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WO2010052811A1 - Composition de résine photodurcissable, film sec et produit durci de ladite composition de résine photodurcissable, et carte de circuit imprimé utilisant la composition de résine photodurcissable, le film sec et le produit durci - Google Patents

Composition de résine photodurcissable, film sec et produit durci de ladite composition de résine photodurcissable, et carte de circuit imprimé utilisant la composition de résine photodurcissable, le film sec et le produit durci Download PDF

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Publication number
WO2010052811A1
WO2010052811A1 PCT/JP2009/003037 JP2009003037W WO2010052811A1 WO 2010052811 A1 WO2010052811 A1 WO 2010052811A1 JP 2009003037 W JP2009003037 W JP 2009003037W WO 2010052811 A1 WO2010052811 A1 WO 2010052811A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
group
photocurable resin
compound
carbon atoms
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2009/003037
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English (en)
Japanese (ja)
Inventor
秋山学
峰岸昌司
有馬聖夫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiyo Holdings Co Ltd
Original Assignee
Taiyo Ink Mfg Co Ltd
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 Taiyo Ink Mfg Co Ltd filed Critical Taiyo Ink Mfg Co Ltd
Priority to KR1020117010397A priority Critical patent/KR101693900B1/ko
Priority to CN200980154123.8A priority patent/CN102272677B/zh
Publication of WO2010052811A1 publication Critical patent/WO2010052811A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
    • C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/141—Polyesters; Polycarbonates
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/161—Coating processes; Apparatus therefor using a previously coated surface, e.g. by stamping or by transfer lamination
    • 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 photocurable resin composition that can be developed with a dilute alkaline aqueous solution, particularly a composition for a solder resist that is photocured by ultraviolet exposure or laser exposure, a dry film and a cured product thereof, and a cure formed using them
  • the present invention relates to a printed wiring board having a film.
  • alkali development type photosensitive resin compositions have been used in large quantities as solder resists for printed wiring boards.
  • the solder resist is intended to protect the circuit of the printed circuit board, and is mainly composed of a carboxyl group-containing resin, a polyfunctional acrylate compound, a photopolymerization initiator, a thermosetting resin, and the like.
  • the polyfunctional acrylate compounds liquid polyfunctional polyester acrylates are widely used mainly from the viewpoints of high sensitivity and development resistance.
  • the dry coating film needs to be dry to the touch (tack-free property).
  • the solder resist is used for the purpose of protecting the surface layer circuit of the printed wiring board, and requires high solder heat resistance and electrical insulation.
  • the photosensitive resin is an acrylate-based compound, there is still a point to be improved in terms of electrical insulation, which is inferior in hydrophobicity and alkali resistance, and has a low insulation resistance value under high temperature humidification conditions. It has been regarded as a problem that it easily causes migration and causes a short circuit between circuits.
  • Patent Document 2 contains a carboxyl group obtained by reacting a polybasic acid anhydride with a reaction product of an epoxy compound having two or more epoxy groups in one molecule and an unsaturated group-containing monocarboxylic acid.
  • Carboxylic group-containing product obtained by reacting a reaction product obtained by reacting an unsaturated group-containing monocarboxylic acid with a reaction product of a photosensitive resin, a novolak-type phenolic resin, and an alkylene oxide.
  • An example of a photosensitive composition having good dryness to the touch and excellent adhesion by using a photosensitive resin in combination is disclosed.
  • a carboxyl group-containing photosensitive resin obtained by reacting a reaction product of a novolak-type phenol resin with an alkylene oxide with an unsaturated group-containing monocarboxylic acid and reacting the resulting reaction product with a polybasic acid anhydride.
  • the present invention has been made in view of the prior art as described above, and is excellent in dryness to touch of a dry coating film, highly sensitive and flexible, solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation. It is an object of the present invention to provide a photo-curable resin composition that can form a cured film such as a solder resist having excellent insulation resistance and particularly high insulation resistance when humidified at high temperature. Furthermore, the object of the present invention is to obtain a dry film and a cured product excellent in various properties as described above obtained by using such a photocurable resin composition, and to cure a solder resist or the like with the dry film or the cured product. It is providing the printed wiring board by which a membrane
  • photosensitive resin having a structure represented by the following general formula (I), a carboxyl group-containing resin, and a photopolymerization initiator
  • An alkali-developable photo-curable resin composition is provided.
  • R 1 is a hydrogen atom or an organic group having 1 to 20 carbon atoms, which may be the same or different
  • R 2 represents at least one functional group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, and a phenylene group
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 5 represents a hydrogen atom or a methyl group
  • p represents an integer of 1 to 5
  • q represents an integer of 3 or more
  • m represents an integer of 1 to 4
  • n represents an integer of 1 to 10.
  • the photosensitive resin is prepared by reacting a compound having three or more phenolic hydroxyl groups in one molecule with a cyclic ether compound or a cyclic carbonate compound, and reacting a compound having an ethylenically unsaturated group with the generated hydroxyl group. It is a photosensitive resin obtained in this way.
