WO2010016256A1 - Flame-retardant photocurable resin composition, dry film and cured product of the same, and printed wiring board using the composition, dry film or cured product - Google Patents
Flame-retardant photocurable resin composition, dry film and cured product of the same, and printed wiring board using the composition, dry film or cured product Download PDFInfo
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- WO2010016256A1 WO2010016256A1 PCT/JP2009/003764 JP2009003764W WO2010016256A1 WO 2010016256 A1 WO2010016256 A1 WO 2010016256A1 JP 2009003764 W JP2009003764 W JP 2009003764W WO 2010016256 A1 WO2010016256 A1 WO 2010016256A1
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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
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
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- 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
-
- 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
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.
- JP 2007-10794 A Patent Document 1 describes (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. Flame retardant for FPC containing photopolymerizable compound having saturated bond in molecule, (C) photopolymerization initiator, (D) blocked isocyanate compound, and (E) phosphorus-containing compound having phosphorus atom in molecule Photosensitive resin compositions have been proposed. However, the use of a halogen compound such as a compound having an unsaturated double bond polymerizable with a halogenated aromatic ring is not preferable from the viewpoint of environmental load. JP 2007-10794 A (Claims)
- 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 flame retardancy, has a flexible cured film, has excellent adhesion to various substrates, and solder.
- An object of the present invention is to provide a flame-retardant photocurable resin composition that can form a cured film with a fine pattern excellent in heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, etc., and is particularly suitable for FPC. It is said.
- 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.
- an organic solvent-soluble phosphorus element-containing polyester (B) a carboxyl group-containing resin, and (C) a photopolymerization initiator are included.
- a flammable photocurable resin composition is provided.
- the carboxyl group-containing resin (B) is a carboxyl group-containing polyurethane resin.
- thermosetting resin (E) preferably contains an epoxy resin having a biphenyl skeleton.
- a flame-retardant photocurable resin composition particularly a flame-retardant photocurable / thermosetting resin composition containing the thermosetting resin (E)
- 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 halogen-free organic solvent-soluble phosphorus element-containing polyester and a carboxyl group-containing resin, the non-halogen composition has low environmental impact and excellent flame retardancy.
- the cured film is rich in flexibility and can form a cured film having a fine pattern excellent in adhesion to various substrates, solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, and the like. Therefore, 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 first feature of the flame-retardant photocurable resin composition of the present invention is that a halogen-free organic solvent-soluble phosphorus element-containing polyester (A) is used.
- halogen-free means that a halogen compound is not actively used unless it is mixed as an inevitable impurity.
- the organic solvent-soluble phosphorus element-containing polyester (A) is used in the production of the polyester to contain a phosphorus-containing carboxylic acid or an esterified product thereof, a phosphoric acid compound, a phosphonic acid compound, a phosphorous acid compound, a phosphonite compound, It is obtained by copolymerizing a phosphorus compound such as a phosphinic acid compound (see, for example, JP 2002-3587 A, JP 2007-204744 A, etc.).
- it is a phosphorus-containing carboxylic acid represented by the following general formula (I) or an organic solvent-soluble phosphorus element-containing polyester obtained by co-polymerizing an ester compound thereof.
- R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group
- R 3 and R 4 each independently represents a hydrogen atom, a hydrocarbon group or a hydroxy group-substituted hydrocarbon group
- l and m each represents an integer of 0 to 4.
- organic solvent-soluble phosphorus element-containing polyesters include Byron (registered trademark) 237 and Byron 337 manufactured by Toyobo Co., Ltd. These phosphorus element-containing polyesters may have a polyester polyurethane structure in which urethane bonds are partially introduced using diisocyanate.
- UR3570 manufactured by Toyobo Co., Ltd. may be mentioned.
- the organic solvent-soluble phosphorus element-containing polyester (A) various high molecular weight polyester resin compounds that are soluble in various industrial organic solvents can be used, and are not limited to specific ones, but preferably have the following properties.
- the weight average molecular weight is preferably in the range of 1,000 to 100,000, more preferably 5,000 to 50,000. If the weight average molecular weight is less than 1,000, the tack-free performance of the resulting coating film may be inferior. On the other hand, when the weight average molecular weight exceeds 100,000, the solubility in various organic solvents is lowered, and the developability of the resulting coating film may be remarkably deteriorated.
- the phosphorus content in the polyester is generally in the range of 0.3 to 20%, more preferably 1 to 5%. If it is less than 0.3%, sufficient flame retardancy may not be obtained. On the other hand, if it exceeds 20%, the flexibility and electrical properties of the cured film may be remarkably deteriorated.
- the amount of the organic solvent-soluble phosphorus element-containing polyester (A) is 0.5 to 50% by mass, preferably 1 to 20% by mass, based on the total composition. When less than the said range, sufficient flame retardance of the cured film obtained is not acquired, and a favorable result is not acquired also in flexibility. On the other hand, when 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.
- organic solvents for industrial use used in organic solvent-soluble phosphorus element-containing polyester (A) include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, and aliphatic hydrocarbons. And petroleum solvents.
- 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 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 carboxyl group-containing resin (B) as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution is possible.
- the acid value of the carboxyl group-containing resin (B) is desirably in the range of 40 to 200 mgKOH / g, 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.
- a particularly preferable photopolymerization initiator is a phosphorus element-containing photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator having a group represented by the following general formula (II-1) can be preferably used.
- R 5 and R 6 are each independently 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 the group represented by the general formula (II-1) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl)- Phenylphosphine oxide, bis (2,6- And 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 5 has the same meaning as described above, and R 7 independently of R 5 is a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, or 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 8 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 9 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 10 and R 11 each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group
- R 12 and R 13 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.
- oxime ester photopolymerization initiator having a group represented by the general formula (III)
- 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (V)
- a compound represented by the following general formula (VI) and a compound represented by the following general formula (VII) Is mentioned.
- R 14 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an 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 15 and R 17 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), or 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 16 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 atom
- 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 18 , R 19 and R 24 each independently represents an alkyl group having 1 to 12 carbon atoms
- R 20 , R 21 , R 22 and R 23 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.
