Classifications

• • 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
• • 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
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • 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

Definitions

• the present invention relates to a photosensitive resin composition, a dry film, a cured product, and a printed wiring board.
• Solder resist is used on the surface of printed wiring boards and substrates for semiconductor packages, and serves to protect the circuit patterns formed on the substrate from external shocks and stresses such as heat and moisture.
• solder resist is now required to have various properties as a constituent material of semiconductor packages, such as high resolution, adaptability to thin films, hiding power, designability, etc., in addition to simply protecting the wiring (e.g., crack resistance, insulation resistance, heat resistance, etc.).
• black solder resists from the standpoint of concealing the wiring patterns of printed wiring boards and improving design.
• Patent Document 1 discloses a black photosensitive resin composition containing at least one black colorant selected from the group consisting of carbon black, perylene black, aniline black, and titanium black.
• the present invention aims to provide a photosensitive resin composition that maintains good resolution, prevents color variation due to the influence of the copper color of the base even when the film is thin, and gives a cured product with hiding properties.
• a photosensitive resin composition containing (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerization initiator, and (D) a photopolymerizable monomer, in which the colorant (A) contains an anthraquinone blue pigment and carbon black, has good resolution, is less susceptible to the influence of the copper color of the base even when the composition is made into a thin film, prevents color variation, and gives a cured product with hiding properties, thus completing the present invention.
• the colorant (A) further contains at least one of an anthraquinone-based yellow pigment and a perylene-based red pigment.
• the anthraquinone blue pigment is contained in an amount of 0.01 to 4 parts by mass per 100 parts by mass of the total solid content in the photosensitive resin composition.
• a dry film according to another aspect of the present invention is characterized by having a first film and a resin layer consisting of a dried coating of the above-mentioned photosensitive resin composition formed on the first film.
• the cured product is characterized in that it is a cured product obtained by curing the above-mentioned photosensitive resin composition or the resin layer of the above-mentioned dry film.
• a further aspect of the present invention is a printed wiring board characterized by having the above-mentioned cured product.
• the present invention provides a photosensitive resin composition that maintains good resolution while preventing color variation due to the influence of the copper color of the base even when the film is thinned, and that gives a cured product with good hiding properties.
• the photosensitive resin composition of the present invention contains an anthraquinone-based blue pigment, and therefore has high transmittance for light with a wavelength of 365 nm, and can give a cured product with good hiding properties while maintaining good resolution.
• the photosensitive resin composition of the present invention can be suitably used as a resin layer in a dry film, and the cured product obtained by curing this composition is also useful as a solder resist or coverlay for printed wiring boards.
• (meth)acrylate is a general term for "acrylate,” “methacrylate,” and mixtures thereof, and the same applies to other similar expressions.
• the photosensitive resin composition according to the present embodiment is a photosensitive resin composition containing (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerization initiator, and (D) a photopolymerizable monomer.
• the resin composition is a photosensitive resin composition, in which the colorant (A) contains an anthraquinone blue pigment and carbon black.
• the photosensitive resin composition according to the present embodiment contains an anthraquinone blue pigment and carbon black as the colorant (A).
• the colorant (A) preferably contains at least one of an anthraquinone yellow pigment and a perylene red pigment.
• the colorant (A) may further contain other colorants.
• the anthraquinone blue pigment is not particularly limited, and any known or commonly used pigment can be used.
• the anthraquinone blue pigment also includes pigments having a skeleton in which two or more anthraquinone skeletons are condensed, such as an indanthrone skeleton.
• anthraquinone-based blue pigments examples include Pigment Blue 22 and Pigment Blue 60. These anthraquinone blue pigments may be used alone or in combination of two or more.
• the content of the anthraquinone blue pigment in the photosensitive resin composition is preferably 0.01 to 4 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the total solid content in the photosensitive resin composition.
• the carbon black is not particularly limited, and any known and commonly used carbon black can be used, including channel black, oil furnace black, gas furnace black, thermal black, acetylene black, bone black, and the like.
• carbon black examples include Pigment Black 6, Pigment Black 7, Pigment Black 8, Pigment Black 9, and Pigment Black 10. These carbon blacks may be used alone or in combination of two or more.
• the content of carbon black in the photosensitive resin composition is preferably 0.01 to 1 part by mass, more preferably 0.01 to 0.7 parts by mass, and even more preferably 0.01 to 0.4 parts by mass, per 100 parts by mass of the total solid content in the photosensitive resin composition.
