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
• • 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
  • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029
• • 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 photosensitive resin composition, and particularly to a photosensitive resin composition suitably used for forming a solder resist layer. Furthermore, the present invention also relates to a method for manufacturing a printed wiring board including a cured product formed using the photosensitive resin composition.
• solder resist layers are patterned by coating a photosensitive resin composition on a substrate, drying, and curing, and then applying the patterned photosensitive resin composition to the substrate.
• the mainstream is to use a so-called photo solder resist that is fully cured by heating or light irradiation.
• the photosensitive resin composition for forming the solder resist layer is generally placed under various environments from its manufacture to its actual use, and in many cases, it is only placed in a normal temperature environment around room temperature. They may be exposed to environments that alternate between room temperature and low temperature environments.
• photosensitive resin compositions are adjusted to maintain sufficient storage stability at room temperature, but when exposed to environments that alternate between room temperature and low temperature environments, the photosensitive resin composition
• the composition and properties of the resin composition may be impaired. If the composition or properties of the photosensitive resin composition are impaired, there is a problem that the formed solder resist layer will not exhibit sufficient performance.
• an object of the present invention is to provide a photosensitive material that suppresses the crystallization of components even when exposed to an environment that repeats a room temperature environment and a low temperature environment, and that has good characteristics required in the production of printed wiring boards. It is an object of the present invention to provide a resin composition with high compatibility. Another object of the present invention is to provide a method for manufacturing a printed wiring board comprising a cured product formed using a photosensitive resin composition having the above-mentioned favorable properties. Means to solve problems
• the present inventors have found that in a photosensitive resin composition containing a carboxyl group-containing resin, a photopolymerization initiator, and an organic solvent, an ⁇ -aminoacetophenone photopolymerization initiator is blended as a photopolymerization initiator, It was also found that the above-mentioned problems can be solved by blending petroleum solvents, carbitol acetates, and dipropylene glycol monomethyl ether as organic solvents. The present invention is based on this knowledge. That is, the gist of the present invention is as follows.
• a photosensitive resin composition containing a carboxyl group-containing resin, a photopolymerization initiator, and an organic solvent The photopolymerization initiator includes an ⁇ -aminoacetophenone photopolymerization initiator, A photosensitive resin composition, wherein the organic solvent contains a petroleum solvent, carbitol acetates, and dipropylene glycol monomethyl ether.
• a photosensitive resin composition according to [1] wherein the organic solvent has a mass ratio of petroleum solvent to carbitol acetate of 1:0.5 to 1:1.
• the crystallization of the components is suppressed even when exposed to an environment that repeats a room temperature environment and a low temperature environment, and the photosensitive resin has various favorable properties required in the production of printed wiring boards.
• a composition can be provided. Furthermore, according to the present invention, it is possible to provide a method for manufacturing a printed wiring board including a cured product formed using a photosensitive resin composition having the above-mentioned favorable properties.
• the photosensitive resin composition of the present invention contains a carboxyl group-containing resin, a photopolymerization initiator, and an organic solvent as essential components, the photopolymerization initiator contains an ⁇ -aminoacetophenone photopolymerization initiator, and the organic solvent contains petroleum It is characterized by containing a system solvent, carbitol acetates, and dipropylene glycol monomethyl ether.
• the photosensitive resin composition of the present invention is formulated by combining a specific photopolymerization initiator and a specific organic solvent, so that the photosensitive resin composition can be exposed to an environment that repeatedly changes between a room temperature environment and a low temperature environment.
• the occurrence of crystals in photosensitive resin compositions may cause pinholes, repelling, clogging of printing plates, etc. during printing, and may also cause unevenness on the surface of the cured product (solder resist layer).
• the yield of the photosensitive resin composition itself, a cured product obtained using the photosensitive resin composition, and a printed wiring board including the cured product may be reduced. Therefore, it can be said that the photosensitive resin composition of the present invention can also solve these problems by suppressing the crystallization after the above-mentioned cooling/heating cycle.
• Each component of the photosensitive resin composition of the present invention will be explained in detail below.