  • the compound having three or more phenolic hydroxyl groups in one molecule is a compound having a phenolic hydroxyl group having a softening point of room temperature or higher, and the compound having the ethylenically unsaturated group.
  • thermosetting component in a preferred embodiment, it further contains a thermosetting component, and preferably further contains a colorant.
  • a photocurable resin composition particularly a photocurable thermosetting resin composition containing a thermosetting component, can be suitably used as a solder resist.
  • the photocurable resin composition obtained by applying and drying the photocurable resin composition on a carrier film, the photocurable resin composition or the dry film is cured.
  • a cured product obtained by photo-curing on copper, and a cured product obtained by photo-curing in a pattern are also provided.
  • a printed wiring board characterized by having a cured film obtained by photocuring the photocurable resin composition or dry film in a pattern and then thermosetting.
  • the photosensitive resin including the structure represented by the general formula (I) does not particularly contain an acid, and the double bond equivalent is 200 or more and 400 or less. It is characterized by.
  • this photosensitive resin reacts a compound having three or more phenolic hydroxyl groups in one molecule with a cyclic ether compound or a cyclic carbonate compound, and reacts a compound having an ethylenically unsaturated group with the generated hydroxyl group.
  • the carboxyl group-containing resin is contained together with the photosensitive resin, the resulting photocurable resin composition can be developed with an alkaline aqueous solution.
  • the photocurable resin composition of the present invention can be advantageously applied to the formation of a cured film such as a solder resist of a printed wiring board or a flexible printed wiring board.
  • the photocurable resin composition of the present invention is characterized in that a photosensitive resin including the structure represented by the general formula (I) is used as the photosensitive resin.
  • the dry photocoating resin composition obtained has excellent dryness to touch.
  • the cured film has a high insulation resistance value under high-temperature humidification conditions, and it has been found that the occurrence of ion migration is not a problem for a long time as compared with the case where the photosensitive resin is not contained.
  • the photosensitive resin contains three or more structures represented by the general formula (I) in one molecule (q ⁇ 3).
  • the structure represented by the general formula (I) is 2 or less in one molecule, high sensitivity which is one of the objects of the present invention cannot be achieved, and in particular, in the case of a solder resist, the surface curability is inferior.
  • the electrical insulation during high temperature humidification is low, and ion migration may occur.
  • a double bond equivalent of 200 or less cannot be structurally, and when it is 400 or more, high sensitivity cannot be achieved, and furthermore, the electrical insulation and ion migration properties are poor, so the double bond equivalent is 200 or more. 400 or less is preferable.
  • the photosensitive resin containing the structure represented by the general formula (I) may be synthesized by a conventionally known method, but preferably a compound having three or more phenolic hydroxyl groups in one molecule.
  • a photosensitive resin obtained by reacting a cyclic ether compound or a cyclic carbonate compound and reacting the resulting alcoholic hydroxyl group with a compound having an ethylenically unsaturated group can be suitably used. Further, if the photosensitive resin obtained by reacting an alcoholic hydroxyl group with a compound having an ethylenically unsaturated group has three or more structures represented by the general formula (1), the alcoholic hydroxyl group may remain. .
  • Examples of the compound having three or more phenolic hydroxyl groups in one molecule include novolak type phenol resins.
  • the novolak-type phenol resin is obtained by a condensation reaction between phenols and formaldehyde, and these reactions are usually performed in the presence of an acidic catalyst.
  • Examples of the phenols used for the synthesis of the novolak type phenol resin include phenol, cresol, ethylphenol, propylphenol, butylphenol, hexylphenol, octylphenol, nonylphenol, phenylphenol, cumylphenol, bisphenol A, bisphenol F, and bixylenol. These may be used alone or in combination.
  • examples of the cyclic ether compound include ethylene oxide, propylene oxide, 1,2-butylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran.
  • examples of the cyclic carbonate compound include ethylene carbonate and / or propylene carbonate. Particularly preferred are ethylene oxide and propylene oxide.
  • acrylic acid and methacrylic acid are preferable, and methacrylic acid is particularly preferable from the viewpoint of alkali resistance and electrical insulation. It is clear that the photosensitive resin using methacrylic acid has a high sensitivity, particularly excellent alkali resistance and electrical characteristics, and gives a cured product having a high insulation resistance value at high temperature humidification. There was no surprising result.
  • the amount of the photosensitive resin is, for example, in the range of 1 to 100 parts by weight, preferably 5 to 60 parts by weight, more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin.
  • the amount is 1 part by mass or less, the image forming ability is impaired.
  • carboxyl group-containing resin various conventionally known carboxyl group-containing resins having a carboxyl group in the molecule for the purpose of imparting alkali developability can be used.
  • 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.
  • 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 is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group.