• the anthraquinone yellow pigment is not particularly limited, and any known and commonly used pigment can be used.
• the anthraquinone yellow pigment also includes pigments having an anthrapyrimidine derivative skeleton, which is an anthraquinone derivative.
• anthraquinone yellow pigments examples include Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 112, Pigment Yellow 147, and Pigment Yellow 193. These anthraquinone yellow pigments may be used alone or in combination of two or more.
• the content of the anthraquinone yellow pigment in the photosensitive resin composition is preferably 0.01 to 2.5 parts by mass, more preferably 0.05 to 2 parts by mass, and even more preferably 0.1 to 1.5 parts by mass, per 100 parts by mass of the total solid content in the photosensitive resin composition.
• the perylene-based red pigment is not particularly limited, and any known and commonly used perylene-based red pigment can be used.
• Examples of the perylene-based red pigment include Pigment Red 123, Pigment Red 149, Pigment Red 178, Pigment Red 179, Pigment Red 190, and Pigment Red 224. These perylene-based red pigments may be used alone or in combination of two or more.
• the content of the perylene-based red pigment in the photosensitive resin composition is preferably 0.01 to 4 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the total solid content in the photosensitive resin composition.
• the photosensitive resin composition according to the present embodiment may contain other colorants.
• known colorants such as red, blue, green, yellow, orange, and black may be used, and may be any of pigments, dyes, and colorants.
• the composition does not contain halogen.
• Red colorants include monoazo, disazo, azo lake, benzimidazolone, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone, and specific examples include those with the following Color Index (C.I.; published by The Society of Dyers and Colourists) numbers:
• Examples of monoazo red colorants include 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, and 269.
• Examples of disazo red colorants include Pigment Red 37, 38, and 41.
• Examples of monoazo lake-based red colorants include 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, and 68.
• Examples of benzimidazolone-based red colorants include Pigment Red 171, 175, 176, 185, and 208.
• Examples of diketopyrrolopyrrole-based red colorants include Pigment Red 254, 255, 264, 270, and 272.
• Condensed azo red colorants include Pigment Red 220, 144, 166, 214, 220, 221, and 242.
• Anthraquinone red colorants include Pigment Red 168, 177, and 216, Solvent Red 52, 149, 150, and 207.
• Quinacridone red colorants include Pigment Red 122, 202, 206, 207, and 209.
• Blue colorants include phthalocyanine-based agents, and pigment-based agents include compounds classified as pigments, such as Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 16.
• Dye-based agents include Solvent Blue 35, 63, 67, 68, 70, 83, 87, 94, 97, 122, and 136.
• metal-substituted or unsubstituted phthalocyanine compounds can also be used.
• Yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, and isoindolinone types.
• isoindolinone yellow colorants include Pigment Yellow 110, 109, 139, 179, and 185.
• Condensed azo yellow colorants include Pigment Yellow 93, 94, 95, 128, 155, 166, and 180.
• Benzimidazolone yellow colorants include Pigment Yellow 120, 151, 154, 156, 175, and 181.
• Examples of monoazo yellow colorants include 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, and 183.
• Examples of disazo yellow colorants include Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, and 198.
• colorants such as purple, orange, brown, black, and white may be added.
• Specific examples include Pigment Black 1, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, and 32, Pigment Violet 19, 23, 29, 32, 36, 38, and 42, Solvent Violet 13 and 36, C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, and 73, Pigment Brown 23 and 25, perylene black, titanium black, zirconium nitride, lactone black, and titanium oxide.
• the photosensitive resin composition according to the present embodiment contains an alkali-soluble resin (B).
• the alkali-soluble resin (B) is not particularly limited and may be any resin that is soluble in alkali, and any known and commonly used resin may be used.
• Alkali-soluble resins include, for example, water-soluble resins such as carboxyl group-containing resins and phenolic hydroxyl group-containing resins. Among them, from the viewpoint of excellent developability, carboxyl group-containing resins and phenolic hydroxyl group-containing resins are preferred, and carboxyl group-containing resins are more preferred.
• the carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group, or a carboxyl group-containing resin not having an ethylenically unsaturated group.
• Alkali-soluble resins may be used alone or in combination of two or more. By including the alkali-soluble resin (B) in the photosensitive resin composition, it becomes easy to form a pattern by alkaline development of a resin layer formed from the photosensitive resin composition.