• Carboxyl group-containing resin In the photosensitive resin composition of the present invention, various conventionally known resins having a carboxyl group in the molecule can be used as the carboxyl group-containing resin.
• the photosensitive resin composition contains a carboxyl group-containing resin, alkaline developability can be imparted to the photosensitive resin composition.
• carboxyl group-containing resins having ethylenically unsaturated double bonds in the molecule are preferred.
• the ethylenically unsaturated double bond in the molecule is preferably derived from acrylic acid or methacrylic acid or derivatives thereof.
• One type of carboxyl group-containing resin may be used alone, or two or more types may be used in combination.
• the photosensitive resin composition is made photocurable.
• carboxyl group-containing resins include the following compounds (which may be oligomers or polymers).
• (meth)acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and includes other similar expressions such as "(meth)acrylic acid” and "(meth)acryloyl.” The same applies to
• 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.
• Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers.
• a carboxyl group-containing urethane resin produced by polyaddition reaction of diol compounds such as polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.
• Diisocyanate and bifunctional epoxy resins such as bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bixylenol epoxy resin, and biphenol epoxy resin ( Carboxyl group-containing photosensitivity resulting from polyaddition reaction of partially acid anhydride-modified products of reactants with monocarboxylic acid compounds having ethylenically unsaturated double bonds such as meth)acrylic acid, carboxyl group-containing dialcohol compounds, and diol compounds.
• Urethane resin Urethane resin.
• a carboxyl group-containing photosensitive resin obtained by reacting (meth)acrylic acid with a bifunctional or higher polyfunctional (solid) epoxy resin and adding a dibasic acid anhydride to the hydroxyl group present in the side chain.
• Group-containing photosensitive resin A carboxyl product obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin in which the hydroxyl groups of a bifunctional (solid) epoxy resin are further epoxidized with epichlorohydrin, and adding a dibasic acid anhydride to the resulting hydroxyl groups.
• Difunctional oxetane resin is reacted with a dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, etc., and the resulting primary hydroxyl group is converted into a dibase such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. Carboxyl group-containing polyester resin with acid anhydride added.
• a dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, etc.
• An epoxy compound having multiple epoxy groups in one molecule a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and (meth) Maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine are reacted with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and the alcoholic hydroxyl group of the resulting reaction product is A carboxyl group-containing photosensitive resin obtained by reacting polybasic acid anhydrides such as acids.
• reaction obtained by reacting a reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid.
• alkylene oxide such as ethylene oxide or propylene oxide
• unsaturated group-containing monocarboxylic acid A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.
• (11) Obtained by reacting a reaction product 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 with an unsaturated group-containing monocarboxylic acid.
• a carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.
• a carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins (1) to (11) described above.
• the acid value of the carboxyl group-containing resin is preferably 30 to 150 mgKOH/g, more preferably 50 to 120 mgKOH/g.
• the acid value of the carboxyl group-containing resin is 30 mgKOH/g or more, the alkali developability of the photosensitive resin composition becomes good. Further, by having an acid value of 150 mgKOH/g or less, it is possible to easily draw a good resist pattern.
• the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally preferably from 2,000 to 150,000, more preferably from 5,000 to 100,000. When the weight average molecular weight is 2,000 or more, tack-free performance and resolution can be improved. Further, by having a weight average molecular weight of 150,000 or less, the developability and storage stability of the photosensitive resin composition can be improved.
• the content of the carboxyl group-containing resin in the photosensitive resin composition is preferably 10 to 40% by mass, more preferably 20 to 35% by mass in terms of solid content.
• the content of the carboxyl group-containing resin is 10% by mass or more, the strength of the coating film can be improved.
• the content of the carboxyl group-containing resin is 40% by mass or less, the viscosity of the photosensitive resin composition becomes appropriate, and processability improves.
• photopolymerizable monomer A photopolymerizable monomer can be added to the photosensitive resin composition of the present invention, if necessary.
• the photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond.
• Examples of such photopolymerizable monomers include commonly known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, and epoxy (meth)acrylates.
