WO2011010461A1 - 光硬化性樹脂組成物 - Google Patents

光硬化性樹脂組成物 Download PDF

Info

Publication number
WO2011010461A1
WO2011010461A1 PCT/JP2010/004678 JP2010004678W WO2011010461A1 WO 2011010461 A1 WO2011010461 A1 WO 2011010461A1 JP 2010004678 W JP2010004678 W JP 2010004678W WO 2011010461 A1 WO2011010461 A1 WO 2011010461A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
manufactured
resin composition
photocurable resin
Prior art date
Application number
PCT/JP2010/004678
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
昌司 峰岸
聖夫 有馬
Original Assignee
太陽ホールディングス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 太陽ホールディングス株式会社 filed Critical 太陽ホールディングス株式会社
Priority to KR1020127001502A priority Critical patent/KR101372202B1/ko
Priority to CN201080033075.XA priority patent/CN102472965B/zh
Publication of WO2011010461A1 publication Critical patent/WO2011010461A1/ja

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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 curable resin composition used as a solder resist for printed wiring boards.
  • the photocurable resin composition can be finely processed by applying the principle of a photographic method (photolithography). Furthermore, since a cured product having excellent physical properties can be obtained, it is used in electronic devices and printing plates.
  • the photocurable resin composition includes a solvent development type and an alkali development type.
  • an alkali development type that can be developed with a dilute weak alkaline aqueous solution has become mainstream from the viewpoint of environmental measures.
  • an alkali development type photocurable resin composition is used in printed wiring board manufacture, liquid crystal display board manufacture, or printing plate making. For example, when used as a solder resist in the production of printed wiring boards, characteristics related to long-term reliability, such as heat resistance that can withstand processing under high temperature conditions such as soldering, and water resistance and moisture resistance are required. It is done.
  • a solder resist used for a high-density mounting substrate having a fine pitch pattern for high-density mounting requires high migration resistance and thermal cycle resistance in the cured product. Accordingly, it is required to reduce the moisture absorption and purity of the photocurable resin composition used as the solder resist, that is, to reduce the water absorption rate and the ionic impurities in the resin composition.
  • a photo-curable resin composition that satisfies migration resistance as a cured product and thermal cycle resistance to some extent, a polyfunctional epoxy resin or (meth) acrylate is used to double the resin skeleton among carboxyl group-containing epoxy (meth) acrylates.
  • a photocurable resin composition into which many bonds are introduced is used. With such a configuration, it is considered that the crosslink density can be increased, and heat resistance and dimensional stability can be improved.
  • the photocurable resin composition it is possible to reduce the water absorption rate by using a polyfunctional curable resin and improving the crosslink density.
  • a polyfunctional curable resin it is possible to reduce the water absorption rate by using a polyfunctional curable resin and improving the crosslink density.
  • the cured product becomes hard and brittle, and the heat cycle resistance is lowered.
  • the present invention provides a photocurable resin composition that suppresses hygroscopicity and can improve the thermal cycle resistance without impairing the migration resistance when used in a printed wiring board or the like in the cured product. For the purpose.
  • a photocurable resin composition comprising a carboxyl group-containing resin, a photopolymerization initiator, a styryl group-containing compound, and a maleimide compound.
  • the photocurable resin composition of one embodiment of the present invention preferably further contains a mercapto compound. With such a configuration, the adhesion can be improved.
  • the carboxyl group-containing resin preferably has a photosensitive group.
  • the photocurability of the photocurable resin composition increases, and the sensitivity can be improved.
  • the photopolymerization initiator is an oxime ester photopolymerization initiator represented by the following general formula (I), and an amino represented by the following general formula (II). It is preferable to include at least one selected from the group consisting of an acetophenone photopolymerization initiator and an acylphosphine oxide photopolymerization initiator represented by the following general formula (III).
  • R 1 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).
  • a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or benzoyl Represents a group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R 2 is a phenyl group (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 (which may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), carbon number 5 -8 cycloalkyl groups,
  • R 3 and R 4 are each independently 1 to 12 carbon atoms
  • R 5 and R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded
  • R 7 and R 8 Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl group substituted with a halogen atom, an al
  • the photocurable resin composition of one embodiment of the present invention preferably further includes a thermosetting component.
  • a thermosetting component By containing a thermosetting component, while providing heat resistance, the tensile elongation rate of a cured film can be increased and crack resistance and punching resistance can be improved.
  • the photocurable resin composition of one embodiment of the present invention may further contain a colorant.
  • a colorant By containing a colorant, it can be suitably used as a solder resist.
  • a dry film obtained by applying and drying the above-described photocurable resin composition on a carrier film.
  • a resist layer can be easily formed without applying a photocurable resin composition on a substrate.
  • the above-described photocurable resin composition or dry film can be used as a cured product obtained by photocuring by active energy ray irradiation.
  • a cured product when used for a printed wiring board or the like, it is possible to improve the thermal cycle resistance without impairing the migration resistance.
  • the above-described photocurable resin composition or a dry film thereof can be used as a printed wiring board having a pattern of a cured product obtained by photocuring by irradiation with active energy rays.
  • a printed wiring board having a pattern of a cured product obtained by photocuring by irradiation with active energy rays.
  • the photocurable resin composition of one embodiment of the present invention hygroscopicity can be suppressed, and the cured product can have good thermal cycle resistance without impairing the migration resistance.
  • the present inventors have found that by using a styryl group-containing compound and a maleimide compound together in a photocurable resin composition, the cured product can achieve excellent electrical characteristics and migration resistance, thereby completing the present invention. It came to. By using the styryl group-containing compound and the maleimide compound in combination, the crosslinking reaction proceeds, and the water absorption of the cured product obtained from the photocurable resin composition of the present embodiment can be suppressed.
  • the photocurable resin composition of the present embodiment will be described in detail.
  • various known carboxyl group-containing resins having a carboxyl group in the molecule are used for the purpose of imparting alkali developability. can do.