• carboxyl group-containing resins include the compounds (which may be either oligomers or polymers) listed below.
• a carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth)acrylate, or isobutylene.
• Carboxylic acid-containing urethane resins obtained by the polyaddition reaction of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and diol compounds such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.
• diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylol
• Carboxylic acid-containing photosensitive urethane resins obtained by polyaddition reaction of diisocyanates with bifunctional epoxy resins such as bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bixylenol type epoxy resins, and biphenol type epoxy resins, and monocarboxylic acid compounds having ethylenically unsaturated double bonds such as (meth)acrylic acid, partially acid anhydride-modified products, carboxyl group-containing dialcohol compounds, and diol compounds.
• bifunctional epoxy resins such as bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bixylenol type epoxy resins, and biphenol type epoxy resins
• monocarboxylic acid compounds having ethylenically unsaturated double bonds such as (meth)acrylic acid, partially acid anhydride-modified products, carboxy
• a photosensitive urethane resin containing a carboxyl group which is terminated with (meth)acrylation by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as hydroxyalkyl (meth)acrylate, during the synthesis of the resin (2) or (3).
• a carboxyl group-containing photosensitive urethane resin that is (meth)acrylated at the end by adding a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, during the synthesis of the resin (2) or (3).
• a carboxyl group-containing photosensitive resin obtained by reacting a difunctional or more polyfunctional (solid) epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride to the hydroxyl groups present in the side chains.
• a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy resin in which the hydroxyl groups of a bifunctional (solid) epoxy resin have been further epoxidized with epichlorohydrin, with (meth)acrylic acid, and then adding a dibasic acid anhydride to the resulting hydroxyl groups.
• a carboxyl group-containing polyester resin obtained by reacting a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid with a bifunctional oxetane resin, and then adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the resulting primary hydroxyl groups.
• a carboxyl group-containing photosensitive resin obtained by reacting an epoxy compound having multiple epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and an unsaturated group-containing monocarboxylic acid, such as (meth)acrylic acid, and then reacting the alcoholic hydroxyl group of the resulting reaction product with a polybasic acid anhydride, such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic acid.
• a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic acid.
• a carboxyl group-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.
• an alkylene oxide such as ethylene oxide or propylene oxide
• a carboxyl group-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.
• a cyclic carbonate compound such as ethylene carbonate or propylene carbonate
• a carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins (1) to (11).
• the phenolic hydroxyl group-containing resin there are no particular limitations on the phenolic hydroxyl group-containing resin, so long as it has a phenolic hydroxyl group in the main chain or side chain, i.e., a hydroxyl group bonded to a benzene ring.
• the resin has two or more phenolic hydroxyl groups in one molecule.
• resins containing two or more phenolic hydroxyl groups per molecule include, but are not limited to, phenolic resins synthesized using catechol, resorcinol, hydroquinone, dihydroxytoluene, naphthalenediol, t-butylcatechol, t-butylhydroquinone, pyrogallol, phloroglucinol, bisphenol A, bisphenol F, bisphenol S, biphenol, bixylenol, etc., novolac-type phenolic resins, novolac-type alkylphenolic resins, bisphenol A novolac resins, dicyclopentadiene-type phenolic resins, Xylok-type phenolic resins, terpene-modified phenolic resins, polyvinylphenols, condensates of phenols with aromatic aldehydes having phenolic hydroxyl groups, and condensates of 1-naphthol or 2-naph
• the acid value of the alkali-soluble resin is preferably 20 to 180 mgKOH/g, more preferably 30 to 150 mgKOH/g, and even more preferably 40 to 120 mgKOH/g.
• the weight-average molecular weight of the alkali-soluble resin is preferably 3,000 to 30,000, more preferably 5,000 to 20,000, and even more preferably 7,000 to 15,000.
• the weight-average molecular weight can be determined from the standard polystyrene equivalent value by gel permeation chromatography (GPC).
• the content of the alkali-soluble resin in the photosensitive resin composition is preferably 10 to 80 parts by mass, more preferably 15 to 70 parts by mass, and even more preferably 20 to 60 parts by mass, per 100 parts by mass of the total solid content in the photosensitive resin composition.
• the photosensitive resin composition according to the present embodiment contains a photopolymerization initiator (C).