  • (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions. Since the carboxyl group-containing resin as described above has many free carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution is possible.
  • the acid value of the carboxyl group-containing resin is in the range of 40 to 200 mgKOH / g, and more preferably in the range of 45 to 120 mgKOH / g.
  • the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult.
  • the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary. In some cases, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.
  • the weight-average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally within the range of 2,000 to 150,000, more preferably 5,000 to 100,000.
  • weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior.
  • weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.
  • the amount of such a carboxyl group-containing resin is 20 to 60% by mass, preferably 30 to 50% by mass in the total composition.
  • the amount of the carboxyl group-containing resin is less than the above range, the film strength is lowered, which is not preferable.
  • the amount is larger than the above range, the viscosity of the composition is increased or the coating property is lowered, which is not preferable.
  • These carboxyl group-containing resins can be used without being limited to those listed above, 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 (II), and an ⁇ -aminoacetophenone photopolymerization initiator having a group represented by the following general formula (III). It is preferable to use at least one photopolymerization initiator selected from the group consisting of acylphosphine oxide photopolymerization initiators having a group represented by the following formula (IV).
  • R 6 represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more). Or a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or benzoyl.
  • R 7 is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups).
  • R 8 and R 9 each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group
  • R 10 and R 11 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded
  • R 12 and R 13 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl substituted with a halogen atom, an alkyl group or an alkoxy group
  • the oxime ester photopolymerization initiator having a group represented by the general formula (II) is preferably 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (V):
  • the compound represented by the following general formula (VI) and the compound represented by the following general formula (VII) are mentioned.
  • R 14 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or 2 carbon atoms
  • R 15 and R 17 are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substitute
  • R 18 , R 19 and R 24 each independently represents an alkyl group having 1 to 12 carbon atoms
  • R 20 , R 21 , R 22 and R 23 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • M represents O, S or NH
  • 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 (V) and a compound represented by the formula (VI) are more preferable.
  • Examples of commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Specialty Chemicals, and N-1919 manufactured by ADEKA.
  • These oxime ester photopolymerization initiators can be used alone or in combination of two or more.
  • Examples of the ⁇ -aminoacetophenone photopolymerization initiator having the group represented by the general formula (III) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like.
  • Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.
  • Examples of the acylphosphine oxide photopolymerization initiator having a group represented by the general formula (IV) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine. And 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 Specialty Chemicals.
  • the blending amount of such a photopolymerization initiator is suitably in the range of 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the blending amount of the photopolymerization initiator is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off or the coating film properties such as chemical resistance are deteriorated. .
  • it exceeds 30 parts by mass light absorption on the surface of the solder resist coating film of the photopolymerization initiator becomes violent and the deep-part curability tends to decrease, which is not preferable.
  • 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, the range of 0.01 to 5 parts by mass is desirable.
  • photopolymerization initiators, photoinitiator assistants and sensitizers that can be suitably used in the photocurable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenones.
  • a compound, a xanthone compound, a tertiary amine compound, etc. can be mentioned.
  • benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
  • acetophenone compound examples include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone.
  • anthraquinone compound examples include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.
  • thioxanthone compound examples include, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.
  • ketal compound examples include acetophenone dimethyl ketal and benzyl dimethyl ketal.
  • benzophenone compound examples include, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyldiphenyl. Sulfide.
  • tertiary amine compound examples include, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylamino.
  • an ethanolamine compound a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylamino.
  • Dialkylamino benzophenones such as benzophenone (EAB manufactured by Hodogaya Chemical Co.), and dialkylamino groups such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin) Contained coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA, Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB, International Bio-Synthetics), 4-dimethylaminobenzoic acid n-butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhe
  • thioxanthone compounds and tertiary amine compounds are preferable.
  • the composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep curability, and among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone
  • a thioxanthone compound such as
  • the amount of such a thioxanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the carboxyl group-containing resin. If the amount of the thioxanthone compound is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.
  • a compound having a dialkylaminobenzene structure is preferable, among which a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable.
  • a dialkylaminobenzophenone compound 4,4'-diethylaminobenzophenone is preferable because of its low toxicity.
  • a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has a maximum absorption wavelength in the ultraviolet region, so that it is less colored and uses a color pigment as well as a colorless and transparent photosensitive composition.
  • a colored solder resist film reflecting the color can be provided.
  • 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.
  • the blending amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • 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.
  • photopolymerization initiators can be used alone or as a mixture of two or more.
  • the total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably in the range of 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. 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 agents include, for example, chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol Chain transfer agents having a hydroxyl group such as 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2 -(Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclo Ntanchioru, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzene
  • heterocyclic compound having a mercapto group acting as a chain transfer agent examples include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto.
  • heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the photocurable resin composition mercaptobenzothiazole, 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.
  • chain transfer agents can be used alone or in combination of two or more.
  • thermosetting resin can be added to the photocurable resin composition of the present invention in order to impart heat resistance.