  • a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is more preferable in terms of photocurability and development resistance.
  • the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof.
  • 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.
  • 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
  • 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 polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group.
  • Added photosensitive carboxyl group-containing resin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group.
  • 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) Reaction obtained by reacting an unsaturated group-containing monocarboxylic acid with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide.
  • a carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.
  • (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions below.
  • the acid value of the above carboxyl group-containing resin is preferably 40 to 200 mgKOH / g.
  • the acid value of the above 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 may be dissolved and separated by the developer without distinction, and it becomes difficult to draw a normal resist pattern. More preferably, it is 45 to 120 mg KOH / g.
  • the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000. If the weight average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, the film may be reduced during development, and the resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior. More preferably, it is 5,000 to 100,000.
  • the blending amount of such a carboxyl group-containing resin is preferably 20 to 60% by mass in the entire composition.
  • the blending amount is less than 20% by mass, the film strength is lowered.
  • it is more than 60% by mass, the viscosity of the composition becomes high, and the applicability and the like deteriorate. More preferably, it is 30 to 50% by mass.
  • These carboxyl group-containing resins are not limited to those listed, and can be used singly or in combination.
  • photopolymerization initiator examples include an oxime ester photopolymerization initiator having a group represented by the following general formula (I), and an ⁇ -aminoacetophenone photopolymerization initiator having a group represented by the following general formula (II). It is preferable to use one or more photopolymerization initiators selected from the group consisting of acylphosphine oxide photopolymerization initiators having a group represented by the following general formula (III).
  • R 1 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). Or a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or benzoyl.
  • R 2 is a phenyl group (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 (which may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), carbon number 5 -8 cycloalkyl groups,
  • R 3 and R 4 are each independently 1 to 12 carbon atoms
  • R 5 and R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded
  • R 7 and R 8 Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl group substituted with a halogen atom, an al
  • the oxime ester photopolymerization initiator having a group represented by the general formula (I) is preferably 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (IV), Examples include compounds represented by the formula (V) and compounds represented by the general formula (VI).
  • R 9 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 carbon atoms
  • R 10 and R 12 each independently represents a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom may be substituted).
  • an alkyl group having 1 to 20 carbon atoms (which may be 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 (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group)
  • R 11 Are 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 (which is substituted with one or more hydroxyl groups).
  • Or 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 may be substituted with 6 alkyl groups or phenyl groups).
  • R 13 , R 14 and R 19 each independently represents an alkyl group having 1 to 12 carbon atoms
  • R 15 , R 16 , R 17 and R 18 each independently represents a hydrogen atom or a carbon atom.
  • Expression 1 represents an alkyl group
  • M represents O, S or NH
  • x and y each independently represents an integer of 0 to 5).
  • oxime ester photopolymerization initiators 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the general formula (IV) and a compound represented by the formula (V) are more preferable.
  • Examples of commercially available products include CGI-325, Irgacure (registered trademark) OXE01, Irgacure OXE02 (all manufactured by Ciba Japan), N-1919 (produced by ADEKA), and the like.
  • These oxime ester photopolymerization initiators can be used alone or in combination of two or more.
  • the ⁇ -aminoacetophenone photopolymerization initiator having a group represented by the general formula (II) includes 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, Irgacure 379 (all manufactured by Ciba Japan).
  • Examples of the acylphosphine oxide photopolymerization initiator having a group represented by the general formula (III) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like. Examples of commercially available products include Lucillin TPO (manufactured by BASF) and Irgacure 819 (manufactured by Ciba Japan).
  • the blending amount of such a photopolymerization initiator is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the blending amount is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off or the coating properties such as chemical resistance are deteriorated.
  • it exceeds 30 parts by mass light absorption on the surface of the solder resist coating film of the photopolymerization initiator becomes intense, and the deep curability tends to decrease. More preferably, it is 0.5 to 15 parts by mass.
  • the blending amount is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the amount is less than 0.01 parts by mass, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are deteriorated.
  • the light absorption in the soldering resist coating-film surface of a photoinitiator becomes intense, and there exists a tendency for deep part curability to fall. More preferably, it is 0.01 to 5 parts by mass.
  • Photopolymerization initiators, photoinitiator assistants and sensitizers that can be suitably used for the photocurable resin composition of the present embodiment include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, Examples include benzophenone compounds, xanthone compounds, and tertiary amine compounds.
  • 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.
  • Examples of the thioxanthone compound include 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 examples include benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4'-methyl diphenyl sulfide, 4-benzoyl-4'-ethyl diphenyl sulfide, and 4-benzoyl-4'-propyl diphenyl sulfide.
  • an ethanolamine compound a compound having a dialkylaminobenzene structure
  • 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylaminobenzophenone (manufactured by Hodogaya Chemical Co., Ltd.) Dialkylaminobenzophenones such as EAB); dialkylamino group-containing coumarin compounds such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin); Ethyl dimethylaminobenzoate (Kayacure (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure® DMB manufactured by International Bio-Synthetics), 4-d
  • a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable.
  • the dialkylaminobenzophenone compound 4,4'-diethylaminobenzophenone is preferable because of its low toxicity.
  • the dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm is not colored because the maximum absorption wavelength is in the ultraviolet region, and uses not only a colorless and transparent photosensitive composition but also a colored pigment. 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.