• the photopolymerization initiator (C) is not particularly limited, and any known and commonly used photopolymerization initiator can be used.
• the photopolymerization initiator may be used alone or in combination of two or more.
• photopolymerization initiator examples include ⁇ -aminoacetophenone-based photopolymerization initiators such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and N,N-dimethylaminoacetophenone; 1-hydroxy-cyclohexylphenylketone; hydroxyacetophenone-based photopolymerization initiators such as 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl ⁇ -2-methyl-propan-1-one, and
• the photopolymerization initiator may be used alone or in combination of two or more.
• the method of combining the photopolymerization initiators is not particularly limited, and for example, it is preferable to use two or more photopolymerization initiators selected from the group consisting of ⁇ -aminoacetophenone-based polymerization initiators, acylphosphine oxide-based photopolymerization initiators, and titanocene-based photopolymerization initiators in combination, it is more preferable to use two or more photopolymerization initiators selected from the group consisting of ⁇ -aminoacetophenone-based polymerization initiators and titanocene-based photopolymerization initiators in combination, and it is even more preferable to select and use one or more ⁇ -aminoacetophenone-based polymerization initiators and one or more titanocene-based photopolymerization initiators in combination.
• ⁇ -aminoacetophenone-based photopolymerization initiators include, for example, Omnirad 907, 369, 369E, and 379 manufactured by IGM Resins.
• An example of a commercially available acylphosphine oxide photopolymerization initiator is Omnirad 819 manufactured by IGM Resins.
• Commercially available titanocene photopolymerization initiators include, for example, JMT-784 manufactured by Yueyang Kimoutain Sci-tech Co., Ltd.
• the amount of the photopolymerization initiator is preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the total solid content in the photosensitive resin composition.
• the amount is 0.5 parts by mass or more, the photocuring property of the photosensitive resin composition is good, the cured product is less likely to peel off, and the coating properties such as chemical resistance are also good.
• the amount is 10 parts by mass or less, the effect of reducing outgassing is obtained, and further, the light absorption at the surface of the resin layer is good, and the deep curing property is not likely to decrease. More preferably, it is 0.8 to 8 parts by mass.
• the amount of the oxime ester photopolymerization initiator is preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the total solid content in the photosensitive resin composition.
• the amount is 0.1 parts by mass or more, the photocuring property of the photosensitive resin composition is good, and the coating properties such as heat resistance and chemical resistance are also good.
• the amount is 5 parts by mass or less, the light absorption at the surface of the resin layer is good, and the deep curing property is not likely to decrease. More preferably, it is 0.5 to 3 parts by mass.
• the photosensitive resin composition according to the present embodiment contains a photopolymerizable monomer (D).
• the photopolymerizable monomer (D) may be any monomer having an ethylenically unsaturated double bond in the molecule, and any known or commonly used monomer may be used.
• Examples of the photopolymerizable monomer include polyester (meth)acrylate, polyether (meth)acrylate, urethane (meth)acrylate, carbonate (meth)acrylate, and epoxy (meth)acrylate.
• Specific examples of the alkyl acrylates include alkyl acrylates such as 2-ethylhexyl acrylate and cyclohexyl acrylate; hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; mono- or diacrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, and N,N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acryl
• Such photopolymerizable monomers can also be
• the photopolymerizable monomer may be used alone or in combination of two or more.
• the amount of the photopolymerizable monomer is preferably 10 to 60 parts by mass per 100 parts by mass of the total solid content in the photosensitive resin composition.
• the amount is 10 parts by mass or more, the photocurability is good and pattern formation is easy in alkaline development after irradiation with active energy rays.
• the amount is 60 parts by mass or less, halation is less likely to occur and good resolution can be obtained.
• the photosensitive resin composition according to this embodiment may contain a thermosetting component, an inorganic filler, an antifoaming agent, other additive components, and the like.
• thermosetting component used in the photosensitive resin composition according to the present embodiment is not particularly limited, and may be any known or commonly used component, such as an epoxy resin, a triazine resin, a phenolic resin, or a polyester resin. It is preferable to use an epoxy resin.
• the thermosetting component may be used alone or in combination of two or more kinds.
• an epoxy resin having two or more epoxy groups in the molecule can be used, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenol type epoxy resin, hydroquinone type epoxy resin, bisphenol fluorene type epoxy resin, naphthalene diol type epoxy resin, bisphenol S type epoxy resin, bisthioether type epoxy resin, resorcinol type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alkyl novolac type epoxy resin, etc.
