WO2011010457A1 - Composition de résine photodurcissable - Google Patents

Composition de résine photodurcissable Download PDF

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Publication number
WO2011010457A1
WO2011010457A1 PCT/JP2010/004670 JP2010004670W WO2011010457A1 WO 2011010457 A1 WO2011010457 A1 WO 2011010457A1 JP 2010004670 W JP2010004670 W JP 2010004670W WO 2011010457 A1 WO2011010457 A1 WO 2011010457A1
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Prior art keywords
group
compound
resin composition
manufactured
photocurable resin
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PCT/JP2010/004670
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English (en)
Japanese (ja)
Inventor
昌司 峰岸
聖夫 有馬
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太陽ホールディングス株式会社
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Priority to JP2011523555A priority Critical patent/JP5091353B2/ja
Publication of WO2011010457A1 publication Critical patent/WO2011010457A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/08—Epoxidised polymerised polyenes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/04—Oxidation
    • C08C19/06—Epoxidation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • 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 photocurable resin composition used as, for example, a solder resist for a printed wiring board.
  • the photo-curable resin composition can be finely processed by applying the principle of photolithography. Furthermore, since a cured product having excellent physical properties can be obtained, it is used in electronic devices and printing plates.
  • the photo-curable 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.
  • characteristics related to long-term reliability such as heat resistance that can withstand processing under high temperature conditions such as soldering, as well as 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 present invention is a photocurable resin composition capable of suppressing hygroscopicity and capable of improving thermal cycle resistance without impairing migration resistance characteristics when used in a printed wiring board or the like in a cured product thereof.
  • the purpose is to provide.
  • a photocurable resin composition comprising a carboxyl group-containing resin, a photopolymerization initiator, an epoxidized polybutadiene compound, and a styryl group-containing 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 preferably a mixture of an acetophenone photopolymerization initiator and one or more photopolymerization initiators selected from the group consisting of acylphosphine oxide photopolymerization initiators 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 photocurable resin composition of one embodiment of the present invention preferably further contains 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 can 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 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.
  • the above-described photocurable resin composition or a dry film thereof can be used as a printed wiring board having a cured product pattern obtained by photocuring by irradiation with active energy rays.
  • hygroscopicity can be suppressed, and in the cured product, when used for a printed wiring board or the like, the thermal cycle resistance without impairing the migration resistance characteristics. Can be improved.
  • the present inventors have found that the above-described object can be achieved by a photocurable resin composition containing a carboxyl group-containing resin, a photopolymerization initiator, an epoxidized polybutadiene compound, and a styryl group-containing compound. It came to complete.
  • an epoxidized polybutadiene compound not only provides flexibility to the cured product of this photo-curable resin composition, but also contributes to stress relaxation during over-curing of the coating film and improves thermal cycle resistance. It becomes possible.
  • crosslinking with an epoxy group and a hydroxyl group introduced into the epoxidized polybutadiene compound the crosslinking density can be improved and the migration resistance can be improved.
  • 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 preferable from the viewpoint of photocurability and development resistance.
  • the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof.
  • carboxyl group-containing resin examples include the following compounds (any of oligomers and polymers) are preferable.
  • 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 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.
  • Reaction product obtained by reacting a compound 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 with an unsaturated group-containing monocarboxylic acid.
  • 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 mixtures thereof, and the same applies to other similar expressions.
  • the acid value of the carboxyl group-containing resin is preferably in the range of 40 to 200 mgKOH / g.
  • the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult.
  • it exceeds 200 mgKOH / g dissolution of the exposed portion by the developer proceeds, so the line becomes thinner than necessary, and in some cases, dissolution and peeling occur with the developer without distinguishing between the exposed portion and the unexposed portion, It becomes difficult to draw a normal resist pattern. More preferably, it is in the range of 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 in the range of 5,000 to 100,000.
  • the amount of such a carboxyl group-containing resin is preferably in the range of 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 in the range of 30 to 50% by mass.
  • carboxyl group-containing resins are not limited to those listed, and can be used either alone 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). Or / and by using one or more photopolymerization initiators selected from the group consisting of acylphosphine oxide photopolymerization initiators having a group represented by the following formula (III), It is possible to obtain high resolution in the resist having the same.