  • thioxanthone compounds and tertiary amine compounds are preferred.
  • the inclusion of a thioxanthone compound is preferable from the viewpoint of deep curing, and among them, thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone are preferable. preferable.
  • the amount of such a thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When the amount exceeds 20 parts by mass, the thick film curability is lowered, leading to an increase in the cost of the product. More preferably, it is 10 parts by mass or less.
  • the amount of the tertiary amine compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the blending amount is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained.
  • the amount exceeds 20 parts by mass light absorption on the surface of the dry solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease. More preferably, it is 0.1 to 10 parts by mass.
  • 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 0.01 to 35 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption. On the other hand, when it is less than 0.01, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are lowered. More preferably, it is 0.01 to 20 parts by mass.
  • the oxime ester is particularly preferable because the ultraviolet absorption of the aromatic maleimide itself is large.
  • N-phenylglycines phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like can be used as chain transfer agents in order to improve sensitivity.
  • chain transfer agent examples include mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof. These chain transfer agents can be used alone or in combination of two or more.
  • the styryl group-containing compound used in the present embodiment is used for imparting heat resistance to a cured product obtained by a curing reaction with a maleimide compound.
  • a styryl group-containing compound may be synthesized by a conventional method, or a commercially available product may be used.
  • methods for synthesizing styryl group-containing compounds include reaction of mono- and polyfunctional phenols with halogenated methylstyrene, and mono- and polyfunctional phenols having functional groups that can react with epoxy groups (for example, amino groups, hydroxyl groups, carboxyl groups, etc.).
  • the reaction of a polyfunctional compound and vinyl benzyl glycidyl ether is mentioned.
  • the styryl group-containing compound examples include vinyl naphthalene, divinyl naphthalene, divinyl biphenyl, polyvinyl benzyl ether compound obtained by reaction of polyphenol and vinyl benzyl halide, oligophenylene ether compound of terminal styrene (manufactured by Mitsubishi Gas Chemical Co., Ltd.) OPE-2St), a compound obtained by a condensation reaction between bisphenol A and halogenated methylstyrene (“Lipoxy (registered trademark) BPV-1X” manufactured by Showa Polymer Co., Ltd.), and the like. These styryl group-containing compounds can be used alone or in combination of two or more.
  • the amount of such a styryl group-containing compound is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the blending amount is less than 1 part by mass, it becomes difficult to obtain sufficient heat resistance.
  • it exceeds 50 mass parts the developability of a composition will fall and a development residue will be produced. More preferably, it is 1 to 25 parts by mass.
  • the maleimide compound used in the present embodiment is used for improving heat resistance by promoting a curing reaction with a styryl compound and / or photocuring.
  • Examples of such maleimide compounds include polyfunctional aliphatic / alicyclic maleimides and polyfunctional aromatic maleimides.
  • polyfunctional aliphatic / alicyclic maleimide examples include N, N′-methylene bismaleimide, N, N′-ethylene bismaleimide, tris (hydroxyethyl) isocyanurate, and aliphatic / alicyclic maleimide carboxylic acid.
  • aromatic polymaleimide ester compounds obtained by dehydrating esterification of maleimide carboxylic acid and various aromatic polyols, or transesterification reaction of maleimide carboxylic acid ester and various aromatic polyols; Aromatic polymaleimide ester compounds obtained by ether ring-opening reaction of carboxylic acid and various aromatic polyepoxides; aromatic polymaleimide urethane compounds obtained by urethanization reaction of maleimide alcohol and various aromatic polyisocyanates And aromatic polyfunctional maleimides.
  • polyfunctional aromatic maleimide examples include N, N ′-(4,4′-diphenylmethane) bismaleimide, N, N′-2,4-tolylene bismaleimide, N, N′-2, 6-tolylene bismaleimide, 1-methyl-2,4-bismaleimide benzene, N, N′-m-phenylene bismaleimide, N, N′-p-phenylene bismaleimide, N, N′-m-toluylene Bismaleimide, N, N′-4,4′-biphenylenebismaleimide, N, N′-4,4 ′-[3,3′-dimethyl-biphenylene] bismaleimide, N, N′-4,4′- [3,3′-dimethyldiphenylmethane] bismaleimide, N, N′-4,4 ′-[3,3′-dimethyldiphenylmethane] bismaleimide, N, N′-4,4 ′-[3,3′-diethyl
  • bismaleimide derivatives may be synthesized by conventional methods, or commercially available products may be used.
  • those that do not contain a halogen atom in the molecule are preferable from the viewpoint of not placing a burden on the environment.
  • These can be used individually by 1 type or in combination of 2 or more types.
  • the blending amount of such a maleimide compound is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the blending amount is less than 1 part by mass, it becomes difficult to obtain sufficient heat resistance.
  • it exceeds 50 mass parts the developability of a composition will fall and a development residue will be produced. More preferably, it is 1 to 25 parts by mass.
  • a mercapto compound can be added to the photocurable resin composition of the present embodiment for the purpose of addition reaction and crosslinking to vinyl groups and maleimide groups. Addition of a mercapto compound can prevent deterioration of coating film characteristics due to oxidation of vinyl groups.
  • a polyfunctional mercapto compound since crosslinking can be obtained, characteristics such as PCT resistance and HAST resistance are improved. Furthermore, since these mercapto compounds function as chain transfer agents and / or adhesion imparting agents, it is possible to simultaneously improve sensitivity and adhesion.
  • Examples of such mercapto compounds include mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl- 3-mercaptopropionate, 2,2- (ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanethiol, Examples include cyclohexanethiol, thioglycerol, 4,4-thiobisbenzenethiol and the like.
  • Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (all manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT (registered trademark) -PE1, Karenz MT -BD1, Karenz (registered trademark) -NR1 (all manufactured by Showa Denko KK) and the like.
  • Examples of the mercapto compound having a heterocyclic ring include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto-4-ethyl-4- Butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N-methyl-2 -Mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl-2-mercapto-4 -Butyrolactam, 2-mercapto-5-valerolactone, 2-mercapto 5-valerolactam, N-methyl-2
  • the blending amount of such a mercapto compound is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the blending amount is less than 0.01 parts by mass, the mercapto compound is not cured and the heat resistance is not improved.
  • it exceeds 20 parts by mass a development residue is generated, which is not preferable. More preferably, it is 0.1 to 5 parts by mass.
  • thermosetting component can be added to the photocurable resin composition of the present embodiment in order to impart heat resistance.
  • thermosetting resins such as amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, and benzoguanamine derivatives, and cyclocarbonate compounds can be used.
