de câblage imprimé comportant un film de revêtement durci ignifuge tel qu'une réserve de soudure obtenue à l'aide de la composition, du film sec ou du produit durci. La composition de résine photodurcissable ignifuge contient (A) un composé de phosphazène à l'état liquide à température ambiante ; (B) une résine contenant un groupe carboxyle ; et (C) un initiateur de photopolymérisation. De préférence, la résine contenant un groupe carboxyle (B) est une résine de polyuréthane contenant un groupe carboxyle. De préférence, la composition de résine photodurcissable ignifuge contient de plus (D) un monomère photopolymérisable ou (E) une résine thermodurcissable. La composition de résine photodurcissable ignifuge, en particulier une composition de résine ignifuge photodurcissable/thermodurcissable contenant la résine thermodurcissable (E), peut être utilisée comme réserve de soudure.
PCT/JP2009/003770 2008-08-07 2009-08-06 Composition de résine photodurcissable ignifuge, film sec et produit durci obtenus à partir de celle-ci, et carte de câblage imprimé utilisant la composition, le film sec ou le produit durci WO2010016258A1 (fr)

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JP2016000782A (ja) * 2014-06-12 2016-01-07 パナソニックＩｐマネジメント株式会社 エポキシ樹脂組成物、金属張積層板、及びパッケージ用基板材料

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