• bisphenol A type epoxy resin bisphenol F type epoxy resin
• biphenol type epoxy resin hydroquinone type epoxy resin
• bisphenol fluorene type epoxy resin bisphenol fluorene type epoxy resin
• naphthalene diol type epoxy resin bisphenol S type epoxy resin
• bisthioether type epoxy resin bisthioether type epoxy resin
• resorcinol type epoxy resin hydrogenated bisphenol A type epoxy resin
• phenol novolac type epoxy resin cresol novolac type epoxy
• epoxy resins include, for example, "jER828”, “jER834", “jER1001”, and “jER1004" manufactured by Mitsubishi Chemical Corporation; "Epicron 840", “Epicron 850”, “Epicron 1050”, and “Epicron 2055” manufactured by DIC Corporation; Epotohto "YD-011", “YD-013", “YD-127", and “YD-128” manufactured by Nippon Steel Chemical & Material Co., Ltd.; “D.E.R.317”, “D.E.R.331", “D.E.R.661", and “D.E.R.664" manufactured by Dow Chemical Company; Sumi-Epoxy "ESA-011", “ESA-014", “ELA-115", and “ELA-128” manufactured by Sumitomo Chemical Co., Ltd.; and “A.E.R.330” and “A.E.R.330” manufactured by Asahi Kasei Corporation.
• glycidylamine type epoxy resins such as "ELM-120” manufactured by Sumitomo Chemical Co., Ltd.; hindathoin type epoxy resins; alicyclic epoxy resins such as “Celloxide 2021P” manufactured by Daicel Corporation and "CY179" manufactured by Huntsman Advanced Materials; trihydroxyphenylmethane type epoxy resins such as “YL-933” manufactured by Mitsubishi Chemical Corporation and “T.E.N.”, "EPPN-501", and “EPPN-502” manufactured by The Dow Chemical Company; bixylenol type or biphenol type epoxy resins or mixtures thereof such as “YL-6056", “YX-4000", and “YL-6121” manufactured by Mitsubishi Chemical Corporation; "EBPS-200” manufactured by Nippon Kayaku Co., Ltd., "EPX-30” manufactured by ADEKA Corporation, and " Bisphenol S type epoxy resins such as "EXA-1514” manufactured by Mitsubishi Chemical Corporation; bisphenol A novolac type epoxy resins such as "jER157S”
• the amount of the thermosetting component is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass, per 100 parts by mass of the total solid content in the photosensitive resin composition.
• the inorganic filler used in the photosensitive resin composition according to the present embodiment is not particularly limited, and any known and commonly used inorganic filler can be used. These inorganic fillers may be used alone or in combination of two or more. Two or more species may be used in combination.
• inorganic fillers include talc, silica, kaolin, montmorillonite, synthetic mica, hydrotalcite, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, gold, aluminum, copper, and nickel.
• the shape of the inorganic filler is not particularly limited, and examples include spherical, fibrous, plate-like, amorphous, and balloon-like shapes.
• the average particle size of the inorganic filler is also not particularly limited, and for example, fillers with a particle size of 0.01 to 3.0 ⁇ m can be used.
• the inorganic filler may be subjected to various surface treatments such as insulation treatment and high-dispersion treatment, if necessary.
• the inorganic filler used in this embodiment is preferably one selected from the group consisting of barium sulfate, hydrotalcite, talc, and silica, from the viewpoint of improving the adhesion of the cured product obtained by curing the photosensitive resin composition after leveling treatment or gold plating treatment.
• the amount of inorganic filler to be blended is preferably 15 to 70 parts by mass, more preferably 20 to 60 parts by mass, even more preferably 25 to 55 parts by mass, and particularly preferably 30 to 50 parts by mass, per 100 parts by mass of the total solid content in the photosensitive resin composition.
• the defoaming agent used in this embodiment is not particularly limited, and any known and commonly used agent can be used. Among them, silicone-based or acrylic copolymer-based defoaming agents can be preferably used.
• silicone defoamers include, for example, BYK-322 and BYK-333, and Shin-Etsu Chemical Co., Ltd.'s KS-66.
• acrylic copolymer defoamers include, for example, BYK-361N, BYK-1794, BYK-350, and BYK-1791.