  • thermosetting component having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.
  • thermosetting component having a plurality of cyclic (thio) ether groups in such a molecule has either one of the three-, four- or five-membered cyclic (thio) ether groups or two types of groups in the molecule.
  • a compound having a plurality of epoxy groups in the molecule that is, a polyfunctional epoxy compound
  • a compound having a plurality of oxetanyl groups in the molecule that is, a polyfunctional oxetane compound
  • thioether groups in the molecule A compound having the same, that is, an episulfide resin.
  • amino resins examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.
  • the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group.
  • the type of the alkoxymethyl group is not particularly limited, and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like.
  • a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.
  • thermosetting components can be used alone or in combination of two or more.
  • the cyclocarbonate compound is not particularly limited as long as it is a cyclic compound and has a carbonate bond.
  • Examples include alkylene carbonate compounds having a polyfunctional structure.
  • Examples of the polyfunctional epoxy compound include jER (registered trademark) 828, jER834, jER1001, jER1004 (all manufactured by Mitsubishi Chemical Corporation), Epicron (registered trademark) 840, Epicron 850, Epicron 1050, and Epicron 2055 (all DIC Corporation).
  • Epototo registered trademark
  • YD-011, YD-013, YD-127, YD-128 all manufactured by Nippon Steel Chemical Co., Ltd.
  • Bisphenol A type epoxy resin such as 664 (all manufactured by Asahi Kasei Kogyo Co., Ltd.); jERYL903 (manufactured by Mitsubishi Chemical), Epicron 152, Epicron 165 (all manufactured by DIC), Epototo YDB-400, YDB-500 (all new) Manufactured by Nippon Steel Chemical Co., Ltd.)
  • E. R. 542 manufactured by Dow Chemical Company
  • Araldite 8011 manufactured by Ciba Japan
  • Sumiepoxy ESB-400, ESB-700 both manufactured by Sumitomo Chemical Co., Ltd.
  • Brominated epoxy resins such as 714 (both manufactured by Asahi Kasei Kogyo Co., Ltd.); jER152, jER154 (both manufactured by Mitsubishi Chemical Co., Ltd.); E. N. 431, D.D. E. N.
  • E. R. Novolak type epoxy resins such as ECN-235 and ECN-299 (both manufactured by Asahi Kasei Kogyo Co., Ltd.); Epicron 830 (manufactured by DIC), jER807 (manufactured by Mitsubishi Chemical), Epototo YDF-170, YDF-175, YDF-2004 Bisphenol F type epoxy resins such as YSLV-80XY (manufactured by Nippon Steel Chemical Co., Ltd.), Araldite XPY306 (manufactured by Ciba Japan Co., Ltd.); Epototo ST-2004, ST-2007, ST Hydrogenated bisphenol A type epoxy resin such as -3000 (all manufactured by Nippon Steel Chemical Co., Ltd.); jER604 (manufactured by Mitsubishi Chemical Co., Ltd.), Epototo YH-434 (manufactured by Nippon Steel Chemical Co., Ltd.), Araldite MY720 (Ciba Japan
  • Glycidylamine type epoxy such as Sumiepoxy ELM-120 (Sumitomo Chemical Co., Ltd.) Shidan resin
  • Hydantoin type epoxy resin such as Araldite CY-350 (manufactured by Ciba Japan); Celoxide (registered trademark) 2021 (manufactured by Daicel Chemical Industries), Araldite CY175, CY179 (all by Ciba Japan) Alicyclic epoxy resin
  • YL-933 manufactured by Mitsubishi Chemical Corporation
  • Trihydroxyphenylmethane type epoxy resins such as EPPN (registered trademark) -501 and EPPN-502 (all manufactured by Nippon Kayaku Co., Ltd.); YL-6056, YX-4000, YL-6121 (all manufactured by Mitsubishi Chemical Corporation) Bisylenol type or biphenol type epoxy resins such as bisphenol S type epoxy resins such as EBPS-200 (manufactured by Nippon Kayaku Co., Ltd.), EPX-30 (manufactured by ADEKA), EXA-1514 (manufactured by DIC) Bisphenol A novolak type epoxy resin such as jER157S (Mitsubishi Chemical); tetraphenylolethane type epoxy resin such as jERYL-931 (Mitsubishi Chemical), Araldite 163 (Ciba Japan); Araldite PT810 (Ciba) ⁇ Product made in Japan, TEPIC (product made in Nissan Chemical Industries) Heterocyclic epoxy resins such as Bremer
  • YR-102 YR-450, etc.
  • YR-450 YR-450, etc.
  • these epoxy resins can be used alone or in combination of two or more.
  • a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.
  • polyfunctional oxetane compound examples 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-ethyl-3- In addition to polyfunctional oxetanes such as 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-hydroxy
  • Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. 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.
  • thermosetting component having a plurality of cyclic (thio) ether groups in the molecule 0.6 to 2.5 equivalents are preferable with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin.
  • the blending amount is less than 0.6, a carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation and the like are lowered.
  • the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, thereby reducing the strength of the coating film. More preferably, it is 0.8 to 2.0 equivalents.
  • the photocurable resin composition of the present embodiment includes a plurality of isocyanate groups in one molecule as a thermosetting component in order to improve the curability of the photosensitive resin composition and the toughness of the resulting cured film.
  • a compound having a blocked isocyanate group can be added.
  • Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule.
  • the compound which has this, ie, a blocked isocyanate compound, etc. are mentioned.
  • polyisocyanate compound for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
  • aromatic polyisocyanate examples include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene.
  • aromatic polyisocyanate examples include range isocyanate and 2,4-tolylene dimer.
  • aliphatic polyisocyanate examples include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate.
  • alicyclic polyisocyanate examples include bicycloheptane triisocyanate.
  • adduct body, burette body, and isocyanurate body of the isocyanate compound mentioned above are mentioned.
  • the blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.
  • blocked isocyanate compound an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used.
  • examples of the isocyanate compound that can react with the blocking agent include the polyisocyanate compounds described above.
  • isocyanate blocking agent examples include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ⁇ -caprolactam, ⁇ -palerolactam, ⁇ -butyrolactam and ⁇ -propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid And alcohol blocking agents such as ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl e
  • the blocked isocyanate compound may be commercially available, for example, Sumijoule (registered trademark) BL-3175, BL-4165, BL-1100, BL-1265-, Desmodur (registered trademark) TPLS-2957, TPLS-2062.
  • TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm 2265 (all manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate (registered trademark) 2512, Coronate 2513, Coronate 2520 (all manufactured by Nippon Polyurethane Industry Co., Ltd.), B-830, B-815, B-846, B-870, B-874, B-882 (all manufactured by Mitsui Takeda Chemical), TPA-B80E, 17B-60PX, E402-B80T (all manufactured by Asahi Kasei Chemicals), etc. Can be mentioned. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.
  • Such compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.
  • the compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin, the compounding amount is less than 1 part by mass, Sufficient toughness of the coating film cannot be obtained. On the other hand, when it exceeds 100 mass parts, storage stability falls. More preferably, it is 2 to 70 parts by mass.
  • thermosetting component having a plurality of cyclic (thio) ether groups it is preferable to contain a thermosetting catalyst.