• alkyl acrylates such as 2-ethylhexyl acrylate and cyclohexyl acrylate; hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; alkylenes such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; Mono- or diacrylates of oxide derivatives; acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, N,N-dimethylaminopropylacrylamide; N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl Aminoalkyl acrylates such as acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, trishydroxyethyl isocyan
• polyhydric acrylates phenols such as phenoxy acrylate and bisphenol A diacrylate, or polyhydric acrylates such as alkylene oxide adducts thereof; glycidyls such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc.
• Ether acrylates not limited to the above, acrylates and melamine acrylates obtained by directly acrylating polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, and polyester polyols, or converting them into urethane acrylates via diisocyanates, and the above-mentioned acrylates. It is possible to appropriately select and use at least one kind of methacrylates corresponding to the above.
• Such photopolymerizable monomers can also be used as reactive diluents.
• the photopolymerizable monomers may be used alone or in combination of two or more.
• the content of the photopolymerizable monomer in the photosensitive resin composition is preferably 10 to 100 parts by weight based on 100 parts by weight of the carboxyl group-containing resin.
• the content of the photopolymerizable monomer is 10 parts by mass or more, the photosensitive resin composition has good photocurability, and pattern formation becomes easy in alkaline development after irradiation with active energy rays.
• the content of the photopolymerizable monomer is 100 parts by mass or less, halation is less likely to occur and good resolution can be obtained.
• the photopolymerizable monomer is used in order to make the photosensitive resin composition photocurable. This is effective because it requires the use of a polymerizable monomer.
• the photopolymerization initiator includes an ⁇ -aminoacetophenone photopolymerization initiator. Any known ⁇ -acetaminophenone photopolymerization initiator can be used.
• ⁇ -acetaminophenone photopolymerization initiators include 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane-1 -one, 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, N,N-dimethylaminoacetophenone, etc. .
• One type of ⁇ -aminoacetophenone photopolymerization initiator may be used alone, or two or more types may be used in combination.
• the photosensitive resin composition contains, as a photopolymerization initiator, an ⁇ -aminoacetophenone photopolymerization initiator having a structure in which a strong electron-donating group such as an alkylthio group or a dialkylamino group is substituted at the para position of a benzoyl group. Accordingly, high curability can be obtained.
• the photosensitive resin composition may contain an additional photopolymerization initiator (hereinafter also referred to as "other photopolymerization initiator”) in addition to the above-mentioned ⁇ -aminoacetophenone photopolymerization initiator.
• additional photopolymerization initiators include hydroxyacetophenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, benzoin alkyl ether photopolymerization initiators, benzophenone photopolymerization initiators, acetophenone photopolymerization initiators, Examples include thioxanthone photopolymerization initiators, anthraquinone photopolymerization initiators, ketal photopolymerization initiators, benzoic acid ester photopolymerization initiators, oxime ester photopolymerization initiators, titanocene photopolymerization initiators, etc. .
• Other photopolymerization initiators may be used alone or in combination of two or more.
• the photopolymerization initiator preferably contains only an ⁇ -aminoacetophenone photopolymerization initiator. Further, as the ⁇ -aminoacetophenone photopolymerization initiator, preferably 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butane-1- On is used.
• Omnirad registered trademark
• 907 (2-methyl-1-[4-(methoxythio)phenyl]-2-morpholinopropane-1 manufactured by IGM Resins) -one
• 369 (2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone)
• 369E (2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone)
• 379 (2- dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one) and the like.
• the content of the photopolymerization initiator in the photosensitive resin composition is preferably 1 to 1 to 100 parts by mass of the carboxyl group-containing resin in terms of solid content.
• the amount is 20 parts by weight, more preferably 5 to 15 parts by weight.
• the photopolymerization initiator contains the other photopolymerization initiators mentioned above, and the other photopolymerization initiators are photopolymerization initiators other than oxime ester photopolymerization initiators, other photopolymerization initiators in the photosensitive resin composition
• the content of the polymerization initiator is preferably 1 to 20 parts by weight, more preferably 5 to 15 parts by weight, based on 100 parts by weight of the carboxyl group-containing resin, in terms of solid content.