  • thermosetting components used in the present invention include amine resins such as melamine resins and benzoguanamine resins, block isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, and the like.
  • a curable 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 two or more cyclic (thio) ether groups in the molecule is either one of the three-, four- or five-membered cyclic ether groups in the molecule, or the cyclic thioether group, or two of them.
  • a compound having at least two epoxy groups in the molecule that is, a polyfunctional epoxy compound, a compound having at least two oxetanyl groups in the molecule, that is, a polyfunctional compound.
  • examples include oxetane compounds, compounds having two or more thioether groups in the molecule, that is, episulfide resins.
  • Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, and Epoto manufactured by Tohto Kasei Co., Ltd. YD-011, YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R.
  • Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Japan Epoxy Resin Co., Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd. D. Chemicals manufactured by Dow Chemical Company.
  • E. R. 542 Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R.
  • E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink & Chemicals, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170 manufactured by Toto Kasei Co., YDF- 175, YDF-2004, Araldide XPY306 manufactured by Ciba Specialty Chemicals (both trade names), bisphenol F type epoxy resin; Etoto ST-2004, ST-2007, ST-3000 manufactured by Toto Kasei Hydrogenated bisphenol A type epoxy resin such as product name); jER604 manufactured by Japan Epoxy Resin, Epototo YH-434 manufactured by Tohto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals, Sumitomo Chemical Industries Epoxy ELM-120 etc.
  • Xylenol type or biphenol type epoxy resins or mixtures thereof bisphenols such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by Dainippon Ink & Chemicals, Inc. S type epoxy resin; bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin; jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals, etc.
  • bisphenols such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by Dainippon Ink & Chemicals, Inc. S type epoxy resin
  • bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin
  • tetraphenylolethane type Xylon resin Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (both trade names), heterocyclic epoxy resins; Diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; Toto Kasei Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Nippon Steel; containing naphthalene groups such as ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. and HP-4032, EXA-4750 and EXA-4700 manufactured by Dainippon Ink & Chemicals, Inc.
  • Epoxy resin Epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink &Chemicals; Glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil &Fats; In addition, cyclohexylmaleimide and glycidyl Copolymerized epoxy resin of acrylate; epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industries), CTBN-modified epoxy resin (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.), etc. However, it is not limited to these. These epoxy resins can be used alone or in combination of two or more. Among these, 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-oxetanyl)
  • polyfunctional oxetanes such as 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-hydroxystyrene
  • Examples of the compound having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resins. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
  • the amount of the thermosetting component having two or more 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. More preferably, a range of 0.8 to 2.0 equivalents is appropriate.
  • the amount of the thermosetting component having two or more cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, and heat resistance, alkali resistance, electrical insulation, etc. Is unfavorable because it decreases.
  • the amount exceeds 2.5 equivalents the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.
  • a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule can be added to the photocurable resin composition of the present invention as a thermosetting component.
  • a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or two in one molecule. Examples thereof include compounds having the above blocked isocyanate groups, that is, blocked isocyanate compounds.
  • polyisocyanate compound for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
  • aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include 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 listed above may be 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.
  • the blocked isocyanate compound an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used.
  • the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type.
  • aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example.
  • aromatic polyisocyanate examples include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include 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.
  • 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 Alcohol-based blocking agents such as chill and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetoaldoxime, acetoxi
  • the blocked isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265-, Desmodur TPLS-295729, TPLS-2062, manufactured by Sumitomo Bayer Urethane Co., Ltd. TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm 2265, Coronate 2512, Coronate 2513, Coronate 2520, manufactured by Nippon Polyurethane Industry Co., Ltd. B-830, B-815, B-846, B-870 manufactured by Mitsui Takeda Chemical Co., Ltd.
  • the compounds having two or more 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 two or more isocyanate groups or blocked isocyanate groups in one molecule is 1 to 100 parts by mass, more preferably 2 parts per 100 parts by mass of the carboxyl group-containing resin. A proportion of up to 70 parts by weight is appropriate. When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 mass parts, storage stability falls and it is not preferable.
  • thermosetting component examples include melamine derivatives and benzoguanamine derivatives.
  • examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.
  • the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the 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 component examples include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, and 272 manufactured by Mitsui Cyanamid Co., Ltd. 202, 1156, 1158, 1158, 1123, 1170, 1174, UFR65, 300, Nikarak Mx-750, Mx-032, Mx-270, Mx made by Sanwa Chemical Co., Ltd. -280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw -100LM, Mw-750LM (trade name), etc.
  • the said thermosetting component can be used individually or in combination of 2 or more types.
  • thermosetting component having two or more 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 bicyclic amidine compounds and salts thereof), and the like.
  • thermosetting catalyst for epoxy resins or oxetane compounds or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used.
  • thermosetting catalysts is sufficient in the usual quantitative ratio, for example, with respect to 100 parts by mass of the carboxyl group-containing resin or thermosetting component having two or more cyclic (thio) ether groups in the molecule.