- Commercially available products include CGI-325 manufactured by Ciba Specialty Chemicals, Irgacure OXE01, Irgacure OXE02, N-1919 of ADEKA Corporation, and the like. 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 25 is an acrylate residue
- R 26 and R 27 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).
- R 28 , R 29 and R 30 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 ( C. I. ; The Society of Dyers and Colorists (issued by the Society of Dyers and Colorists) can be listed: 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.
- 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. can be used. 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.
- compositions of the above Examples and Comparative Examples are applied onto the patterned polyimide film substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature.
- This substrate was exposed to a solder resist pattern at 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. was applied under a spray pressure of 0.2 MPa. Development was performed for 2 seconds to obtain a resist pattern.
- This substrate was cured by heating at 150 ° C. for 60 minutes.
- the characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.
- ⁇ 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. A: No soaking or peeling is observed. ⁇ : Slight penetration is confirmed after plating, but does not peel off after tape peeling. ⁇ : Slight penetration after plating and peeling after tape peel. X: There is peeling after plating.
- ⁇ Acid resistance> The evaluation substrate was immersed in a 10 vol% H 2 SO 4 aqueous solution at room temperature for 30 minutes, and soaking and dissolution of the coating film were confirmed. Further, peeling due to tape peeling was confirmed. Judgment criteria are as follows. ⁇ : No soaking, melting or peeling. ⁇ : Slight penetration, dissolution or peeling is confirmed. X: Significant infiltration, dissolution or 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.
- Example 4 A photocurable / thermosetting resin composition prepared with the same formulation as in Example 1 was diluted with methyl ethyl ketone, applied onto a carrier film, and dried by heating to form a resin composition layer having a thickness of 20 ⁇ m. It was dried for 30 minutes with a hot air drier at 0 ° C. Further, a cover film was laminated thereon to obtain a dry film. Thereafter, the cover film was peeled off and bonded to the patterned polyimide substrate using a laminator.
- This substrate is exposed to a solder resist pattern with an optimum exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, the carrier film is peeled off, and a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. is sprayed. Development was performed at 0.2 MPa for 60 seconds to obtain a substrate on which a resist pattern was formed. 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
Abstract
Description
さらに本発明の目的は、このような光硬化性樹脂組成物を用いることによって得られる上記のような諸特性に優れた難燃性のドライフィルム及び硬化物、並びに該ドライフィルムや硬化物によりソルダーレジスト等の難燃性の硬化皮膜が形成されてなるプリント配線板を提供することにある。 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 flame retardancy, has a flexible cured film, has excellent adhesion to various substrates, and solder. An object of the present invention is to provide a flame-retardant photocurable resin composition that can form a cured film with a fine pattern excellent in heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, etc., and is particularly suitable for FPC. It is said.
Furthermore, 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.
さらに本発明によれば、前記難燃性光硬化性樹脂組成物又はドライフィルムを硬化させて得られる難燃性硬化皮膜を有することを特徴とするプリント配線板も提供される。 Further, according to the present invention, 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.
Furthermore, according to this invention, the printed wiring board characterized by having the flame-retardant cured film obtained by hardening | curing the said flame-retardant photocurable resin composition or a dry film is also provided.
従って、本発明の難燃性光硬化性樹脂組成物は、プリント配線板、特にFPCのソルダーレジスト等の難燃性硬化皮膜の形成に有利に適用できる。 Since the flame-retardant photocurable resin composition of the present invention uses a halogen-free organic solvent-soluble phosphorus element-containing polyester and a carboxyl group-containing resin, the non-halogen composition has low environmental impact and excellent flame retardancy. The cured film is rich in flexibility and can form a cured film having a fine pattern excellent in adhesion to various substrates, solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, and the like.
Therefore, 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.
有機溶剤可溶性リン元素含有ポリエステル(A)は、ポリエステルの製造の際に含リンカルボン酸やそのエステル化物、リン酸系化合物、ホスホン酸系化合物、亜リン酸系化合物、亜ホスホン酸系化合物、亜ホスフィン酸系化合物等のリン化合物を共重合させて得られるものである(例えば、特開2002-3587号公報、特開2007-204744号公報等参照)。
好ましくは下記一般式(I)で表されるリン含有カルボン酸あるいは、そのエステル化合物を共重して得られる有機溶剤可溶性リン元素含有ポリエステルである。
R3及びR4、はそれぞれ独立に、水素原子、炭化水素基またはヒドロキシ基置換炭化水素基を表し、
l、mは0~4の整数を表す。
前記の有機溶剤可溶性リン元素含有ポリエステルの市販品としては、東洋紡(株)製バイロン(登録商標)237、バイロン337等が挙げられる。
これらリン元素含有ポリエステルは部分的にジイソシアネートを用いてウレタン結合を導入したポリエステルポリウレタン構造であってもかまわない。例えば、市販されているものとしては、東洋紡(株)製UR3570等が挙げられる。 As described above, the first feature of the flame-retardant photocurable resin composition of the present invention is that a halogen-free organic solvent-soluble phosphorus element-containing polyester (A) is used. In the present specification, the term “halogen-free” means that a halogen compound is not actively used unless it is mixed as an inevitable impurity.
The organic solvent-soluble phosphorus element-containing polyester (A) is used in the production of the polyester to contain a phosphorus-containing carboxylic acid or an esterified product thereof, a phosphoric acid compound, a phosphonic acid compound, a phosphorous acid compound, a phosphonite compound, It is obtained by copolymerizing a phosphorus compound such as a phosphinic acid compound (see, for example, JP 2002-3587 A, JP 2007-204744 A, etc.).
Preferably, it is a phosphorus-containing carboxylic acid represented by the following general formula (I) or an organic solvent-soluble phosphorus element-containing polyester obtained by co-polymerizing an ester compound thereof.
R 3 and R 4 each independently represents a hydrogen atom, a hydrocarbon group or a hydroxy group-substituted hydrocarbon group,
l and m each represents an integer of 0 to 4.