• the photopolymerization initiator contains the other photopolymerization initiator mentioned above and the other photopolymerization initiator is an oxime ester photopolymerization initiator
• the oxime ester photopolymerization initiator in the photosensitive resin composition The content is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the carboxyl group-containing resin, in terms of solid content.
• the photosensitive resin composition has good photocurability, and has good peeling resistance, heat resistance, and The coating properties such as chemical properties are also improved, and the effect of reducing outgassing is obtained.Furthermore, the light absorption on the surface of the solder resist coating is improved, and deep curability is less likely to deteriorate. Furthermore, since the content of each photopolymerization initiator is within the above-mentioned range, the photopolymerization initiator is sufficiently dissolved in the organic solvent, so that crystallization of the photopolymerization initiator can be suppressed even under cooling/heating cycles. As a result, even when the photosensitive resin composition of the present invention is used after a cooling/heating cycle, its composition and properties are maintained, and it can have various good properties required during the production of printed wiring boards.
• a photoinitiation aid or a sensitizer may be used in combination with the above-mentioned photopolymerization initiator.
• the photoinitiation aid or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds.
• a thioxanthone compound and a tertiary amine compound are preferably used as the photoinitiation aid or sensitizer, and a thioxanthone compound is more preferably used.
• the above-mentioned photoinitiation aids and sensitizers may be used alone or in combination of two or more.
• thermosetting component The photosensitive resin composition of the present invention may contain a thermosetting component, if necessary.
• the thermosetting components used in the present invention include known and commonly used components such as isocyanate compounds, blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, epoxy compounds, oxetane compounds, and episulfide resins. can be mentioned.
• the thermosetting components may be used alone or in combination of two or more. Among these, the preferred thermosetting component is epoxy resin.
• epoxy resin examples include bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol S epoxy resin, novolac epoxy resin, and phenol novolac epoxy resin.
• examples include polymerized epoxy resins, copolymerized epoxy resins of cyclohexylmaleimi
• epoxy resins include, for example, jER (registered trademark) 828, 834, 1001, 1004 manufactured by Mitsubishi Chemical Corporation, and EPICLON (registered trademark) 840, 850, 850-S, 1050, 2055 manufactured by DIC Corporation. , Epotote (registered trademark) YD-011, YD-013, YD-127, YD-128 manufactured by Nippon Steel Chemical & Materials Co., Ltd., D. E. R.
• Novolac type epoxy resins such as EPICLON (registered trademark) N-680, N-690, N-695 manufactured by the company; EPICLON (registered trademark) 830 manufactured by DIC Corporation, jER (registered trademark) 807 manufactured by Mitsubishi Chemical Corporation , Bisphenol F type epoxy resins such as Epototh (registered trademark) YDF-170, YDF-175, YDF-2004 manufactured by Nippon Steel Chemical & Materials Co., Ltd.; Epototh (registered trademark) ST- manufactured by Nippon Steel Chemical & Materials Co., Ltd.
• Hydrogenated bisphenol A type epoxy resins such as 2004, ST-2007, ST-3000, YX8034 manufactured by Mitsubishi Chemical Corporation; jER (registered trademark) 604 manufactured by Mitsubishi Chemical Corporation, Epotote manufactured by Nippon Steel Chemical & Materials Corporation (registered trademark) YH-434, glycidylamine type epoxy resin such as Sumiepoxy (registered trademark) ELM-120 manufactured by Sumitomo Chemical Co., Ltd.; hydantoin type epoxy resin; Celloxide (registered trademark) 2021 manufactured by Daicel Corporation, Epolead (registered) Trademark) Alicyclic epoxy resins such as PB3600; trihydroxyphenylmethane type epoxy resins such as YL-933 manufactured by Mitsubishi Chemical Corporation, EPPN-501 and EPPN-502 manufactured by Nippon Kayaku Co., Ltd.; manufactured by Mitsubishi Chemical Corporation Bixylenol type or biphenol type epoxy resin such as YL-6056, YX-4000, YL-6
• the content of the thermosetting component in the photosensitive resin composition is preferably such that the number of functional groups in the reacting thermosetting component is 0.3 to 3.0 mol per mol of carboxyl group contained in the above-mentioned carboxyl group-containing resin. , more preferably 0.5 to 2.5 mol.