  • the amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.
  • an adhesion promoter can be used in order to improve adhesion between layers or adhesion between the photosensitive resin layer and the substrate.
  • Specific examples include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione.
  • the compound having two or more ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention is photocured by irradiation with active energy rays to contain the ethylenically unsaturated group-containing carboxyl group.
  • the resin is insolubilized in an alkaline aqueous solution, or helps insolubilization.
  • 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 the like each methacrylates corresponding to the acrylates.
  • 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.
  • a polyfunctional epoxy resin such as a cresol novolac type epoxy resin
  • a hydroxy acrylate such as pentaerythritol triacrylate
  • a diisocyanate such as isophorone diisocyanate
  • the compounding amount of the compound having two or more ethylenically unsaturated groups in the molecule is 5 to 100 parts by mass, more preferably 1 to 70 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the ratio is appropriate.
  • 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, which is not preferable.
  • the amount exceeds 100 parts by mass the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.
  • the photocurable resin composition of the present invention can contain a colorant.
  • a colorant conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.
  • Red colorant examples include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. It is done.
  • Monoazo Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
  • Disazo type Pigment Red 37, 38, 41.
  • Monoazo lake system 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.
  • Condensed azo 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.
  • Quinacridone series Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.
  • Blue colorant include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds classified as Pigment, specifically, the following color index (CI; The Society of Dyers and Colorists) (Issued by The Society of Dyers and Colorists) can be listed with numbers: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pig: Blue 15: 3, Pig Pigment Blue 15: 6, Pigment Blue 16, and Pigment Blue 60.
  • CI The Society of Dyers and Colorists
  • 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, Solvent Blue 97, SolBlu 97, SolBlu 97, SolBlu 97, SolBlu 97, SolBlu 97 Blue 70 or the like can be used.
  • a metal-substituted or unsubstituted phthalocyanine compound can also be used.
  • the green colorant includes phthalocyanine, anthraquinone, and perylene. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like are used. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
  • Yellow colorant examples include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
  • Anthraquinone series Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
  • Isoindolinone series Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
  • Condensed azo type 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 type 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.
  • a colorant such as purple, orange, brown, or black may be added.
  • the blending ratio of the colorant as described above is not particularly limited, but is preferably 0 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin. It is enough.
  • the photocurable resin composition of the present invention prevents oxidation, (1) 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 can be added.
  • the radical scavenger may be commercially available, for example, Adeka Stub AO-30, Adeka Stub AO-330, Adeka Stub AO-20, Adeka Stub LA-77, Adeka Stub LA-57, Adeka Stub LA-67, manufactured by Asahi Denka Co., Ltd.
  • ADK STAB LA-68, ADK STAB LA-87 both trade names
  • antioxidant that acts as a peroxide decomposer
  • phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 ′.
  • -Sulfur compounds such as thiodipropionate.
  • the peroxide decomposing agent may be commercially available, for example, Adeka Stub TPP manufactured by Asahi Denka Co., Ltd., Mark AO-412S manufactured by Adeka Argus Chemical, Sumitizer TPS manufactured by Sumitomo Chemical (both are trade names), and the like. Can be mentioned.
  • Said antioxidant can be used individually by 1 type or in combination of 2 or more types. Since the polymer material absorbs light and thereby decomposes and deteriorates, the photocurable resin composition of the present invention is not limited to the above-described antioxidant, but an ultraviolet absorber in order to take measures against stabilization against ultraviolet rays. Can be used.
  • ultraviolet absorber examples include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like.
  • benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxy.
  • benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, p-tert-butylphenyl salicylate, 2,4-di-tert- Butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc .; specific examples of benzotriazole derivatives include 2- ( 2'-Hydroxy-5'-t-butylphenol ) Benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) enzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-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 manufactured by Ciba Specialty Chemicals 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (all are trade names), and the like.
  • Said ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, Stabilization of the molding obtained from the photocurable resin composition of this invention by using together with the said antioxidant. Can be planned.
  • a filler can be blended as necessary in order to increase the physical strength of the coating film.
  • known and commonly used inorganic or organic fillers can be used.
  • barium sulfate, spherical silica 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, more preferably 0.1 to 60% by mass of the total amount of the composition. If the blending amount of the filler exceeds 75% by mass of the total amount of the composition, the viscosity of the insulating composition is increased, and the coating and moldability are lowered, and the cured product becomes brittle.
  • the photocurable resin composition of the present invention may use an organic solvent for the synthesis of the carboxyl group-containing resin and the preparation of the composition, or for adjusting the viscosity 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 photo-curable resin composition of the present invention may further comprise, as necessary, known and commonly used thermal polymerization inhibitors, known and commonly used thickeners such as finely divided silica, organic bentonite, and montmorillonite, silicone-based, fluorine-based, and polymer-based Known additives such as antifoaming agents and / or leveling agents such as silane coupling agents such as imidazole, thiazole and triazole, antioxidants, rust inhibitors and the like can be blended.