Examples of commercially available organic solvent-soluble phosphorus element-containing polyesters include Byron (registered trademark) 237 and Byron 337 manufactured by Toyobo Co., Ltd.
These phosphorus element-containing polyesters may have a polyester polyurethane structure in which urethane bonds are partially introduced using diisocyanate. For example, as a commercially available product, UR3570 manufactured by Toyobo Co., Ltd. may be mentioned.
(1)重量平均分子量は、一般的に1,000~100,000、さらには5,000~50,000の範囲にあるものが好ましい。重量平均分子量が1,000未満であると、得られる塗膜のタックフリー性能が劣ることがある。一方、重量平均分子量が100,000を超えると、各種有機溶剤への溶解性が低下し、また得られる塗膜の現像性が著しく悪くなることがある。
(2)ポリエステル中のリン含有量は、一般的に0.3~20%、さらには1~5%の範囲であることが好ましい。0.3%未満であると充分な難燃性を得られないことがある。一方、20%を超えると、硬化皮膜の可撓性、電気特性が著しく悪くなることがある。 As the organic solvent-soluble phosphorus element-containing polyester (A), various high molecular weight polyester resin compounds that are soluble in various industrial organic solvents can be used, and are not limited to specific ones, but preferably have the following properties.
(1) The weight average molecular weight is preferably in the range of 1,000 to 100,000, more preferably 5,000 to 50,000. If the weight average molecular weight is less than 1,000, the tack-free performance of the resulting coating film may be inferior. On the other hand, when the weight average molecular weight exceeds 100,000, the solubility in various organic solvents is lowered, and the developability of the resulting coating film may be remarkably deteriorated.
(2) The phosphorus content in the polyester is generally in the range of 0.3 to 20%, more preferably 1 to 5%. If it is less than 0.3%, sufficient flame retardancy may not be obtained. On the other hand, if it exceeds 20%, the flexibility and electrical properties of the cured film may be remarkably deteriorated.
上記範囲より少ない場合、得られる硬化皮膜の充分な難燃性が得られず、また可撓性においても良好な結果が得られない。一方、上記範囲より多い場合、塗膜のタックフリー性能が低下したり、組成物の粘性が高くなったりするので好ましくない。 The amount of the organic solvent-soluble phosphorus element-containing polyester (A) is 0.5 to 50% by mass, preferably 1 to 20% by mass, based on the total composition.
When less than the said range, sufficient flame retardance of the cured film obtained is not acquired, and a favorable result is not acquired also in flexibility. On the other hand, when 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.
このような有機溶剤は、単独で又は2種以上の混合物として用いられ、また高分子量ポリエステル樹脂化合物の加水分解を促進しないものであることがより好ましい。 Various organic solvents for industrial use used in organic solvent-soluble phosphorus element-containing polyester (A) include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, and aliphatic hydrocarbons. And petroleum solvents. More specifically, 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, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha.
Such an organic solvent is used alone or as a mixture of two or more, and more preferably does not accelerate hydrolysis of the high molecular weight polyester resin compound.
カルボキシル基含有樹脂(B)の具体例としては、以下に列挙するような化合物(オリゴマー及びポリマーのいずれでもよい)を好適に使用できる。 As 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. In addition, when using only the carboxyl group-containing resin which does not have an ethylenically unsaturated double bond, in order to make a composition photocurable, it has two or more ethylenically unsaturated groups in the molecule | numerator mentioned later. It is necessary to use a photopolymerizable monomer (D) in combination.
As specific examples of the carboxyl group-containing resin (B), compounds listed below (any of oligomers and polymers) can be suitably used.
(2)ジイソシアネートと、ビスフェノールA型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ビキシレノール型エポキシ樹脂、ビフェノール型エポキシ樹脂等の2官能エポキシ樹脂の(メタ)アクリレートもしくはその部分酸無水物変性物、カルボキシル基含有ジアルコール化合物及びジオール化合物の重付加反応による感光性カルボキシル基含有ウレタン樹脂。
(3)上記(1)又は(2)の樹脂の合成中に、ヒドロキシアルキル(メタ)アクリレート等の分子内に1つの水酸基と1つ以上の(メタ)アクリル基を有する化合物を加え、末端(メタ)アクリル化したカルボキシル基含有ウレタン樹脂。
(4)上記(1)又は(2)の樹脂の合成中に、イソホロンジイソシアネートとペンタエリスリトールトリアクリレートの等モル反応物など、分子内に1つのイソシアネート基と1つ以上の(メタ)アクリル基を有する化合物を加え、末端(メタ)アクリル化したカルボキシル基含有ウレタン樹脂。
(5)(メタ)アクリル酸等の不飽和カルボン酸と、スチレン、α-メチルスチレン、低級アルキル(メタ)アクリレート、イソブチレン等の不飽和基含有化合物との共重合により得られるカルボキシル基含有樹脂。
(6)後述するような2官能又はそれ以上の多官能(固形)エポキシ樹脂に(メタ)アクリル酸を反応させ、側鎖に存在する水酸基に2塩基酸無水物を付加させた感光性カルボキシル基含有樹脂。
(7)2官能(固形)エポキシ樹脂の水酸基をさらにエピクロロヒドリンでエポキシ化した多官能エポキシ樹脂に(メタ)アクリル酸を反応させ、生じた水酸基に2塩基酸無水物を付加させた感光性カルボキシル基含有樹脂。
(8)後述するような2官能オキセタン樹脂にジカルボン酸を反応させ、生じた1級の水酸基に2塩基酸無水物を付加させたカルボキシル基含有ポリエステル樹脂。
(9)上記(1)~(8)の樹脂にさらに1分子内に1つのエポキシ基と1つ以上の(メタ)アクリル基を有する化合物を付加してなる感光性カルボキシル基含有樹脂。 (1) 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.
(2) 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.
(3) During the synthesis of the resin of the above (1) or (2), 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.
(4) During the synthesis of the resin of the above (1) or (2), 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.