  • thermosetting catalysts examples 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 compounds include imidazole compounds such as 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both manufactured by Shikoku Kasei Kogyo Co., Ltd.), and dimethylamine blocked isocyanate compounds such as U- CAT3503N, U-CAT (registered trademark) 3502T (all manufactured by San-Apro), bicyclic amidine compounds and salts thereof, DBU, DBN, U-CATSA (registered trademark) 102, U-CAT5002 (all manufactured by San-Apro) ) And the like.
  • imidazole compounds such as 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • dimethylamine blocked isocyanate compounds such as U- CAT3503N, U-CAT (registered trademark) 3502T (all manufactured by San-Apro), bicyclic amidine
  • 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 catalysts is sufficient at a normal quantitative ratio, for example, for 100 parts by mass of a thermosetting component having a carboxyl group-containing resin 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 parts by mass.
  • the photocurable resin composition of the present embodiment can contain a colorant.
  • a colorant for example, known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and pigments 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.
  • red colorant examples include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, and the like.
  • the color index (CI; issued by The Society of Dyers and Colorists) number is given.
  • 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.
  • blue colorants include phthalocyanine and anthraquinone
  • pigment types include 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
  • dye systems such as 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, and the like can be used.
  • a metal-substituted or unsubstituted phthalocyanine compound can also be used.
  • green colorant examples include phthalocyanine series, anthraquinone series, and perylene series, and 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, and anthraquinone, and specific examples include the following.
  • 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.
  • the blending ratio of such a colorant is not particularly limited, but is preferably 10 parts by mass or less, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. .
  • the photocurable resin composition of the present embodiment has a plurality of ethylenically unsaturated groups in the molecule in order to insolubilize or help insolubilize the ethylenically unsaturated group-containing carboxyl group-containing resin in an alkaline aqueous solution.
  • Compounds may be added. Examples of such compounds include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, and the like.
  • Polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts or propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycy Ethers, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or each methacrylates corresponding to the above acrylate.
  • an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate half such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin.
  • a polyfunctional epoxy resin such as a cresol novolac type epoxy resin
  • a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate half
  • isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin.
  • an epoxy urethane acrylate compound obtained by reacting a urethane compound.
  • Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.
  • the blending amount of the compound having a plurality of ethylenically unsaturated groups in the molecule is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays.
  • it exceeds 100 mass parts the solubility with respect to alkaline aqueous solution falls, and a coating film becomes weak. More preferably, it is 10 to 70 parts by mass.
  • a filler can be blended as necessary in order to increase the physical strength of the coating film.
  • known inorganic or organic fillers can be used, but barium sulfate, spherical silica, hydrotalcite and talc are particularly preferable.
  • metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers.
  • the amount of such filler is preferably 75% by mass or less of the total amount of the composition.
  • the blending amount of the filler exceeds 75% by mass of the total amount of the composition, the viscosity of the insulating composition increases, the coating and moldability deteriorate, and the cured product becomes brittle. More preferably, the content is 0.1 to 60% by mass.
  • the photocurable resin composition of the present embodiment may use an organic solvent for the synthesis of a carboxyl group-containing resin, the preparation of the composition, or the viscosity adjustment for application to a substrate or a carrier film. it can.
  • organic solvents examples 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 a
  • the photocurable resin composition of the present embodiment is used to prevent oxidation.
  • antioxidants such as radical scavengers that invalidate the generated radicals and / or peroxide decomposers that decompose the generated peroxides into harmless substances and prevent the generation of new radicals can do.
  • Antioxidants that act as radical scavengers include, for example, hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2 -Methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2 , 4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-t-butyl-4-hydroxybenzyl)- Phenolic compounds such as S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6-tetramethyl) 4-piperidyl) - se
  • the radical scavenger may be commercially available, for example, ADK STAB (registered trademark) AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (all manufactured by ADEKA), IRGANOX 1010, IRGANOX (registered trademark) 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN (registered trademark) 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, (Both manufactured by Ciba Japan).
  • the peroxide decomposing agent may be commercially available, for example, Adeka Stub TPP (manufactured by ADEKA), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd.), Sumilyzer (registered trademark) TPS (manufactured by Sumitomo Chemical Co., Ltd.) Etc. These antioxidants can be used alone or in combination of two or more.
  • the photocurable resin composition of the present embodiment is used in addition to the above-described antioxidant in order to take a countermeasure against stabilization of ultraviolet rays.
  • UV absorbers can be used.
  • Examples of such an ultraviolet absorber include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4- Benzophenone derivatives such as methoxybenzophenone and 2,4-dihydroxybenzophenone; 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5 -Benzoate derivatives such as di-t-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; 2- (2'-hydroxy-5'-t-butylphenyl) benzo Triazole, 2- (2'-hydroxy-5'-methylphenyl) ene Zotriazole, 2- (2'-hydroxy-3 ' -T-butyl-5'-methylphenyl)
  • Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460 TINUVIN® 479 (both manufactured by Ciba Japan).
  • Such ultraviolet absorbers can be used singly or in combination of two or more, and the stability of the molded product obtained from the photocurable resin composition of the present embodiment when used in combination with an antioxidant. Can be achieved.
  • the photocurable resin composition of the present embodiment is a known thickener such as fine silica, organic bentonite, montmorillonite, silicone-based, fluorine-based, polymer-based antifoaming agent and / or leveling as required.
  • Known additives such as silane coupling agents such as imidazole, thiazole and triazole, antioxidants, rust inhibitors and the like can be blended.
  • a polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the polymerizable compound contained in the photocurable resin composition in the present embodiment.