  • 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),
  • the compound represented by general formula (V) and the compound represented by the following general formula (VI) are mentioned.
  • 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 And 6 may be substituted with an alkyl group or a phenyl group)
  • 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.
  • 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.
  • Commercially available products include CGI-325 manufactured by Ciba Japan, Irgacure (registered trademark) OXE01, Irgacure OXE02, N-1919 manufactured 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, and Irgacure 379 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 Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Japan.
  • the blending amount of such a photopolymerization initiator is preferably in the range of 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 in the range of 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. 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, 1,1-dichloroacetophenone, and the like.
  • anthraquinone compound examples include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.
  • thioxanthone compound examples include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.
  • 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, 4-benzoyl-4′-propyl diphenyl sulfide, and the like. It is done.
  • an ethanolamine compound a compound having a dialkylaminobenzene structure
  • 4,4′-dimethylaminobenzophenone (Nisso MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylaminobenzophenone (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-dimethylaminobenzoic
  • 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 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 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
  • a compounding quantity of a thioxanthone compound 20 mass parts or less are preferable with respect to 100 mass parts of carboxyl group-containing resin.
  • the compounding quantity of a thioxanthone compound exceeds 20 mass parts, thick film sclerosis
  • the compounding 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 amount of the tertiary amine compound 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 35 parts by mass or less 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.
  • 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 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 epoxidized polybutadiene compound used in the photocurable resin composition of the present embodiment not only improves the flexibility of the resulting cured product (cured coating film), but also provides stress relaxation during solder resist overcuring. Used.
  • Such an epoxidized butadiene compound is not particularly limited as long as it is a polybutadiene compound containing an epoxy group.
  • Epofriend registered trademark (produced by Daicel Chemical Industries, Ltd.) obtained by copolymerizing styrene and butadiene and then epoxidizing a double bond in the copolymer with an oxidizing agent such as peracetic acid. Epoxidized product of butadiene and styrene block copolymer).
  • Epofriend A1005 (butadiene / styrene weight ratio, 60/40, epoxy equivalent 1800 to 2100)
  • Epofriend A1010 (butadiene / styrene weight ratio, 60/40, epoxy equivalent 950 to 1050)
  • Epofriend Friend A1020 (butadiene / styrene weight ratio 60/40, epoxy equivalent 480 to 540), and the like.
  • Epolide registered trademark
  • PB3600 manufactured by Daicel Chemical Industries
  • Ricon657 manufactured by Sartomer
  • These epoxidized polybutadiene compounds can be used alone or as a mixture of two or more.
  • the amount of such an epoxidized butadiene compound is preferably 3 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the blending amount is less than 3 parts by mass, it becomes difficult to obtain sufficient flexibility and stress relaxation.
  • it exceeds 100 parts by mass the developability of the composition is lowered, and it is difficult to obtain good resolution. More preferably, it is 10 to 60 parts by mass.
  • the styryl group-containing compound used in this embodiment is used for imparting heat resistance.
  • 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, for example, reaction of mono- and polyfunctional phenols with halogenated methylstyrene, functional groups that can react with epoxy groups (for example, amino groups, hydroxyl groups, carboxyl groups, etc.).
  • the reaction of the mono- and polyfunctional compound which has and vinylbenzyl glycidyl ether is mentioned.
  • a styryl compound can be used individually by 1 type or in combination of 2 or more types.
  • 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 parts by mass the developability of the composition is lowered and it is difficult to obtain good resolution. More preferably, it is 1 to 10 parts by mass.
  • the photocurable resin composition of the present embodiment includes a mercapto that acts as an additional reagent, a chain transfer agent, and / or an adhesion imparting agent for the purpose of improving the curability of the photosensitive resin composition and the adhesion of the resulting cured film.
  • a mercapto that acts as an additional reagent, a chain transfer agent, and / or an adhesion imparting agent for the purpose of improving the curability of the photosensitive resin composition and the adhesion of the resulting cured film.
  • Compounds can be added.