(5) 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, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
(6) A photosensitive carboxyl group obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin as described later with (meth) acrylic acid and adding a dibasic acid anhydride to the hydroxyl group present in the side chain. Containing resin.
(7) Photosensitivity in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group. Functional carboxyl group-containing resin.
(8) 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.
(9) 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).
尚、本明細書において、(メタ)アクリレートとは、アクリレート、メタクリレート及びそれらの混合物を総称する用語であり、他の類似の表現についても同様である。 Among these 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. From the viewpoint of photosensitivity and flexibility, (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. Further, in another aspect, 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.
In the present specification, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
また、前記カルボキシル基含有樹脂(B)の酸価は、40~200mgKOH/gの範囲、より好ましくは45~120mgKOH/gの範囲にあることが望ましい。カルボキシル基含有樹脂の酸価が40mgKOH/g未満であるとアルカリ現像が困難となり、一方、200mgKOH/gを超えると現像液による露光部の溶解が進むために、必要以上にラインが痩せたり、場合によっては、露光部と未露光部の区別なく現像液で溶解剥離してしまい、正常なレジストパターンの描画が困難となるので好ましくない。 Since the carboxyl group-containing resin (B) as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution is possible.
The acid value of the carboxyl group-containing resin (B) is desirably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary. Depending on the case, 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.
特に好ましい光重合開始剤としてはリン元素含有光重合開始剤があり、下記一般式(II-1)で表される基を有するアシルホスフィンオキサイド系光重合開始剤を好適に用いることができる。
A particularly preferable photopolymerization initiator is a phosphorus element-containing photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator having a group represented by the following general formula (II-1) can be preferably used.
ジメトキシベンゾイル)-2,4,4-トリメチル-ペンチルホスフィンオキサイドなど
が挙げられる。市販品としては、BASF社製のルシリンTPO、チバ・スペシャルティ・ケミカルズ社製のイルガキュアー(登録商標)819などが挙げられる。 Examples of the acylphosphine oxide photopolymerization initiator having the group represented by the general formula (II-1) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl)- Phenylphosphine oxide, bis (2,6-
And 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.
表される基を有するα-アミノアセトフェノン系光重合開始剤がある。
R9は、フェニル基(炭素数1~6のアルキル基、フェニル基もしくはハロゲン原子で置換されていてもよい)、炭素数1~20のアルキル基(1個以上の水酸基で置換されていてもよく、アルキル鎖の中間に1個以上の酸素原子を有していてもよい)、炭素数5~8のシクロアルキル基、炭素数2~20のアルカノイル基又はベンゾイル基(炭素数が1~6のアルキル基もしくはフェニル基で置換されていてもよい)を表し、
R10及びR11は、それぞれ独立に、炭素数1~12のアルキル基又はアリールアルキル基を表し、
R12及びR13は、それぞれ独立に、水素原子、炭素数1~6のアルキル基、又は2つが結合した環状アルキルエーテル基を表す。 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 α-aminoacetophenone photopolymerization initiators having the following groups.
R 9 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). It 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 (having 1 to 6 carbon atoms) Which may be substituted with an alkyl group or a phenyl group of
R 10 and R 11 each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,
R 12 and R 13 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.
好ましくは、下記式(V)で表される2-(アセチルオキシイミノメチル)チオキサンテン-9-オン、下記一般式(VI)で表される化合物及び下記一般式(VII)で表される化
合物が挙げられる。
Preferably, 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (V), a compound represented by the following general formula (VI), and a compound represented by the following general formula (VII) Is mentioned.
R15、R17は、それぞれ独立に、フェニル基(炭素数1~6のアルキル基、フェニル基もしくはハロゲン原子で置換されていてもよい)、炭素数1~20のアルキル基(1個以上の水酸基で置換されていてもよく、アルキル鎖の中間に1個以上の酸素原子を有していてもよい)、炭素数5~8のシクロアルキル基、炭素数2~20のアルカノイル基又はベンゾイル基(炭素数が1~6のアルキル基もしくはフェニル基で置換されていてもよい)を表し、
R16は、水素原子、フェニル基(炭素数1~6のアルキル基、フェニル基もしくはハロゲン原子で置換されていてもよい)、炭素数1~20のアルキル基(1個以上の水酸基で置換されていてもよく、アルキル鎖の中間に1個以上の酸素原子を有していてもよい)、炭素数5~8のシクロアルキル基、炭素数2~20のアルカノイル基又はベンゾイル基(炭素数が1~6のアルキル基もしくはフェニル基で置換されていてもよい)を表す。
R 15 and R 17 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), or 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 16 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 (substituted with one or more hydroxyl groups). 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 (having a carbon number). Optionally substituted with 1 to 6 alkyl groups or phenyl groups.
R20、R21、R22及びR23は、それぞれ独立に、水素原子又は炭素数1~6のアルキル基を表し、
Mは、O、S又はNHを表し、
n及びpは、それぞれ独立に0~5の整数を表す。
R 20 , R 21 , R 22 and R 23 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.
尚、前記式(III)で表される基を有するオキシムエステル系光重合開始剤の場合、そ
の配合量は、前記カルボキシル基含有樹脂(B)100質量部に対して、好ましくは0.01~20質量部、より好ましくは0.01~5質量部の範囲から選ぶことが望ましい。 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.
In the case of the oxime ester-based photopolymerization initiator having a group represented by the formula (III), 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.
アセトフェノン化合物の具体例を挙げると、例えば、アセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン、2,2-ジエトキシ-2-フェニルアセトフェノン、1,1-ジクロロアセトフェノンである。 Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone.
チオキサントン化合物の具体例を挙げると、例えば、2,4-ジメチルチオキサントン、2,4-ジエチルチオキサントン、2-クロロチオキサントン、2,4-ジイソプロピルチオキサントンである。 Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.
Specific examples of the thioxanthone compound include, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.