• the equivalent of the epoxy group of the epoxy resin in the photosensitive resin composition is 0.3 per equivalent of the carboxyl group of the carboxyl group-containing resin in terms of solid content. It is preferably 3.0 to 3.0.
• the epoxy group of the epoxy resin By setting the epoxy group of the epoxy resin to 0.3 equivalent or more, it is possible to prevent carboxyl groups from remaining in the cured film and obtain good heat resistance, alkali resistance, electrical insulation, etc.
• the epoxy group of the epoxy resin to 3.0 equivalents or less, it is possible to prevent low molecular weight cyclic (thio)ether groups from remaining in the dried coating film and ensure good strength etc. of the cured coating. be able to.
• thermosetting catalyst can be added to the photosensitive resin composition of the present invention, if necessary.
• the thermosetting catalyst used in the present invention include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2- Imidazole derivatives such as phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N , N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide, sebacic acid dihydrazide, and phosphorus compounds such as tripheny
• thermosetting catalysts include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all brand names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT manufactured by San-Apro Co., Ltd. 3513N (trade name of a dimethylamine compound), DBU, DBN, U-CAT SA (registered trademark) 102 (all bicyclic amidine compounds and salts thereof), and the like.
• thermosetting catalyst is not particularly limited to these, and may be any thermosetting catalyst for epoxy resins or oxetane compounds, or any catalyst that promotes the reaction of at least one of epoxy groups and oxetanyl groups with carboxyl groups.
• thermosetting catalyst
• the content of the thermosetting catalyst in the photosensitive resin composition is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the carboxyl group-containing resin.
• the content of the thermosetting catalyst is 0.1 parts by mass or more, the cured product of the photosensitive resin composition has excellent heat resistance.
• the content of the thermosetting catalyst is 20 parts by mass or less, the storage stability of the photosensitive resin composition is improved.
• the photosensitive resin composition of the present invention contains a petroleum solvent, carbitol acetates, and dipropylene glycol monomethyl ether as an organic solvent.
• the petroleum solvents, carbitol acetates, and dipropylene glycol monomethyl ether may be used alone or in combination of two or more.
• the components of the photosensitive resin composition can be sufficiently dissolved and the components can be prevented from crystallizing even under a cooling/heating cycle where the components are exposed to environments that alternate between room temperature and low temperature environments. This makes it possible to suppress precipitation.
• the composition and properties of the photosensitive resin composition can be maintained, and the photosensitive resin composition can have various favorable properties required for manufacturing printed wiring boards.
• Crystallization of the components of the photosensitive resin composition can be suppressed by using a combination of the three types of organic solvents described above.
• the reason why crystallization of the components can be suppressed even under cooling/heating cycles by using a combination of the three types of organic solvents described above is not clear, but it can be inferred as follows. That is, when using the three types of organic solvents contained in the photosensitive resin composition, petroleum solvents, carbitol acetates, and dipropylene glycol monomethyl ether, the change in solubility with respect to temperature changes is small (gradual).
• the components of the photosensitive resin composition can be stably dissolved in these organic solvents even under cooling/heating cycles, so that crystallization of the components under cooling/heating cycles can be suppressed.
• the solvent has a higher solubility at room temperature than the three organic solvents mentioned above, if the solubility changes significantly (suddenly) with temperature changes, the photosensitivity under cooling/heating cycles may decrease. Since the dissolved state of the components of the resin composition is unstable, as a result, it may not be possible to sufficiently suppress the crystallization of the components under cooling/heating cycles.
• the petroleum solvent specifically refers to a hydrocarbon solvent containing an aromatic hydrocarbon or a mixture thereof derived from petroleum, such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.
• the boiling point of the petroleum solvent is not particularly limited, and may be, for example, 150 to 200°C.
• the number of carbon atoms in the petroleum solvent is also not particularly limited, and examples include carbon numbers of 10 or more.