  • Examples of mercapto compounds include chain transfer agents having a hydroxyl group such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopro Pionate, methyl-3-mercaptopropionate, 2,2- (ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol , Cyclopentanethiol, cyclohexanethiol, thioglycerol, 4,4-thiobisbenzenethiol and the like.
  • chain transfer agents having a hydroxyl group such as mercaptoethanol, mer
  • 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-PE1, Karenz MT-BD1, and 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- Lucapto-5-valerolactam, N-
  • Disnet F 2-dibutylamino-4,6-dimercapto-s-triazine
  • Disnet DB 2-dibutylamino-4,6-dimercapto-s-triazine
  • 2-anilino-4,6- Dimercapto-s-triazine manufactured by Sankyo Kasei Co., Ltd. Disnet (registered trademark) AF
  • 3-mercapto-4-methyl-4H-1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, and 1-phenyl-5-mercapto-1H-tetrazole are preferred.
  • These mercapto compounds can be used alone or in combination of two or more.
  • thermosetting component can be added to the photocurable resin composition of the present embodiment in order to impart heat resistance.
  • thermosetting components used in the present embodiment include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, and benzoguanamine derivatives, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and episulfide resins.
  • a known thermosetting resin can be used.
  • Particularly preferred is a 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 the molecule has either one of the three-, four- or five-membered cyclic (thio) ether groups or a plurality of 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, a compound having a plurality of thioether groups in the molecule That is, an episulfide resin etc. are mentioned.
  • 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)
  • 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 epoxy resins such as Araldite XPY306 (manufactured by Ciba Japan); Epototo ST-2004, ST-2007, ST-3000 (all manufactured by Nippon Steel Chemical Co., Ltd.) Hydrogenated bisphenol A type epoxy resin such as: jER604 (Mitsubishi Chemical Co., Ltd.), Epototo YH-434 (Nippon Steel Chemical Co., Ltd.), Araldite MY720 (Ciba Japan Co., Ltd.), Sumiepoxy ELM-120 (Sumitomo Chemical Co., Ltd.) Glycidylamine type epoxy resin such as Aral
  • EPPN registered trademark
  • EPPN-502 all manufactured by Nippon Kayaku Co., Ltd.
  • other trihydroxyphenylmethane type epoxy resins 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) ⁇ Made by Japan), TEPIC (made by Nissan Chemical Industries) A heterocyclic epoxy resin; dig
  • Epoxy resins having a dicyclopentadiene skeleton glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M (manufactured by NOF Corporation); further, a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Polybutadiene rubber derivatives (for example, PB manufactured by Daicel Chemical Industries, Ltd.) -3600), CTBN-modified epoxy resins (for example, YR-102 and YR-450 manufactured by Nippon Steel Chemical Co., Ltd.) and the like.
  • 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 substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin by the sulfur atom using the same synthesis method can also be used.
  • the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents relative 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.
  • thermosetting components include amino resins such as melamine derivatives and benzoguanamine derivatives.
  • amino resins such as melamine derivatives and benzoguanamine derivatives.
  • methylol melamine compounds there are 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.
  • a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule may be added to the photocurable resin composition of the present embodiment. It can.
  • examples of such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule include polyisocyanate compounds or blocked isocyanate compounds.
  • the blocked isocyanate group is a group in which the isocyanate group is protected by the reaction with the blocking agent and temporarily inactivated, and the blocking agent is dissociated when heated to a predetermined temperature. Produces.
  • polyisocyanate compound for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
  • aromatic polyisocyanate examples include, for example, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, Examples thereof include m-xylylene diisocyanate 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 bodies, burette bodies and isocyanurate bodies of the isocyanate compounds mentioned above may be mentioned.
  • the blocked isocyanate compound an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used.
  • an isocyanate compound which can react with a blocking agent the above-mentioned polyisocyanate compound etc. are mentioned, for example.
  • 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 compounds may be commercially available, for example, Sumidur (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.
  • a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used alone 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 preferably 1 to 100 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, sufficient coating film toughness cannot be obtained.
  • 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 in the molecule
  • 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 trade names of bicyclic amidine compounds and salts thereof), etc. It is done.
  • 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 in the usual quantitative ratio.