ベンゾフェノン化合物の具体例を挙げると、例えば、ベンゾフェノン、4-ベンゾイルジフェニルスルフィド、4-ベンゾイル-4’-メチルジフェニルスルフィド、4-ベンゾイル-4’-エチルジフェニルスルフィド、4-ベンゾイル-4’-プロピルジフェニルスルフィドである。 Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.
Specific examples of the benzophenone compound include, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyldiphenyl. Sulfide.
このようなチオキサントン化合物の配合量としては、前記カルボキシル基含有樹脂(B)100質量部に対して、好ましくは20質量部以下、より好ましくは10質量部以下の割合が適当である。チオキサントン化合物の配合量が多すぎると、厚膜硬化性が低下して、製品のコストアップに繋がるので、好ましくない。 Among the above-mentioned compounds, thioxanthone compounds and tertiary amine compounds are preferable. 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.
このような光重合開始剤、光開始助剤、及び増感剤の総量は、前記カルボキシル基含有樹脂(B)100質量部に対して35質量部以下となる範囲であることが好ましい。35質量部を超えると、これらの光吸収により深部硬化性が低下する傾向にある。 These photopolymerization initiators, photoinitiator assistants, and sensitizers 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.
上記一般式(IX)表される化合物の市販品としてはHCA、SANKO-220、M-ESTER、HCA-HQ等がある。 The photocurable resin composition of the present invention can further contain a phosphorus-containing compound as a flame retardant auxiliary. As the 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).
Commercially available products of the compound represented by the general formula (IX) include HCA, SANKO-220, M-ESTER, HCA-HQ and the like.
青色着色剤としてはフタロシアニン系、アントラキノン系があり、顔料系はピグメント(Pigment)に分類されている化合物、具体的には、下記のようなカラーインデックス(
C.I.;ザ ソサイエティ オブ ダイヤーズ アンド カラリスツ(The Society of Dyers and Colourists)発行)番号が付されているものを挙げることができる: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。
染料系としては、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等を使用することができる。上記以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。 Blue colorant:
Blue colorants include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds classified as Pigment, specifically, the following color index (
C. I. ; The Society of Dyers and Colorists (issued by the Society of Dyers and Colorists) can be listed: 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.
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. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
緑色着色剤としては、同様にフタロシアニン系、アントラキノン系、ペリレン系があり、具体的にはPigment Green 7、Pigment Green 36、Solvent Green 3、Solvent Green 5
、Solvent Green 20、Solvent Green 28等を使用することができる。上記以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。 Green colorant:
Similarly, green colorants 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. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
黄色着色剤としてはモノアゾ系、ジスアゾ系、縮合アゾ系、ベンズイミダゾロン系、イソインドリノン系、アントラキノン系等があり、具体的には以下のものが挙げられる。
アントラキノン系:Solvent Yellow 163、Pigment Yellow 24、Pigment Yellow 108、Pigment Yellow 193、Pigment Yellow 147、Pigment Yellow 199、Pigment Yellow 202。
イソインドリノン系:Pigment Yellow 110、Pigment Yellow 109、Pigment Yellow 139、Pigment Yellow 179、Pigment Yellow 185。
縮合アゾ系:Pigment Yellow 93、Pigment Yellow 94、Pigment Yellow 95、Pigment Yellow 128、Pigment Yellow 155、Pigment Yellow 166、Pigment Yellow 180。
ベンズイミダゾロン系:Pigment Yellow 120、Pigment Yellow 151、Pigment Yellow 154、Pigment Yellow 156、Pigment Yellow 175、Pigment Yellow 181。
モノアゾ系: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。
ジスアゾ系:Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198。 Yellow colorant:
Examples of yellow colorants 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.
赤色着色剤としてはモノアゾ系、ジズアゾ系、アゾレーキ系、ベンズイミダゾロン系、ペリレン系、ジケトピロロピロール系、縮合アゾ系、アントラキノン系、キナクリドン系などがあり、具体的には以下のものが挙げられる。
モノアゾ系: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。
ジスアゾ系:Pigment Red 37, 38, 41。
モノアゾレーキ系: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。
ベンズイミダゾロン系:Pigment Red 171、Pigment Red 175、Pigment Red 176、Pigment Red 185、Pigment Red 208。
ぺリレン系: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。
ジケトピロロピロール系:Pigment Red 254、Pigment Red 255、Pigment Red 264、Pigment Red 270、Pigment Red 272。
縮合アゾ系:Pigment Red 220、Pigment Red 144、Pigment Red 166、Pigment Red 214、Pigment Red 220、Pigment Red 221、Pigment Red 242。
アンスラキノン系:Pigment Red 168、Pigment Red 177、Pigment Red 216、Solvent Red 149、Solvent Red 150、Solvent Red 52、Solvent Red 207。
キナクリドン系:Pigment Red 122、Pigment Red 202、Pigment Red 206、Pigment Red 207、Pigment Red 209。 Red colorant:
Examples of red colorants 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.
具体的に例示すれば、Pigment Violet 19、23、29、32、36、38、42、Solvent Violet 13、36、C.I.ピグメントオレンジ1、C.I.ピグメントオレンジ5、C.I.ピグメントオレンジ13、C.I.ピグメントオレンジ14、C.I.ピグメントオレンジ16、C.I.ピグメントオレンジ17、C.I.ピグメントオレンジ24、C.I.ピグメントオレンジ34、C.I.ピグメントオレンジ36、C.I.ピグメントオレンジ38、C.I.ピグメントオレンジ40、C.I.ピグメントオレンジ43、C.I.ピグメントオレンジ46、C.I.ピグメントオレンジ49、C.I.ピグメントオレンジ51、C.I.ピグメントオレンジ61、C.I.ピグメントオレンジ63、C.I.ピグメントオレンジ64、C.I.ピグメントオレンジ71、C.I.ピグメントオレンジ73、C.I.ピグメントブラウン23、C.I.ピグメントブラウン25、C.I.ピグメントブラック1、C.I.ピグメントブラック7等がある。 In addition, for the purpose of adjusting the color tone, a colorant such as purple, orange, brown, or black may be added.
Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black And the like.