• aromatic hydrocarbons having 10 or more carbon atoms include, for example, aromatic compounds such as benzene, naphthalene, anthracene, etc., in which one or more hydrogen atoms are, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, etc. , or may be formed by substitution with an alkylene group such as an ethylene group, a propylene group, or a tetramethylene group.
• aromatic hydrocarbons contained in petroleum solvents include benzene, naphthalene, anthracene, isopropylbenzene, n-propylbenzene, 1-methyl-3-ethylbenzene, 1-methyl-4-ethylbenzene, 1,3,5 -Trimethylbenzene, 1-methyl-2-ethylbenzene, t-butylbenzene, 1,2,4-trimethylbenzene, isobutylbenzene, s-butylbenzene, 1-methyl-3-isopropylbenzene, 1,2,3-trimethyl Benzene, 1-methyl-4-isopropylbenzene, indane, 1-methyl-2-isopropylbenzene, 1,3-diethylbenzene, 1-methyl-3-propylbenzene, n-butylbenzene, 1-methyl-4-propylbenzene , 1,2-diethylbenzene, 1,4-diethylbenzene, 1,2-
• Petroleum solvents include, for example, Ipsol (registered trademark) #100 and #150 manufactured by Idemitsu Kosan Co., Ltd., T-SOL (trademark) 100 and 150 manufactured by ENEOS Corporation, and Cactus Solvent P-100 and P. -150, Swazol (registered trademark) 310, 1000 from Maruzen Petrochemical Co., Ltd., Solvesso (registered trademark) 100, 150, 200 from Ando Parachemy Co., Ltd., Shellzol A100, Shellzol A150 from Shell Chemicals Japan Co., Ltd. Examples include Scherzol S and the like.
• carbitol acetates refer to esters of acetic acid and diethylene glycol alkyl ether.
• Examples of carbitol acetates include diethylene glycol monomethyl ether acetate (methyl carbitol acetate), which is an ester of acetic acid and diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether acetate (ethyl carbitol), which is an ester of acetic acid and diethylene glycol monoethyl ether.
• acetate diethylene glycol monobutyl ether acetate
• butyl carbitol acetate diethylene glycol monobutyl ether acetate
• carbitol acetate One type of carbitol acetate may be used alone, or two or more types may be used in combination.
• carbitol acetates diethylene glycol monoethyl ether acetate (ethyl carbitol acetate) is preferably used, and diethylene glycol monoethyl ether acetate (ethyl carbitol acetate) is particularly preferably used alone.
• the mass ratio of the petroleum solvent and carbitol acetate in the organic solvent is preferably 1:0.5 to 1. :1.2, more preferably 1:0.5 to 1:1.
• the mass ratio of the petroleum solvent and dipropylene glycol monomethyl ether in the organic solvent is preferably 1:0. .7 to 1:1.2.
• the above-mentioned three types of organic solvents may be blended at the time of preparing the photosensitive resin composition of the present invention, and each component such as the carboxyl group-containing resin constituting the photosensitive resin composition of the present invention. It may be blended at the time of preparation, or it may be included as a solvent for each component. Preferably, all three kinds of organic solvents mentioned above are mixed at the time of preparing the photosensitive resin composition of the present invention.
• the organic solvent may contain additional solvent components in addition to the above-mentioned petroleum solvents, carbitol acetates, and dipropylene glycol monomethyl ether.
• Additional solvent components include ketones such as methyl ethyl ketone and cyclohexanone; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, and tripropylene glycol monomethyl ether; acetic acid.
• Esters such as ethyl, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate; known and commonly used solvents such as aliphatic hydrocarbons such as octane and decane. components can be used. These additional components may be used alone or in combination of two or more.
• the content of the organic solvent in the photosensitive resin composition is not particularly limited as long as the effects of the present invention are achieved, but petroleum solvents, carbitol acetates, etc.
• the total content of dipropylene glycol monomethyl ether is preferably adjusted to 50 to 90 parts by mass.
• the content of the organic solvent in the photosensitive resin composition is such that the total content of the petroleum solvent, carbitol acetates, and dipropylene glycol monomethyl ether is within the above-mentioned range.