  • thermal polymerization inhibitors examples include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride.
  • Phenothiazine chloranil, naphthylamine, ⁇ -naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, Examples include picric acid, 4-toluidine, methylene blue, copper and an organic chelating agent reaction product, methyl salicylate, and phenothiazine, a nitroso compound, a chelate of a nitroso compound and Al, and the like.
  • an adhesion promoter can be used in order to improve adhesion between layers or adhesion between the photosensitive resin layer and the substrate.
  • adhesion promoters include benzimidazole, benzoxazole, benzothiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, Examples include triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, and silane coupling agent.
  • the photocurable resin composition of the present embodiment configured as described above is prepared with a predetermined composition, it is adjusted to a viscosity suitable for the coating method with an organic solvent, It is applied by a method such as a flow coating method, a roll coating method, a bar coater method, a screen printing method, or a curtain coating method.
  • Volatile drying after coating can be done by using hot air circulation drying oven, IR furnace, hot plate, convection oven, etc. Can be carried out at a temperature of about 60 to 100 ° C. using a method of spraying on a support.
  • a resin insulating layer may be formed by forming a dry film from the photocurable resin composition and pasting it on a substrate.
  • the dry film has a structure in which, for example, a carrier film such as polyethylene terephthalate, a resin insulating layer such as a solder resist layer, and a peelable cover film used as necessary are laminated in this order.
  • a carrier film such as polyethylene terephthalate
  • a resin insulating layer such as a solder resist layer
  • a peelable cover film used as necessary are laminated in this order.
  • the resin insulation layer is a layer obtained by applying and drying a photocurable resin composition on a carrier film or a cover film.
  • the photocurable resin composition of the present embodiment is uniformly applied to a carrier film with a thickness of 10 to 150 ⁇ m using a blade coater, a lip coater, a comma coater, a film coater, etc., and then dried. Formed. And a dry film is formed by laminating
  • the carrier film may be laminated after the photocurable resin composition is applied to the cover film and dried.
  • thermoplastic film such as a polyester film having a thickness of 2 to 150 ⁇ m is used.
  • cover film a polyethylene film, a polypropylene film or the like can be used, but it is preferable that the adhesive force with the solder resist layer is smaller than that of the carrier film.
  • paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy All grades (FR-4, etc.) of copper clad laminates such as copper clad laminates for high frequency circuits using fluorine, polyethylene, PPO, cyanate esters, etc., other polyimide films, PET films, A glass substrate, a ceramic substrate, a wafer board, etc. can be mentioned.
  • exposure is selectively performed with an active energy ray or directly with a laser direct exposure machine through a photomask having a pattern formed by a contact method (or non-contact method).
  • a direct drawing device for example, a laser direct imaging device that draws an image directly with a laser using CAD data from a computer
  • an exposure device equipped with a metal halide lamp for example, an exposure machine mounted, an exposure machine equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high pressure mercury lamp.
  • the active energy ray it is preferable to use laser light having a wavelength of 350 to 410 nm. By setting the wavelength within this range, radicals can be efficiently generated from the photoinitiator. If a laser beam in this range is used, either a gas laser or a solid laser may be used.
  • the exposure amount varies depending on the film thickness and the like, but is generally 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 wavelength of 350 to 410 nm.
  • the exposed portion portion irradiated with the active energy ray
  • the unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 to 3 wt% Na 2 CO 3 aqueous solution).
  • Development is performed to form a cured product (pattern).
  • the developing method can be a dipping method, a shower method, a spray method, a brush method, or the like.
  • an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used.
  • thermosetting component for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, a carboxyl group of the carboxyl group-containing resin and a heat having a plurality of cyclic (thio) ether groups in the molecule.
  • the cured component reacts to form a cured product having excellent characteristics such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.
  • compositions of Examples and Comparative Examples described in Table 1 were dried by a screen printing method on a copper solid substrate, applied to about 25 ⁇ m, and dried for 30 minutes in a hot air circulation drying oven at 80 ° C. . After drying, development was performed with a 1% by mass aqueous sodium carbonate solution, and the time until the dried coating film was removed was measured with a stopwatch.
  • This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then cured by heating at 170 ° C. for 60 minutes.
  • the characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.
  • ⁇ Electroless gold plating resistance> Using commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 0.5 ⁇ m and gold 0.03 ⁇ m, and the presence or absence of peeling of the resist layer or plating penetration by tape peel After the presence or absence was evaluated, the presence or absence of peeling of the resist layer was evaluated with a tape peel. 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.
  • HAST ⁇ Insulation after humidification test
  • ⁇ TCT resistance> The composition of each Example and Comparative Example shown in Table 1 was applied to a substrate on which a 2 mm copper line pattern was formed, exposed and developed, then thermally cured, and a 3 mm square resist pattern on the copper line.
  • substrate with which was formed was produced. This evaluation substrate was put into a thermal cycle machine in which a temperature cycle was performed between ⁇ 65 ° C. and 150 ° C., and TCT (Thermal Cycle Test) was performed. The appearance at 600 cycles, 800 cycles and 1000 cycles was observed. A: No abnormality at 1000 cycles. ⁇ : No abnormality at 800 cycles, cracks occurred at 1000 cycles. ⁇ : No abnormality at 600 cycles, crack occurred at 800 cycles. X: Cracks occurred at 600 cycles.
  • ⁇ PCT resistance> The evaluation board
  • Dry film evaluation Evaluation substrates were prepared for the photosensitive resin compositions of Example 1 and Comparative Example 1 by the method shown below and evaluated in the same manner.
  • Example 1 ⁇ Dry film production>
  • the photocurable resin compositions of Example 1 and Comparative Example 1 were each appropriately diluted with methyl ethyl ketone, and then PET film (FB-50 manufactured by Toray Industries, Inc.) was used so that the film thickness after drying was 20 ⁇ m using an applicator. 16 ⁇ m) and dried at 80 ° C. for 30 minutes to obtain a dry film.
  • PET film FB-50 manufactured by Toray Industries, Inc.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
PCT/JP2010/004678 2009-07-21 2010-07-21 光硬化性樹脂組成物 WO2011010461A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020127001502A KR101372202B1 (ko) 2009-07-21 2010-07-21 광경화성 수지 조성물
CN201080033075.XA CN102472965B (zh) 2009-07-21 2010-07-21 光固化性树脂组合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009-170136 2009-07-21
JP2009170136A JP5559999B2 (ja) 2009-07-21 2009-07-21 光硬化性樹脂組成物