このような有機溶剤としては、ケトン類、芳香族炭化水素類、グリコールエーテル類、グリコールエーテルアセテート類、エステル類、アルコール類、脂肪族炭化水素、石油系溶剤などを挙げることができる。より具体的には、メチルエチルケトン、シクロヘキサノン等のケトン類;トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類;セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類;酢酸エチル、酢酸ブチル、ジプロピレングリコールメチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールブチルエーテルアセテートなどのエステル類;エタノール、プロパノール、エチレングリコール、プロピレングリコール等のアルコール類;オクタン、デカン等の脂肪族炭化水素;石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤などである。このような有機溶剤は、単独で又は2種以上の混合物として用いられる。 Furthermore, 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. can do.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, 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, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.
ドライフィルム化に際しては、本発明の光硬化性樹脂組成物を前記有機溶剤で希釈して適切な粘度に調整し、コンマコーター、ブレードコーター、リップコーター、ロッドコーター、スクイズコーター、リバースコーター、トランスファロールコーター、グラビアコーター、スプレーコーター等でキャリアフィルム上に均一な厚さに塗布し、通常、50~130℃の温度で1~30分間乾燥して膜を得ることができる。塗布膜厚については特に制限はないが、一般に、乾燥後の膜厚で、10~150μm、好ましくは20~60μmの範囲で適宜選択される。 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. .
When forming a dry 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 μm, preferably 20 to 60 μm.
剥離可能なカバーフィルムとしては、例えば、ポリエチレンフィルム、ポリテトラフルオロエチレンフィルム、ポリプロピレンフィルム、表面処理した紙等を用いることができ、カバーフィルムを剥離するときに膜とキャリアフィルムとの接着力よりも膜とカバーフィルムとの接着力がより小さいものであればよい。 After the film is formed on the carrier film, it is desirable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film.
As the 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.
上記活性エネルギー線照射に用いられる露光機としては、レーザー直接描画装置(レーザーダイレクトイメージング装置)、メタルハライドランプを搭載した露光機、(超)高圧水銀ランプを搭載した露光機、水銀ショートアークランプを搭載した露光機、もしくは(超)高圧水銀ランプなどの紫外線ランプを使用した直接描画装置を使用することができる。尚、活性エネルギー線として最大波長が350~410nmの範囲にあるレーザー光を用いていれば、ガスレーザー、固体レーザーどちらでもよい。また、その露光量は膜厚等によって異なるが、一般には5~200mJ/cm2、好ましくは5~100mJ/cm2、さらに好ましくは5~50mJ/cm2の範囲内とすることができる。上記直接描画装置としては、例えば日本オルボテック社製、ペンタックス社製等のものを使用することができ、最大波長が350~410nmのレーザー光を発振する装置であればいずれの装置を用いてもよい。 As mentioned above, after apply | coating the photocurable resin composition of this invention and evaporating and drying, exposure (irradiation of an active energy ray) is performed with respect to the obtained coating film. In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.
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. As long as 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 . As 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. .
表1に示す各成分を表1に示す割合(質量部)にて配合し、攪拌機にて予備混合した後、3本ロールミルで混練し、ソルダーレジスト用光硬化性・熱硬化性樹脂組成物を調製した。ここで、得られた光硬化性・熱硬化性樹脂組成物の分散度をエリクセン社製グラインドメータによる粒度測定にて評価したところ15μm以下であった。 Examples 1 to 3, Comparative Examples 1 and 2
Each component shown in Table 1 was blended in the proportions (parts by mass) shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and a photocurable / thermosetting resin composition for a solder resist. Prepared. Here, when the degree of dispersion of the obtained photocurable / thermosetting resin composition was evaluated by particle size measurement using a grindometer manufactured by Eriksen, it was 15 μm or less.
<最適露光量>
前記各実施例及び比較例の光硬化性・熱硬化性樹脂組成物を、銅厚35μmの回路パターン基板をバフロール研磨後、水洗し、乾燥してからスクリーン印刷法により全面に塗布し、80℃の熱風循環式乾燥炉で30分間乾燥させる。乾燥後、メタルハライドランプ搭載の露光装置(HMW-680-GW20)を用いてステップタブレット(コダック No.2)を介して露光し、現像(30℃、0.2MPa、1wt%Na2CO3水溶液)を60秒で行った際残存するステップタブレットのパターンが6段の時を最適露光量とした。 Performance evaluation:
<Optimum exposure amount>
The photocurable / thermosetting resin compositions of the above Examples and Comparative Examples were applied to the entire surface by screen printing after applying a circuit board having a copper thickness of 35 μm to buffing, washing with water and drying. For 30 minutes in a hot air circulation drying oven. After drying, exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and development (30 ° C., 0.2 MPa, 1 wt% Na 2 CO 3 aqueous solution) When the pattern of the step tablet remaining when performing for 60 seconds was 6 steps, the optimum exposure amount was set.
前記各実施例及び比較例の組成物を、パターン形成されたポリイミドフィルム基板上にスクリーン印刷で全面塗布し、80℃で30分乾燥し、室温まで放冷する。この基板にメタルハライドランプ搭載の露光装置(HMW-680-GW20)を用いて最適露光量でソルダーレジストパターンを露光し、30℃の1wt%Na2CO3水溶液をスプレー圧0.2MPaの条件で60秒間現像を行い、レジストパターンを得た。この基板を、150℃で60分加熱して硬化した。得られたプリント基板(評価基板)に対して以下のように特性を評価した。 Characteristic test:
The compositions of the above Examples and Comparative Examples are applied onto the patterned polyimide film substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. This substrate was exposed to a solder resist pattern at 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. was applied under a spray pressure of 0.2 MPa. Development was performed for 2 seconds to obtain a resist pattern. This substrate was cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.
ロジン系フラックスを塗布した評価基板を、予め260℃に設定したはんだ槽に浸漬し、変性アルコールでフラックスを洗浄した後、目視によるレジスト層の膨れ・剥がれについて評価した。判定基準は以下のとおりである。
○:10秒間浸漬を2回以上繰り返しても剥がれが認められない。
△:10秒間浸漬を2回以上繰り返すと少し剥がれる。
×:10秒間浸漬を1回でレジスト層に膨れ、剥がれがある。 <Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
○: No peeling is observed even if the immersion for 10 seconds is repeated twice or more.