• the total content of all organic solvent components is preferably adjusted to 100 to 150 parts by mass based on 100 parts by mass of the carboxyl group-containing resin.
• the organic solvent is evaporated and dried using a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, etc. (equipped with an air heating type heat source using steam, and a method in which the hot air in the dryer is brought into countercurrent contact. and a method of spraying onto the support from a nozzle).
• a hot air circulation drying oven an IR oven, a hot plate, a convection oven, etc. (equipped with an air heating type heat source using steam, and a method in which the hot air in the dryer is brought into countercurrent contact. and a method of spraying onto the support from a nozzle).
• the photosensitive resin composition of the present invention may contain a filler, if necessary, in order to increase the physical strength of the coating film.
• a filler any known inorganic or organic filler can be used, and barium sulfate, spherical silica, hydrotalcite, and talc are particularly preferably used.
• barium sulfate, spherical silica, hydrotalcite, and talc are particularly preferably used.
• metal oxides and metal hydroxides such as aluminum hydroxide can also be used as extender pigment fillers.
• the content of the filler is preferably 40% by mass or less based on the total mass of the photosensitive resin composition in terms of solid content.
• the filler content exceeds 40% by mass, the viscosity of the photosensitive resin composition increases, coating and moldability deteriorate, and the cured product becomes brittle. More preferably, it is 5 to 40% by mass.
• the photosensitive resin composition of the present invention optionally contains a colorant, a photoinitiation aid, a cyanate compound, an elastomer, a mercapto compound, a urethanization catalyst, a thixation agent, an adhesion promoter, a block copolymer, and a chain transfer agent.
• a polymerization inhibitor a copper inhibitor, an antioxidant, a rust preventive, a thickener such as organic bentonite or montmorillonite, an antifoaming agent such as a silicone type, a fluorine type, or a polymer type, and a leveling agent.
• Components such as a silane coupling agent such as an imidazole type, a thiazole type, or a triazole type, a flame retardant such as a phosphorus compound such as a phosphinate, a phosphoric acid ester derivative, or a phosphazene compound can be further blended.
• a silane coupling agent such as an imidazole type, a thiazole type, or a triazole type
• a flame retardant such as a phosphorus compound such as a phosphinate, a phosphoric acid ester derivative, or a phosphazene compound can be further blended.
• materials known in the field of electronic materials can be used.
• the photosensitive resin composition of the present invention may be used in liquid form, or may be used in the form of a dry film as described below. Furthermore, when used as a liquid, it may be one-liquid or two-liquid or more.
• the photosensitive resin composition of the present invention can also be in the form of a dry film including a first film and a resin layer made of a photosensitive resin composition formed on the first film.
• the first film in the present invention is formed by laminating by heating etc. so that a base material such as a substrate and a layer (resin layer) made of a photosensitive resin composition formed on a dry film are in contact with each other and integrally formed. In this case, it refers to one that is at least adhered to the resin layer.
• the first film may be peeled off from the resin layer in a step after lamination. Particularly in the present invention, it is preferable to peel off the resin layer in the step after exposure.
• the photosensitive resin composition of the present invention is diluted with the above-mentioned organic solvent to adjust the viscosity to an appropriate level, and then coated with a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, or transfer roll coater.
• a film can be obtained by coating the first film to a uniform thickness using a , gravure coater, spray coater, etc., and drying for 1 to 30 minutes, usually at a temperature of 50 to 130°C.
• the coating film thickness is generally appropriately selected within the range of 1 to 150 ⁇ m, preferably 10 to 60 ⁇ m after drying.
• any known film can be used without particular limitation, such as polyester films such as polyethylene terephthalate and polyethylene naphthalate, thermoplastic films such as polyimide films, polyamide-imide films, polypropylene films, and polystyrene films.
• a film made of resin can be suitably used.
• polyester films are preferred from the viewpoints of heat resistance, mechanical strength, handleability, and the like.
• a laminate of these films can also be used as the first film.
• thermoplastic resin film as described above is preferably a film stretched in a uniaxial direction or a biaxial direction.