• the amount of antifoaming agent is not particularly limited, and can be 0.1 to 10 parts by mass per 100 parts by mass of the total solid content in the photosensitive resin composition.
• the photosensitive resin composition according to the present embodiment may further contain, as necessary, components such as organic solvents, photopolymerization initiators, cyanate compounds, elastomers, mercapto compounds, curing catalysts, polymerization inhibitors, thixotropic agents, adhesion promoters, block copolymers, chain transfer agents, copper inhibitors, antioxidants, rust inhibitors, thickeners such as organic bentonite and montmorillonite, silane coupling agents such as imidazoles, thiazoles, and triazoles, and flame retardants such as phosphorus compounds such as phosphinates, phosphate ester derivatives, and phosphazene compounds. These may be known in the field of electronic materials.
• components such as organic solvents, photopolymerization initiators, cyanate compounds, elastomers, mercapto compounds, curing catalysts, polymerization inhibitors, thixotropic agents, adhesion promoters, block copolymers, chain transfer agents, copper inhibitors,
• the photosensitive resin composition according to this embodiment can also be in the form of a dry film comprising a first film and a resin layer formed on the first film, the resin layer being a dry coating of the photosensitive resin composition.
• the first film in this embodiment refers to a film that is at least adhered to the resin layer when the resin layer side formed on the dry film is laminated by heating or the like so as to be in contact with a substrate or other base material, and integrally molded.
• the first film may be peeled off from the resin layer in a process after lamination. In particular, in this embodiment, it is preferable to peel off from the resin layer in a process after exposure.
• the photosensitive resin composition according to this embodiment is diluted with the organic solvent to adjust the viscosity to an appropriate level, and applied to a uniform thickness on the first film using a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, or the like, and usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to obtain a film.
• a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, or the like and usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to obtain a film.
• the coating thickness is generally selected appropriately in the range of 1 to 150 ⁇ m, preferably 10 to 60 ⁇ m, in terms of the thickness after drying.
• any known film can be used without particular restriction.
• polyester films such as polyethylene terephthalate and polyethylene naphthalate
• films made of thermoplastic resins such as polyimide films, polyamideimide films, polypropylene films, and polystyrene films
• polyester films are preferred from the standpoints of heat resistance, mechanical strength, and ease of handling.
• a laminate of these films can also be used as the first film.
• thermoplastic resin film described above is a film that has been oriented uniaxially or biaxially.
• the thickness of the first film is not particularly limited, but can be, for example, 10 ⁇ m to 150 ⁇ m.
• the second film in this embodiment refers to a film that is peeled off from the photosensitive resin layer before lamination when the resin layer side of the photosensitive film laminate is laminated by heating or the like so as to be in contact with a base material such as a substrate and integrally molded.
• peelable second film examples include polyethylene film, polytetrafluoroethylene film, polypropylene film, and surface-treated paper, and any film can be used as long as the adhesive strength between the resin layer and the second film is smaller than the adhesive strength between the resin layer and the first film when the second film is peeled off.
• the thickness of the second film is not particularly limited, but can be, for example, 10 ⁇ m to 150 ⁇ m.
• the photosensitive resin composition according to this embodiment may be applied to the second film and dried to form a resin layer, and the first film may be laminated on the surface of the resin layer.
• the first film or the second film may be used as the film to which the photosensitive resin composition according to this embodiment is applied.
• the photosensitive resin composition is applied onto a substrate, and the organic solvent is evaporated and dried to obtain a resin layer, which is then exposed (irradiated with light) to cure the exposed portion (the portion irradiated with light).
• the photosensitive resin composition is selectively exposed to active energy rays through a photomask on which a pattern has been formed by a contact or non-contact method, or the pattern is directly exposed by a laser direct exposure machine, and the unexposed portion is developed with an alkaline aqueous solution (for example, a 0.3 to 3% by mass aqueous solution of sodium carbonate), thereby forming a resist pattern.
• the first film is peeled off from the dry film and development is performed to form a patterned cured product on the substrate.
• the first film may be peeled off from the dry film before exposure, and the exposed resin layer may be exposed and developed.
• the cured product by subjecting the cured product to irradiation with active energy rays and then heat curing (for example, at 100 to 220° C.), or by subjecting the cured product to heat curing and then irradiating active energy rays, or by subjecting the product to heat curing alone for final finish curing (main curing), it is possible to form a cured product that has excellent solder heat resistance, gold plating resistance, and insulation reliability.