  • 100 parts by mass of the thermosetting component having a carboxyl group-containing resin or a plurality of cyclic (thio) ether groups in the molecule is 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 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, etc. (Numbers issued by The Society of Dyers and Colorists).
  • Pigment Red 1 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 Diketopyrrolopyrrol
  • 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, and pigments 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, and dye series 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 97 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, and the like can be used. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
  • the green colorant there are phthalocyanine series, anthraquinone series, and perylene series.
  • Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. may be used. it can.
  • metal-substituted or unsubstituted phthalocyanine compounds can also be used.
  • yellow colorants 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 Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185 Condensed Azo: 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
  • the blending ratio of such a colorant is not particularly limited, but is preferably 10 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When it exceeds 10 mass parts, deep part sclerosis
  • the compound having a plurality of ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present embodiment is photocured by irradiation with active energy rays, and an ethylenically unsaturated group-containing carboxyl group-containing resin is obtained. Insolubilizes or helps insolubilize in a dilute alkaline aqueous solution.
  • 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
  • Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols
  • an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin.
  • the epoxy urethane acrylate compound etc. which made the half urethane compound react are mentioned.
  • Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.
  • the compounding 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 dilute alkaline aqueous solution falls, and a coating film becomes weak. More preferably, it is 1 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.
  • barium sulfate, spherical silica, hydrotalcite and talc are preferably used.
  • metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers.
  • the blending amount of the 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 becomes high, the coating and moldability are lowered, 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 uses 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. Can do.
  • 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 thermosetting resin composition of this embodiment is oxidized.
  • radical scavengers that invalidate the generated radicals and / or (2) peroxide decomposers that decompose the generated peroxides into harmless substances and prevent the generation of new radicals.
  • Antioxidants such as can be added.
  • 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 (registered trademark) 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN (registered trademark) 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 29, 2 TINUVIN 5100 (both manufactured by Ciba Japan).
  • antioxidant that acts as a peroxide decomposer
  • examples of the antioxidant that acts as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3′-thiodipro Sulfur compounds such as pionate can be mentioned.
  • the peroxide decomposing agent may be commercially available, for example, Adeka Stub TPP (manufactured by ADEKA), Mark AO-412S (manufactured by Adeka Argus Chemical), Sumilyzer (registered trademark) TPS (manufactured by Sumitomo Chemical), etc. Is mentioned.
  • Adeka Stub TPP manufactured by ADEKA
  • Mark AO-412S manufactured by Adeka Argus Chemical
  • Sumilyzer registered trademark
  • TPS manufactured by Sumitomo Chemical
  • the photocurable resin composition of the present invention includes an ultraviolet absorber in addition to the antioxidant in order to take a countermeasure against stabilization against ultraviolet rays. Can be used.
  • ultraviolet absorbers examples include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like.
  • benzophenone derivatives examples include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and 2 , 4-dihydroxybenzophenone and the like.
  • benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl- Examples thereof include 4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.
  • benzotriazole derivatives examples include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) enzotriazole, 2- (2′- Hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, Examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole.
  • triazine derivative examples include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.
  • 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 in combination with an antioxidant, the molded product obtained from the photocurable resin composition of the present embodiment can be used. Stabilization can be achieved.
  • the photo-curable resin composition of the present embodiment further includes a known thickener such as a known thermal polymerization inhibitor, finely divided silica, organic bentonite, and montmorillonite, silicone-based, fluorine-based, polymer-based, etc.
  • a known thickener such as a known thermal polymerization inhibitor, finely divided silica, organic bentonite, and montmorillonite, silicone-based, fluorine-based, polymer-based, etc.
  • the known antifoaming agent and / or leveling agent, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, rust inhibitors, and the like can be blended.
  • the thermal polymerization inhibitor can be used to prevent thermal polymerization or polymerization with time of the polymerizable compound.
  • the thermal polymerization inhibitor 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, picric acid, 4-Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.
  • an adhesion promoter can be used in order to improve adhesion between layers or adhesion between the formed resin insulation layer and the substrate.
  • adhesion promoters include, for example, benzimidazole, benzoxazole, benzothiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione.