(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated twice or more.
X: The resist layer swells and peels off once in 10 seconds.
市販品の無電解ニッケルめっき浴及び無電解金めっき浴を用いて、ニッケル3μm、金0.03μmの条件でめっきを行い、テープピーリングにより、レジスト層の剥がれの有無やめっきのしみ込みの有無を評価した後、テープピーリングによりレジスト層の剥がれの有無を評価した。判定基準は以下のとおりである。
◎:染み込み、剥がれが見られない。
○:めっき後に少し染み込みが確認されるが、テープピール後は剥がれない。
△:めっき後にほんの僅かしみ込みが見られ、テープピール後に剥がれも見られる。
×:めっき後に剥がれが有る。 <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 μm and gold 0.03 μm, 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.
A: No soaking or peeling is observed.
○: Slight penetration is confirmed after plating, but does not peel off after tape peeling.
Δ: Slight penetration after plating and peeling after tape peel.
X: There is peeling after plating.
銅箔基板に代えてIPC B-25のクシ型電極Bクーポンを用い、上記の条件で評価基板を作製し、このクシ型電極にDC100Vのバイアス電圧を印加し、85℃、85%R.H.の恒温恒湿槽にて1,000時間後のマイグレーションの有無を確認した。判定基準は以下のとおりである。
○:全く変化が認められないもの
△:ほんの僅か変化したもの
×:マイグレーションが発生しているもの <Electrical characteristics>
Using an IPC B-25 comb-type electrode B coupon instead of the copper foil substrate, an evaluation board was prepared under the above conditions, and a bias voltage of DC 100 V was applied to the comb-type electrode, and 85 ° C., 85% R.D. H. The presence or absence of migration after 1,000 hours was confirmed in a constant temperature and humidity chamber. The judgment criteria are as follows.
○: No change is observed Δ: Only a slight change ×: Migration occurs
評価基板を10vol%H2SO4水溶液に室温で30分間浸漬し、染み込みや塗膜の溶け出し、さらにテープピーリングによる剥がれを確認した。判定基準は以下のとおり。
○:染み込み、溶け出し、剥がれなし。
△:染み込み、溶け出し、もしくは剥がれが少し確認される。
×:染み込み、溶け出し、もしくは剥がれが大きく確認される。 <Acid resistance>
The evaluation substrate was immersed in a 10 vol% H 2 SO 4 aqueous solution at room temperature for 30 minutes, and soaking and dissolution of the coating film were confirmed. Further, peeling due to tape peeling was confirmed. Judgment criteria are as follows.
○: No soaking, melting or peeling.
Δ: Slight penetration, dissolution or peeling is confirmed.
X: Significant infiltration, dissolution or peeling.
各実施例及び比較例の組成物を、25um厚のポリイミドフィルム(カプトン100H)にスクリーン印刷で全面塗布し、80℃で20分乾燥して室温まで放冷する。さらに裏面を同様にスクリーン印刷で全面塗布し、80℃で20分乾燥して室温まで放冷し両面塗布基板を得た。この基板にメタルハライドランプ搭載の露光装置(HMW-680-GW20)を用いて最適露光量でソルダーレジストを全面露光し、30℃の1wt%Na2CO3水溶液をスプレー圧0.2MPaの条件で60秒間現像を行い、150℃で60分間熱硬化を行い評価サンプルとした。この難燃性評価用サンプルついて、UL94規格に準拠した薄材垂直燃焼試験を行った。評価はUL94規格に基づいて、VTM-0又はVTM-1と表した。 <Flame retardance>
The composition of each Example and Comparative Example is applied to a 25-um thick polyimide film (Kapton 100H) by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature. Further, the entire back surface was similarly applied by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature to obtain a double-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. Development was performed for 1 second, and 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.
各実施例及び比較例の組成物を、25μmのポリイミドフィルム(カプトン100H)にスクリーン印刷で全面塗布し、80℃で30分乾燥して室温まで放冷し、片面塗布基板を得た。この基板にメタルハライドランプ搭載の露光装置(HMW-680-GW20)を用いて最適露光量でソルダーレジストを全面露光し、30℃の1wt%Na2CO3水溶液をスプレー圧0.2MPaの条件で60秒現像を行い、150℃で60分間熱硬化を行った。得られたサンプルのソルダーレジストを外側にして、ハゼ折による180°折り曲げを数回繰り返して行い、その際の塗膜におけるクラック発生状況を目視及び倍率200の光学顕微鏡で観察し、クラックが発生しない回数を評価した。 <Flexibility>
The compositions of each Example and Comparative Example were applied to a 25 μm 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.
実施例1と同じ配合で調製した光硬化性・熱硬化性樹脂組成物をメチルエチルケトンで希釈し、キャリアフィルム上に塗布し、加熱乾燥して、厚さ20μmの樹脂組成物層を形成し、80℃の熱風乾燥器で30分乾燥させた。さらにその上にカバーフィルムを貼り合わせてドライフィルムを得た。その後、カバーフィルムを剥がし、パターン形成されたポリイミド基板に、ラミネーターを用いて貼り合わせた。この基板にメタルハライドランプ搭載の露光装置(HMW-680-GW20)を用いて最適露光量でソルダーレジストパターンに露光し、キャリアフィルムを剥がした後、30℃の1wt%Na2CO3水溶液をスプレー圧0.2MPaの条件で60秒間現像を行い、レジストパターンを形成した基板を得た。その後、150℃の熱風乾燥器で60分加熱硬化を行ない、試験基板を作製した。得られた硬化皮膜を有する試験基板について、前述した試験方法及び評価方法と同様にして、各特性の評価試験を行なった。
得られたドライフィルムのハンドリング性は問題なく、得られたドライフィルムの特性は実施例1の結果とほぼ同等であった。 Example 4
A photocurable / thermosetting resin composition prepared with the same formulation as in Example 1 was diluted with methyl ethyl ketone, applied onto a carrier film, and dried by heating to form a resin composition layer having a thickness of 20 μm. It was dried for 30 minutes with a hot air drier at 0 ° C. Further, a cover film was laminated thereon to obtain a dry film. Thereafter, the cover film was peeled off and bonded to the patterned polyimide substrate using a laminator. This substrate is exposed to a solder resist pattern with an optimum exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, the carrier film is peeled off, and a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. is sprayed. Development was performed at 0.2 MPa for 60 seconds to obtain a substrate on which a resist pattern was formed. 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 | substrate which has the obtained cured film, the evaluation test of each characteristic was done like the test method and evaluation method which were mentioned above.