  • thermal polymerization inhibitors such as finely divided silica, organic bentonite, and montmorillonite
  • silicone-based, fluorine-based, and polymer-based silicone-based, fluorine-based, and polymer-based
  • Known additives such as antifoaming agents and / or leveling agents such as silane coupling agents such as imidazole, thiazole and triazole, antioxidants, rust inhibitors and the like can be blended.
  • the thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization 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, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.
  • the photocurable resin composition of the present invention is, for example, adjusted to a viscosity suitable for the coating method with the organic solvent, and on the substrate, dip coating method, flow coating method, roll coating method, bar coater method, screen printing.
  • a tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C., followed by volatile drying (temporary drying).
  • a resin insulation layer can be formed by apply
  • thermosetting having a carboxyl group of the carboxyl group-containing resin and two or more cyclic ether groups and / or cyclic thioether groups in the molecule.
  • the reactive component reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.
  • the base material examples include printed circuit boards and flexible printed circuit boards that are pre-formed with a circuit, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin. , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminates of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET A film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.
  • Volatile drying performed after applying the photocurable resin composition of the present invention is performed in a dryer using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (equipped with an air heating heat source using steam). Can be performed using a method in which the hot air is brought into countercurrent contact and a method in which the hot air is blown onto the support from the nozzle.
  • the resulting coating film is exposed (irradiated with active energy rays).
  • the exposed portion (the portion irradiated by the active energy ray) is cured.
  • a direct drawing apparatus for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer
  • an exposure apparatus equipped with a metal halide lamp and an (ultra) high pressure mercury lamp.
  • a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used.
  • the exposure amount varies depending on the film thickness and the like, but can be generally in the range of 5 to 200 mJ / cm 2 , preferably 5 to 100 mJ / cm 2 , more preferably 5 to 50 mJ / cm 2 .
  • the direct drawing apparatus for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any apparatus may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .
  • the developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.
  • the photo-curable resin composition of the present invention is in the form of a dry film having a solder resist layer formed by applying and drying a solder resist in advance on a film of polyethylene terephthalate or the like in addition to the method of directly applying the liquid curable resin composition to a substrate. Can also be used.
  • the case where the photocurable resin composition of this invention is used as a dry film is shown below.
  • the dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film used as necessary are laminated in this order.
  • the solder resist layer is a layer obtained by applying and drying an alkali-developable photocurable resin composition on a carrier film or a cover film. After forming a solder resist layer on the carrier film, a cover film is laminated thereon, or a solder resist layer is formed on the cover film, and this laminate is laminated on the carrier film to obtain a dry film.
  • thermoplastic film such as a polyester film having a thickness of 2 to 150 ⁇ m is used.
  • the solder resist layer is formed by uniformly applying an alkali-developable photocurable resin composition to a carrier film or cover film with a thickness of 10 to 150 ⁇ m using a blade coater, lip coater, comma coater, film coater, etc., and then drying. Is done.
  • 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.
  • a protective film permanent protective film
  • peel off the cover film layer the solder resist layer and the substrate on which the circuit is formed, and bond them together using a laminator, etc.
  • a solder resist layer is formed on the formed substrate. If the formed solder resist layer is exposed, developed, and heat cured in the same manner as described above, a cured coating film can be formed.
  • the carrier film may be peeled off either before exposure or after exposure.
  • a novolac type phenol resin manufactured by Showa Polymer Co., Ltd., hydroxyl equivalent 106
  • reaction solution was washed with 5% NaCl aqueous solution, toluene was distilled off with an evaporator, and carbitol acetate was added to obtain a novolak-type PO-added methacrylate resin solution having a nonvolatile content of 70% (double Bond equivalent 250 g / eq. Acid value 0). This is called A-1 varnish.
  • Photosensitive resin synthesis example 2 164 parts of an alkylene oxide adduct of the novolak type phenol resin obtained in Synthesis Example 1, 72 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.05 part of hydroquinone monomethyl ether, and 100 parts of toluene were stirred and heated. The reactor was equipped with a total and an air blowing tube, stirred while blowing air, and reacted at 90 ° C. for 12 hours. After the water produced by the reaction began to distill as an azeotrope with toluene, the reaction was continued for an additional 5 hours and cooled to room temperature.
  • reaction solution was washed with 5% NaCl aqueous solution, toluene was distilled off with an evaporator, and carbitol acetate was added to obtain a novolac-type PO-added acrylate resin solution having a nonvolatile content of 70% (double Bond equivalent 236 g / eq.acid value 0). This is called A-2 varnish.