  • the photocurable resin composition of the present embodiment configured as described above is prepared to a predetermined composition, it is adjusted to a viscosity suitable for a coating method with an organic solvent, for example, on a substrate, a dip coating method, 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.
  • the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of about 60 to 100 ° C. to form a tack-free coating film (resin insulating layer).
  • the volatile drying is performed by using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (using a method having a heat source of an air heating method using steam in a countercurrent contact with hot air in the dryer) 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 in the range of 350 to 410 nm. By setting the maximum 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 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 wavelength of 350 to 410 nm.
  • the exposed portion (the portion irradiated with the active energy ray) is cured, and the unexposed portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3 wt% sodium carbonate aqueous solution).
  • a dilute alkaline aqueous solution for example, 0.3 to 3 wt% sodium carbonate aqueous solution.
  • 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 when added, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing resin and, for example, a plurality of cyclic ether groups and / or cyclic groups in the molecule
  • a thermosetting component having a thioether group reacts to form a cured product (pattern) excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.
  • the photocurable resin composition contains a carboxyl group-containing resin, a photopolymerization initiator, an epoxidized polybutadiene compound, and a styryl group-containing compound
  • the cured product is used for an electronic component or the like. Reliability such as heat cycle resistance can be obtained without impairing required heat resistance and migration resistance. And it becomes possible by using such hardened
  • Examples 1 to 12 and Comparative Examples 1 to 3 Using the resin solution of each synthesis example, blended in various components and proportions (parts by mass) shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and photosensitive resin composition for solder resist was prepared. Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the grindometer by an Erichsen company.
  • ⁇ Optimum exposure amount> The photocurable / thermosetting resin compositions of the examples and comparative examples were coated on the entire surface by screen printing after applying a circuit board with a copper thickness of 35 ⁇ m after buffing, washing with water and drying, and heated at 80 ° C. Dry in a circulating drying oven for 60 minutes. After drying, using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), exposure is performed through a step tablet (Kodak No. 2), and development (30 ° C., 0.2 MPa, 1 wt% Na 2 CO 3 aqueous solution) is performed. When it was performed in 60 seconds, the optimal exposure amount was obtained when the remaining step tablet pattern had 7 steps.
  • ⁇ Developability> The photocurable / thermosetting resin composition of each example and comparative example was applied to a copper solid substrate by a screen printing method so as to have a thickness of about 25 ⁇ m after drying, and then heated at 80 ° C. in a hot air circulation drying oven. Dry for 30 minutes. After drying, development was performed with a 1 wt% Na 2 CO 3 aqueous 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 150 ° 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 evaluating the presence or absence, the presence or absence of peeling of the resist layer was evaluated. 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
  • PCT resistance> The evaluation substrate on which the cured solder resist coating film was formed was PCT (Pressure Cooker Test) using a PCT apparatus (HEST SYSTEM TPC-412MD manufactured by Espec Co., Ltd.) at 121 ° C., saturation, and 0.2 MPa for 168 and 192 hours. Went. And the state of the coating film after PCT was evaluated. Judgment criteria are as follows. ⁇ : No swelling, peeling, discoloration, or dissolution 192 hours ⁇ : No swelling, peeling, discoloration, or dissolution of 168 hours ⁇ : Some swelling, peeling, discoloration, or dissolution ⁇ : Expansion, peeling, discoloration, Many elutions
  • Dry film evaluation Evaluation substrates were prepared for the resin compositions of Example 2 and Comparative Example 1 by the method shown below, and evaluated in the same manner.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Epoxy Resins (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

La présente invention concerne une composition de résine qui permet de prévenir l'absorption d'humidité et permet également d'améliorer la résistance aux cycles thermiques sans dégrader les propriétés antimigration. L'invention concerne en particulier une composition de résine photodurcissable qui comprend une résine contenant un groupe carboxyle, un initiateur de photopolymérisation, un composé de polybutadiène epoxydé et un composé contenant un groupe styryle.