Publications (1)

Publication Number Publication Date
WO2011010461A1 true WO2011010461A1 (ja) 2011-01-27

Family

ID=43498943

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/004678 WO2011010461A1 (ja) 2009-07-21 2010-07-21 光硬化性樹脂組成物

Country Status (5)

Country Link
JP (1) JP5559999B2 (ko)
KR (1) KR101372202B1 (ko)
CN (1) CN102472965B (ko)
TW (1) TWI489201B (ko)
WO (1) WO2011010461A1 (ko)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015001873A1 (ja) * 2013-07-01 2015-01-08 富士フイルム株式会社 着色硬化性組成物、これを用いた硬化膜、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子、液晶表示装置、および有機ｅｌ表示装置
US11434313B2 (en) * 2020-12-16 2022-09-06 Canon Kabushiki Kaisha Curable composition for making cured layer with high thermal stability

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5439075B2 (ja) 2009-07-21 2014-03-12 太陽ホールディングス株式会社 光硬化性樹脂組成物
JP5654927B2 (ja) * 2011-03-30 2015-01-14 住友理工株式会社 液体封入式防振ゴム装置
JP6317253B2 (ja) 2012-05-17 2018-04-25 太陽インキ製造株式会社 液状現像型のマレイミド組成物、プリント配線板
JP6953758B2 (ja) * 2017-03-24 2021-10-27 昭和電工マテリアルズ株式会社 感光性樹脂組成物、それを用いたドライフィルム、プリント配線板、及びプリント配線板の製造方法
JP6670009B1 (ja) * 2018-11-07 2020-03-18 ナガセケムテックス株式会社 光造形用トレイおよびその製造方法
US11639398B2 (en) * 2019-12-30 2023-05-02 Rohm And Haas Electronic Materials Llc Photosensitive bismaleimide composition
JPWO2021220982A1 (ko) * 2020-04-27 2021-11-04