• the photosensitive resin composition according to this embodiment can be adjusted to a viscosity suitable for the application method using an organic solvent, and applied to a substrate by a method such as inkjet, dip coating, flow coating, roll coating, bar coating, screen printing, or curtain coating.
• the organic solvent contained in the composition can then be evaporated and dried at a temperature of about 60 to 100°C to form a tack-free resin layer.
• Substrates include printed wiring boards and flexible printed wiring boards with circuits already formed using copper, etc., as well as materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, copper-clad laminates for high-frequency circuits using fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc., including copper-clad laminates of all grades (FR-4, etc.), as well as metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, and wafer plates.
• materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, copper-clad laminates for high-frequency circuits using fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc., including copper-clad laminates of all
• the volatilization drying or thermal curing can be carried out using a hot air circulation drying oven, IR oven, hot plate, convection oven, etc. (a method in which hot air in the dryer is brought into countercurrent contact using a heat source that uses steam for air heating, or a method in which hot air is blown onto the support from a nozzle).
• a resin layer can be formed on the substrate by laminating the dry film onto the substrate using a laminator or the like so that the resin layer comes into contact with the substrate.
• the lamination of the dry film onto the substrate is preferably performed under pressure and heat using a vacuum laminator or the like.
• a vacuum laminator By using such a vacuum laminator, when a substrate on which a circuit is formed is used, even if the surface of the circuit substrate is uneven, the dry film adheres to the substrate, preventing the inclusion of air bubbles and improving the filling of recesses in the substrate surface.
• the pressure conditions are preferably about 0.1 to 2.0 MPa, and the heating conditions are preferably 40 to 120°C.
• the exposure machine used for the above-mentioned active energy ray irradiation may be a machine equipped with a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like, and irradiates active energy rays in the range of 350 to 450 nm, and further may be a direct imaging machine (for example, a laser direct imaging machine that draws an image directly with a laser based on CAD data from a computer).
• the lamp light source or laser light source of the direct imaging machine may have a maximum wavelength in the range of 350 to 410 nm.
• the exposure dose for image formation varies depending on the film thickness, etc., but is generally preferably 20 to 1000 mJ/ cm2 , and may be within the range of 20 to 800 mJ/ cm2 .
• the above-mentioned developing method can be a dipping method, a shower method, a spray method, a brush method, etc.
• the developing solution can be an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc.
• the photosensitive resin composition or the resin layer of the dry film according to the present embodiment can be suitably used to form a surface protection film such as a solder resist on a printed wiring board.
• the photosensitive resin composition according to the present embodiment may be used as an interlayer insulating layer of a multilayer printed wiring board.
• a printed wiring board By applying the photosensitive resin composition or dry film resin layer according to this embodiment to a substrate of a printed wiring board or the like and curing it, a printed wiring board can be manufactured that has a cured product with excellent solder heat resistance, gold plating resistance, and insulation reliability.
• each component shown in Table 1 The details of each component shown in Table 1 are as follows. The amount of each component is expressed as a solid content value.
• Paliogen Blue L6480 manufactured by BASF: anthraquinone-based blue pigment
• FA5380 manufactured by DIC Corporation
• Pigment Blue 80 benzimidazolone-dioxazine-based blue pigment
• Cromophthal Yellow S1515 manufactured by BASF
• Paliogen Red K3580 manufactured by BASF, C.I.
• Pigment Red 149) perylene-based red pigment
• MA-100 manufactured by Mitsubishi Chemical Corporation
• MA-100 manufactured by Mitsubishi Chemical Corporation
• MA-100 manufactured by Mitsubishi Chemical Corporation
• MA-100 manufactured by Mitsubishi Chemical Corporation
• MA-100 manufactured by Mitsubishi Chemical Corporation
• *1 Alkali-soluble resin synthesized above (carboxyl group-containing photosensitive resin)
• C Photopolymerization initiator>
• Omnirad 379 manufactured by IGM Resins
• JMT-784 manufactured by Yueyang Kimoutain Sci-tech Co., Ltd.
• JMT-784 manufactured by Yueyang Kimoutain Sci-tech Co., Ltd.
• solder dam shape A circuit pattern board with a copper thickness of 33 ⁇ m was pretreated by etching equivalent to 1.0 ⁇ m using a copper surface roughening treatment (MEC Etch Bond (TM) CZ-8101B manufactured by MEC Co., Ltd.)