  • a novolac type phenol resin manufactured by Showa Polymer Co., Ltd., hydroxyl equivalent 106
  • reaction solution was washed with 5% NaCl aqueous solution, toluene was distilled off with an evaporator, and carbitol acetate was added to obtain a novolak EO-added methacrylate resin solution having a nonvolatile content of 70% (double Bond equivalent 236 g / eq.acid value 0). This is called A-3 varnish.
  • reaction solution was washed with 5% NaCl aqueous solution, toluene was distilled off with an evaporator, and carbitol acetate was added to obtain an EO-added methacrylate resin solution having a nonvolatile content of 70% (double bond equivalent). 224 g / eq ⁇ acid value 0). This is called A-4 varnish.
  • Example of synthesis of carboxyl group-containing resin (B-3) A novolac-type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name “Shonol CRG951”, OH equivalent: 119.4) 119. 4 g, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually dropped and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm 2 for 16 hours.
  • reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide, and the novolac type having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq.
  • a propylene oxide reaction solution of cresol resin was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
  • Examples 1 to 15 and Comparative Examples 1 to 5 Using the resin solutions of the above synthesis examples, blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and used for solder resist A photosensitive resin composition 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 Eriksen.
  • Pigment Blue 15 3 * 13 : C.I. Pigment Yellow 147 * 14 : Barium sulfate (B-30: Sakai Chemical Co., Ltd.) * 15 : Dipropylene glycol monomethyl ether * 16 : Block isocyanate (Asahi Kasei Chemicals) * 17 : Methylated melamine resin (manufactured by Sanwa Chemical Co., Ltd.) * 18 : Antioxidant (Ciba Specialty Chemicals)
  • ⁇ Optimum exposure amount> The photocurable thermosetting resin compositions of the examples and comparative examples were coated on the entire surface by screen printing after the circuit pattern substrate having a copper thickness of 35 ⁇ m was buffed, washed with water, dried, and heated at 80 ° C. Dry in a circulating drying oven for 60 minutes. After drying, exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and development (30 ° C., 0.2 MPa, 1 wt% Na 2 CO 3 aqueous solution) is performed at 60. When the measurement was performed in seconds, the optimal exposure amount was obtained when the remaining step tablet pattern was 7 steps.
  • the active energy ray was irradiated so that the exposure amount became the optimal exposure amount of the photosensitive resin composition.
  • development was performed with a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. to draw a pattern, and a cured coating film was obtained by heat curing at 150 ° C. for 60 minutes. It calculated
  • composition of each of the above composition examples and comparative composition examples was applied to a PTFE (polytetrafluoroethylene) plate that had been washed and dried in advance by a screen printing method, and dried at 80 ° C. for 30 minutes in a hot-air circulating drying oven. . This was cooled to room temperature, exposed at an appropriate exposure amount, and developed with a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. for 60 seconds under a spray pressure of 2 kg / cm 2 .
  • PTFE polytetrafluoroethylene
  • 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 at 150 ° C. for 60 minutes in a hot air circulating drying furnace. After cooling this to room temperature, the cured coating film was peeled off from the PTFE plate to obtain an evaluation sample.
  • the tensile elasticity modulus, tensile strength (tensile fracture strength), and elongation rate (tensile fracture elongation) of the above evaluation samples were measured with a tension-compression tester (manufactured by Shimadzu Corporation).
  • compositions of the above Examples and Comparative Examples were applied by screen printing to a Kapton material (thickness 25 ⁇ m) that had been washed and dried in advance, and dried at 80 ° C. for 30 minutes in a hot air circulating drying furnace. After cooling this to room temperature, it is exposed with an appropriate exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. is applied under a spray pressure of 2 kg / cm 2. Development was performed for 2 seconds.
  • a high-pressure mercury lamp short arc lamp
  • 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 to obtain an evaluation sample for a folding resistance test and a flexibility test. .
  • the maximum load applied to the electronic balance was evaluated as the repulsive force according to the following criteria. ⁇ : Less than 10 g ⁇ : 10 to less than 30 g ⁇ : 30 g or more
  • 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. ⁇ Solder heat resistance> The evaluation board
  • Judgment criteria are as follows. ⁇ : No soaking, melting or peeling. ⁇ : Slight penetration, dissolution or peeling is confirmed. X: Significant infiltration, dissolution or peeling. ⁇ Dry film production> After each of the photosensitive resin compositions for solder resists of Example 1 and Comparative Example 1 were appropriately diluted with methyl ethyl ketone, a PET film (Toray FB-50: manufactured by Toray Industries, Inc.) was prepared using an applicator so that the film thickness after drying was 20 ⁇ m. 16 ⁇ m) and dried at 80 ° C. for 30 minutes to obtain a dry film.
  • Toray FB-50 manufactured by Toray Industries, Inc.
  • a photocurable resin composition that is excellent in dryness to touch of a dry coating film, is highly sensitive and flexible, and can form a cured film having high insulation resistance especially when humidified at high temperature, and its dry film and cured product
  • a printed wiring board in which a cured film such as a solder resist is formed can be provided.