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006285174A (ja) * 2004-12-08 2006-10-19 Fuji Photo Film Co Ltd 感光性組成物及び感光性フィルム、並びに、永久パターン及びその形成方法
JP2007164126A (ja) * 2005-11-21 2007-06-28 Hitachi Chem Co Ltd 永久レジスト用感光性エレメント、レジストパターンの形成方法、プリント配線板及び半導体素子
JP2007256445A (ja) * 2006-03-22 2007-10-04 Mitsubishi Paper Mills Ltd 光重合性組成物および感光性平版印刷版材料
JP2007256845A (ja) * 2006-03-24 2007-10-04 Fujifilm Corp 感光性組成物、感光性フィルム、永久パターン形成方法、及びプリント基板
JP2008274003A (ja) * 2007-04-25 2008-11-13 Hitachi Chem Co Ltd リン含有化合物、このリン含有化合物を含有してなる樹脂組成物及び樹脂組成物を用いた感光性フィルム、レジストパターンの形成方法及びプリント配線板

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1832617B1 (en) * 2006-03-10 2018-09-19 Mitsubishi Gas Chemical Company, Inc. Polyfunctional phenylene ether oligomer, derivative thereof, resin composition containing the same, and use thereof
JP4663679B2 (ja) * 2007-05-08 2011-04-06 太陽ホールディングス株式会社 光硬化性樹脂組成物、ドライフィルム、硬化物、及びプリント配線板

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006285174A (ja) * 2004-12-08 2006-10-19 Fuji Photo Film Co Ltd 感光性組成物及び感光性フィルム、並びに、永久パターン及びその形成方法
JP2007164126A (ja) * 2005-11-21 2007-06-28 Hitachi Chem Co Ltd 永久レジスト用感光性エレメント、レジストパターンの形成方法、プリント配線板及び半導体素子
JP2007256445A (ja) * 2006-03-22 2007-10-04 Mitsubishi Paper Mills Ltd 光重合性組成物および感光性平版印刷版材料
JP2007256845A (ja) * 2006-03-24 2007-10-04 Fujifilm Corp 感光性組成物、感光性フィルム、永久パターン形成方法、及びプリント基板
JP2008274003A (ja) * 2007-04-25 2008-11-13 Hitachi Chem Co Ltd リン含有化合物、このリン含有化合物を含有してなる樹脂組成物及び樹脂組成物を用いた感光性フィルム、レジストパターンの形成方法及びプリント配線板

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015001873A1 (ja) * 2013-07-01 2015-01-08 富士フイルム株式会社 着色硬化性組成物、これを用いた硬化膜、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子、液晶表示装置、および有機ｅｌ表示装置
JP2015028602A (ja) * 2013-07-01 2015-02-12 富士フイルム株式会社 着色硬化性組成物、これを用いた硬化膜、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子、液晶表示装置、および有機ｅｌ表示装置
US11434313B2 (en) * 2020-12-16 2022-09-06 Canon Kabushiki Kaisha Curable composition for making cured layer with high thermal stability

Also Published As

Publication number Publication date
JP2011027770A (ja) 2011-02-10
JP5559999B2 (ja) 2014-07-23
KR101372202B1 (ko) 2014-03-07
TWI489201B (zh) 2015-06-21
KR20120036987A (ko) 2012-04-18
CN102472965B (zh) 2014-08-13
CN102472965A (zh) 2012-05-23
TW201116928A (en) 2011-05-16

Similar Documents

Publication Publication Date Title
JP5583941B2 (ja) 光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP5537864B2 (ja) 光硬化性樹脂組成物
JP5439075B2 (ja) 光硬化性樹脂組成物
JP6061449B2 (ja) 光硬化性熱硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
WO2011007566A1 (ja) 光硬化性樹脂組成物
JP5559999B2 (ja) 光硬化性樹脂組成物
JP5619443B2 (ja) 光硬化性熱硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
TWI420243B (zh) A photohardenable resin composition, a dry film thereof and a hardened product, and a printed circuit board using the same
WO2010125721A1 (ja) 光硬化性熱硬化性樹脂組成物
WO2011001485A1 (ja) 光硬化性熱硬化性樹脂組成物
WO2011001484A1 (ja) 光硬化性熱硬化性樹脂組成物
JPWO2011122025A1 (ja) 光硬化性樹脂組成物
JP2011043565A (ja) 光硬化性樹脂組成物
JP5091353B2 (ja) 光硬化性樹脂組成物
JP5422319B2 (ja) 感光性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP5338009B2 (ja) 光硬化性熱硬化性樹脂組成物及びその硬化物並びにそれらを用いたプリント配線板
JP5951820B2 (ja) 光硬化性樹脂組成物
WO2010113478A1 (ja) 硬化性樹脂組成物およびプリント配線板
JP5864524B2 (ja) 光硬化性樹脂組成物
WO2010125720A1 (ja) 光硬化性熱硬化性樹脂組成物
JP2011053421A (ja) 光硬化性熱硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP5917602B2 (ja) 光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP2013047818A (ja) 光硬化性樹脂組成物
WO2011034124A1 (ja) 感光性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP5439255B2 (ja) 光硬化性熱硬化性樹脂組成物

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080033075.X

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10802082

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20127001502

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10802082

Country of ref document: EP

Kind code of ref document: A1