PCT/JP2010/004670 2009-07-21 2010-07-21 Composition de résine photodurcissable WO2011010457A1 (fr)

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Cited By (6)

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JP2012180390A (ja) * 2011-02-28 2012-09-20 Nippon Zeon Co Ltd アクリルゴム組成物およびゴム架橋物
JP2013522659A (ja) * 2010-03-08 2013-06-13 エルジー・ケム・リミテッド 耐熱性および機械的性質に優れた感光性樹脂組成物および印刷回路基板用保護フィルム
WO2013172432A1 (fr) * 2012-05-17 2013-11-21 太陽インキ製造株式会社 Composition de résine thermodurcissable développable en milieu alcalin et carte de circuit imprimé
WO2015060240A1 (fr) * 2013-10-21 2015-04-30 日産化学工業株式会社 Composition de résine photosensible négative
FR3017394A1 (fr) * 2014-02-12 2015-08-14 Astrium Sas Composition d'ensimage pour fibres de renfort et ses applications
WO2017126536A1 (fr) * 2016-01-20 2017-07-27 三菱瓦斯化学株式会社 Composition de résine, feuille de résine avec support, carte imprimée multicouche et dispositif semi-conducteur

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JP2004138752A (ja) * 2002-10-17 2004-05-13 Tamura Kaken Co Ltd 感光性樹脂組成物及びプリント配線板
JP2005062451A (ja) * 2003-08-12 2005-03-10 Kyocera Chemical Corp 感光性熱硬化型樹脂組成物
JP2006285177A (ja) * 2005-03-10 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
JP2008299294A (ja) * 2007-06-04 2008-12-11 Taiyo Ink Mfg Ltd 光硬化性・熱硬化性樹脂組成物及びそれを用いて得られるプリント配線

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JP2004138752A (ja) * 2002-10-17 2004-05-13 Tamura Kaken Co Ltd 感光性樹脂組成物及びプリント配線板
JP2005062451A (ja) * 2003-08-12 2005-03-10 Kyocera Chemical Corp 感光性熱硬化型樹脂組成物
JP2006285177A (ja) * 2005-03-10 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
JP2008299294A (ja) * 2007-06-04 2008-12-11 Taiyo Ink Mfg Ltd 光硬化性・熱硬化性樹脂組成物及びそれを用いて得られるプリント配線

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013522659A (ja) * 2010-03-08 2013-06-13 エルジー・ケム・リミテッド 耐熱性および機械的性質に優れた感光性樹脂組成物および印刷回路基板用保護フィルム
JP2012180390A (ja) * 2011-02-28 2012-09-20 Nippon Zeon Co Ltd アクリルゴム組成物およびゴム架橋物
WO2013172432A1 (fr) * 2012-05-17 2013-11-21 太陽インキ製造株式会社 Composition de résine thermodurcissable développable en milieu alcalin et carte de circuit imprimé
WO2015060240A1 (fr) * 2013-10-21 2015-04-30 日産化学工業株式会社 Composition de résine photosensible négative
JPWO2015060240A1 (ja) * 2013-10-21 2017-03-09 日産化学工業株式会社 ネガ型感光性樹脂組成物
KR20210106011A (ko) * 2013-10-21 2021-08-27 닛산 가가쿠 가부시키가이샤 네가티브형 감광성 수지 조성물
KR102468581B1 (ko) * 2013-10-21 2022-11-18 닛산 가가쿠 가부시키가이샤 네가티브형 감광성 수지 조성물
FR3017394A1 (fr) * 2014-02-12 2015-08-14 Astrium Sas Composition d'ensimage pour fibres de renfort et ses applications
WO2015121274A1 (fr) * 2014-02-12 2015-08-20 Airbus Defence And Space Sas Composition d'ensimage pour fibres de renfort et ses applications
US10745530B2 (en) 2014-02-12 2020-08-18 Airbus Safran Launchers Sas Sizing composition for reinforcing fibres and applications thereof
WO2017126536A1 (fr) * 2016-01-20 2017-07-27 三菱瓦斯化学株式会社 Composition de résine, feuille de résine avec support, carte imprimée multicouche et dispositif semi-conducteur
JPWO2017126536A1 (ja) * 2016-01-20 2018-11-08 三菱瓦斯化学株式会社 樹脂組成物、支持体付き樹脂シート、多層プリント配線板及び半導体装置

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