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  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials For Photolithography (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

La présente invention concerne une composition de résine photodurcissable apte à former un film de revêtement séché qui est extrêmement sec au toucher, présente une forte sensibilité, et peut former un film durci qui est doux et qui présente en particulier une forte résistance d'isolement à haute température et dans des conditions d'humidité. L'invention concerne également un film sec et un produit durci de ladite composition de résine photodurcissable, ainsi qu'une carte de circuit imprimé comprenant un film durci tel qu'une réserve de soudure formée au moyen de la composition de résine photodurcissable, du film sec et du produit durci. La composition de résine photodurcissable est développable en milieu alcalin et comprend une résine photosensible  ayant une structure représentée par la formule générale (I), une résine contenant un groupe carboxyle, et un initiateur de photopolymérisation.  De préférence, la composition de résine photodurcissable comprend en outre un composant thermodurcissable et mieux encore, elle comprend en outre un colorant.  Dans la formule générale (I), les R1, qui peuvent être identiques ou différents, représentent un atome d'hydrogène et un groupe organique ayant de 1 à 20 atomes de carbone ; R2 représente au moins un groupe fonctionnel choisi dans le groupe comprenant les groupes alkyle ayant de 1 à 10 atomes de carbone, les groupes alkylène ayant de 1 à 10 atomes de carbone, et les groupes phénylène ; R3 représente un atome d'hydrogène ou un groupe alkyle ayant de 1 à 4 atomes de carbone ; R4 représente un atome d'hydrogène ou un groupe alkyle ayant de 1 à 4 atomes de carbone ; R5 représente un atome d'hydrogène ou un groupe méthyle ; p est un entier de 1 à 5 ; q est un entier égal à 3 ou plus ; m est un entier de 1 à 4 ; et n est un entier de 1 à 10.
PCT/JP2009/003037 2008-11-07 2009-06-30 Composition de résine photodurcissable, film sec et produit durci de ladite composition de résine photodurcissable, et carte de circuit imprimé utilisant la composition de résine photodurcissable, le film sec et le produit durci Ceased WO2010052811A1 (fr)

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KR1020117010397A KR101693900B1 (ko) 2008-11-07 2009-06-30 광경화성 수지 조성물, 그의 드라이 필름 및 경화물, 및 이들을 이용한 인쇄 배선판
CN200980154123.8A CN102272677B (zh) 2008-11-07 2009-06-30 光固化性树脂组合物、其干膜及固化物以及使用它们的印刷电路板

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JP2008287021A JP2010113241A (ja) 2008-11-07 2008-11-07 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

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JP5707154B2 (ja) * 2011-01-31 2015-04-22 旭化成イーマテリアルズ株式会社 感光性樹脂組成物及びその用途
CN104950574A (zh) * 2014-03-31 2015-09-30 太阳油墨（苏州）有限公司 光固化性热固化性树脂组合物、干膜、固化物及印刷电路板
CN106916261B (zh) * 2015-12-25 2020-05-19 太阳油墨（苏州）有限公司 孔穴填埋用固化性树脂组合物及其固化物、和印刷电路板
CN106916262B (zh) * 2015-12-25 2020-03-13 太阳油墨（苏州）有限公司 孔穴填埋用固化性树脂组合物及其固化物、和印刷电路板
WO2018146821A1 (fr) * 2017-02-07 2018-08-16 株式会社有沢製作所 Composition de résine photosensible, film d'épargne de soudage mettant en œuvre cette composition, carte de circuit imprimé souple, et dispositif d'affichage d'image
WO2018147295A1 (fr) * 2017-02-07 2018-08-16 株式会社有沢製作所 Composition de résine photosensible, film d'épargne de soudage mettant en œuvre cette composition, carte de circuit imprimé souple, et dispositif d'affichage d'image
CN111133344A (zh) * 2017-09-26 2020-05-08 大阪有机化学工业株式会社 光间隔体形成用感光性树脂组合物、光间隔体的形成方法、带光间隔体的基板、及滤色器
US12273996B2 (en) * 2019-03-27 2025-04-08 Panasonic Intellectual Property Management Co., Ltd. Fiber sheet, and layered body, circuit board and electronic board using same
CN118235089A (zh) * 2021-11-15 2024-06-21 太阳控股株式会社 固化性树脂组合物、层叠结构体、固化物和电子部件
KR102734984B1 (ko) * 2023-01-17 2024-11-28 주식회사 케이씨씨 감광성 수지 조성물
KR102793408B1 (ko) * 2023-01-17 2025-04-09 주식회사 케이씨씨 감광성 수지 조성물

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CN103282828B (zh) * 2010-12-28 2016-07-06 太阳油墨制造株式会社 光固化性树脂组合物

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KR101693900B1 (ko) 2017-01-06
CN102272677B (zh) 2013-09-04
JP2010113241A (ja) 2010-05-20

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