The handling property of the obtained dry film was satisfactory, and the characteristics of the obtained dry film were almost the same as the results of Example 1.
Claims (9)
- (A)有機溶剤可溶性リン元素含有ポリエステル、(B)カルボキシル基含有樹脂、及び(C)光重合開始剤を含有することを特徴とする難燃性光硬化性樹脂組成物。 (A) An organic solvent-soluble phosphorus element-containing polyester, (B) a carboxyl group-containing resin, and (C) a photopolymerization initiator.
- さらに(D)光重合性モノマーを含有することを特徴とする請求項1に記載の難燃性光硬化性樹脂組成物。 The flame-retardant photocurable resin composition according to claim 1, further comprising (D) a photopolymerizable monomer.
- さらに(E)熱硬化性樹脂を含有することを特徴とする請求項1に記載の難燃性光硬化性樹脂組成物。 The flame retardant photocurable resin composition according to claim 1, further comprising (E) a thermosetting resin.
- 前記熱硬化性樹脂(E)が、ビフェニル骨格を有するエポキシ樹脂を含むことを特徴とする請求項3に記載の難燃性光硬化性樹脂組成物。 The flame retardant photocurable resin composition according to claim 3, wherein the thermosetting resin (E) includes an epoxy resin having a biphenyl skeleton.
- 前記カルボキシル基含有樹脂(B)が、カルボキシル基含有ポリウレタン樹脂であることを特徴とする請求項1に記載の難燃性光硬化性樹脂組成物。 The flame retardant photocurable resin composition according to claim 1, wherein the carboxyl group-containing resin (B) is a carboxyl group-containing polyurethane resin.
- ソルダーレジストである請求項1乃至5のいずれか一項に記載の難燃性光硬化性樹脂組成物。 It is a solder resist, The flame-retardant photocurable resin composition as described in any one of Claims 1 thru | or 5.
- 請求項1乃至5のいずれか一項に記載の難燃性光硬化性樹脂組成物を、キャリアフィルム上に塗布・乾燥させて得られる難燃性光硬化性のドライフィルム。 A flame-retardant photocurable dry film obtained by applying and drying the flame-retardant photocurable resin composition according to any one of claims 1 to 5 on a carrier film.
- 請求項1乃至5のいずれか一項に記載の難燃性光硬化性樹脂組成物又は前記難燃性光硬化性樹脂組成物をキャリアフィルム上に塗布・乾燥させて得られるドライフィルムを硬化させて得られる難燃性硬化物。 A flame retardant photocurable resin composition according to any one of claims 1 to 5 or a dry film obtained by applying and drying the flame retardant photocurable resin composition on a carrier film is cured. Flame-retardant cured product obtained by
- 請求項1乃至5のいずれか一項に記載の難燃性光硬化性樹脂組成物又は前記難燃性光硬化性樹脂組成物をキャリアフィルム上に塗布・乾燥させて得られるドライフィルムを硬化させて得られる難燃性硬化皮膜を有することを特徴とするプリント配線板。 A flame retardant photocurable resin composition according to any one of claims 1 to 5 or a dry film obtained by applying and drying the flame retardant photocurable resin composition on a carrier film is cured. A printed wiring board having a flame-retardant cured film obtained by
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KR1020117002698A KR101693053B1 (en) | 2008-08-07 | 2009-08-06 | Flame-retardant photocurable resin composition, dry film and cured product of the same, and printed wiring board using the composition, dry film or cured product |
CN2009801305502A CN102112920B (en) | 2008-08-07 | 2009-08-06 | Flame-retardant photocurable resin composition, dry film and cured product of same, and printed circuit board using composition thereof |
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CN102792226A (en) * | 2010-03-31 | 2012-11-21 | 太阳控股株式会社 | Photosensitive resin composition |
CN102822747A (en) * | 2010-03-31 | 2012-12-12 | 太阳控股株式会社 | Photo-curable thermosetting resin composition |
TWI499633B (en) * | 2010-03-11 | 2015-09-11 | Namics Corp | Compositon for film and adhesive film using the same, and coverlay film |
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JP5415923B2 (en) * | 2009-12-14 | 2014-02-12 | 太陽ホールディングス株式会社 | Photosensitive resin composition, dry film thereof, and printed wiring board using them |
JP6061440B2 (en) * | 2010-02-25 | 2017-01-18 | 太陽ホールディングス株式会社 | Resin composition for polyester substrate, dry film and printed wiring board using the same |
US9596754B2 (en) | 2011-12-22 | 2017-03-14 | Taiyo Ink Mfg. Co., Ltd. | Dry film, printed wiring board using same, method for producing printed wiring board, and flip chip mounting substrate |
JP5743042B1 (en) * | 2013-09-26 | 2015-07-01 | 東洋紡株式会社 | Polyurethane resin composition, adhesive composition using the same, laminate and printed wiring board |
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KR101693053B1 (en) | 2017-01-04 |
TWI435173B (en) | 2014-04-21 |
JP5043775B2 (en) | 2012-10-10 |
CN102112920B (en) | 2013-11-20 |
CN102112920A (en) | 2011-06-29 |
KR20110039452A (en) | 2011-04-18 |
JP2010039388A (en) | 2010-02-18 |
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