• MEC Etch Bond (TM) CZ-8101B manufactured by MEC Co., Ltd.
• the test photosensitive resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were applied to the entire surface of the board by a screen printing method so that the dry film thickness was 30 ⁇ m, and the board was dried for 30 minutes in a hot air circulation drying oven at 80° C. After drying, the film was exposed to light using a high-pressure mercury lamp exposure device.
• the exposure pattern used was a pattern that drew 100 ⁇ m lines in the space portion.
• the film was irradiated with light using an exposure device so that the exposure amount was 400 mJ/cm 2 , and in Examples 2, 3, and 5, the exposure amount was 200 mJ/cm 2. Thereafter, the film was developed with an aqueous sodium carbonate solution (30° C., 0.2 MPa, 1 wt % aqueous sodium carbonate solution) to form a pattern. Further, the film was thermally cured at 150° C. for 60 minutes to obtain a cured product.
• an aqueous sodium carbonate solution (30° C., 0.2 MPa, 1 wt % aqueous sodium carbonate solution
• a cross section of the cured solder dam with a line width of 100 ⁇ m was observed using an optical microscope, and the line width at the bottom of the solder dam was subtracted from the line width at the top of the solder dam to determine the value, and the evaluation was performed according to the following criteria.
• the results are shown in Table 1.
• ⁇ The absolute value of the line width of the upper part of the solder dam minus the line width of the lower part of the solder dam is 20 ⁇ m or less.
• ⁇ The absolute value of the line width of the upper part of the solder dam minus the line width of the lower part of the solder dam is more than 20 ⁇ m.
• a copper solid substrate with a copper thickness of 18 ⁇ m was pretreated by etching equivalent to 1.0 ⁇ m using a copper surface roughening treatment (MEC Etch Bond (TM) CZ-8101B manufactured by MEC Co., Ltd.).
• MEC Etch Bond (TM) CZ-8101B manufactured by MEC Co., Ltd.
• the test photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were applied to the entire surface of the substrate by a screen printing method so that the dry film thickness was 10 ⁇ m or 20 ⁇ m, and the substrate was dried for 30 minutes in a hot air circulation drying oven at 80° C.
• the appearance color of the solder resist layer on the copper foil was measured using a spectrophotometer CM-2600d (manufactured by Konica Minolta Japan, Inc.) and quantified for a * in the CIE 1976 color system.
• the a* value was measured under conditions including total reflected light in accordance with JIS Z 8792.
• the surface of the copper substrate that had been subjected to the copper surface roughening treatment was measured using a spectrophotometric colorimeter CM-2600d (manufactured by Konica Minolta Japan, Inc.) and quantified for L * , a *, and b * in the CIE 1976 color system.
• the copper solid substrate has a reddish color, as the a * value of the underlying copper solid substrate is 21.
• the solder resist layer is made thinner, if the concealment ability of the solder resist layer is low, it will be affected by the reddish color of the underlying copper solid substrate, and the a * value of the solder resist layer on the copper solid substrate will change to the positive side compared to the case of only the solder resist layer.
• the absolute value ⁇ a * value was calculated by subtracting the a * value of the 10 ⁇ m thick solder resist layer on the copper foil from the a * value of the 20 ⁇ m thick solder resist layer on the copper foil, and the degree of influence of the copper color of the base and the concealing ability when the solder resist layer was thinned were evaluated according to the following criteria. The results are shown in Table 1. ⁇ : ⁇ a * value is 1.0 or less ⁇ : ⁇ a * value is greater than 1.0

Landscapes

• Engineering & Computer Science (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Manufacturing & Machinery (AREA)
• Materials For Photolithography (AREA)
• Non-Metallic Protective Coatings For Printed Circuits (AREA)
• Polymerisation Methods In General (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=92905443

Family Applications (1)

Country Status (4)

Citations (6)

• 2024
  • 2024-03-26 WO PCT/JP2024/012078 patent/WO2024204265A1/ja not_active Ceased
  • 2024-03-26 JP JP2025510971A patent/JPWO2024204265A1/ja active Pending
  • 2024-03-26 CN CN202480015102.2A patent/CN120770007A/zh active Pending
  • 2024-03-28 TW TW113111752A patent/TW202442729A/zh unknown

Patent Citations (6)

Also Published As

Similar Documents

Legal Events