• the thickness of the first film is not particularly limited, but can be, for example, 10 ⁇ m to 150 ⁇ m.
• the second film is a film that is formed by laminating and integrally molding by heating etc. so that the base material such as a substrate and the layer (resin layer) made of a photosensitive resin composition formed on the dry film are in contact with each other. , which is peeled off from the resin layer before lamination.
• the second peelable film for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used.
• the second film may be one in which the adhesive force between the resin layer and the second film is smaller than the adhesive force 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 dry film may be one in which a resin layer is formed by coating and drying the photosensitive resin composition of the present invention on the second film, and the first film is laminated on the surface of the resin layer. good. That is, when manufacturing a dry film in the present invention, either the first film or the second film may be used as the film to which the photosensitive resin composition of the present invention is applied.
• the cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention or the resin layer of the dry film described above, and has good resolution required for a solder resist layer.
• the above-described photosensitive resin composition of the present invention suppresses crystallization of the components even under cooling and heating cycles, and maintains its composition and properties, so it cannot be used after being exposed to such heating and cooling cycles. Even when the cured product is cured, good resolution is maintained.
• the printed wiring board of the present invention has a cured product obtained from the photosensitive resin composition of the present invention or a resin layer of a dry film.
• the photosensitive resin composition of the present invention is adjusted to a viscosity suitable for the coating method using the above-mentioned organic solvent, and then coated on the base material using a dip coating method. After coating by a method such as a flow coating method, a roll coating method, a bar coating method, a screen printing method, or a curtain coating method, the organic solvent contained in the composition is volatilized and dried at a temperature of 60 to 100°C (temporary drying). By doing so, a tack-free resin layer is formed.
• the resin layer is bonded onto the base material using a laminator or the like so that the resin layer is in contact with the base material, and then the first film is peeled off to form the resin layer on the base material.
• the base materials for printed wiring boards include printed wiring boards with circuits formed in advance using copper, etc., flexible printed wiring boards, as well as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven epoxy, and glass cloth.
• Paper epoxy, synthetic fiber epoxy, fluororesin/polyethylene/polyphenylene ether, polyphenylene oxide/cyanate, etc. are used in materials such as copper-clad laminates for high frequency circuits, and all grades (FR-4 etc.) are used. Examples include copper-clad laminates, metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, and the like.
• the dry film is preferably laminated onto the base material under pressure and heat using a vacuum laminator or the like.
• a vacuum laminator By using such a vacuum laminator, when using a circuit board with a circuit formed thereon, even if the circuit board surface is uneven, the dry film will adhere to the circuit board, so there will be no air bubbles mixed in, and the board The ability to fill in the recesses on the surface is also improved.
• the pressurizing condition is preferably about 0.1 to 2.0 MPa, and the heating condition is preferably 40 to 120°C.
• Volatilization drying performed after applying the photosensitive resin composition of the present invention is carried out using a hot air circulation drying oven, IR oven, hot plate, convection oven, etc. (equipped with an air heating type heat source using steam). This can be carried out using a method in which hot air is brought into countercurrent contact and a method in which hot air is blown onto the support from a nozzle.
• a resin layer on the base material After forming a resin layer on the base material, it is selectively exposed to active energy rays through a photomask with a predetermined pattern formed thereon, and the unexposed areas are treated with a dilute alkaline aqueous solution (for example, 0.3 to 3 mass% sodium carbonate aqueous solution). The cured product is developed to form a pattern.
• a dilute alkaline aqueous solution for example, 0.3 to 3 mass% sodium carbonate aqueous solution.
• the first film is peeled off from the dry film and developed to form a patterned cured product on the base material. Note that, as long as the properties are not impaired, the first film may be peeled off from the dry film before exposure, and the exposed resin layer may be exposed and developed.
• the exposure machine used for active energy ray irradiation may be a device equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and irradiates ultraviolet rays in the range of 350 to 450 nm.
• a direct drawing device for example, a laser direct imaging device that draws an image directly with a laser using CAD data from a computer
• the lamp light source or laser light source of the direct drawing machine may have a maximum wavelength in the range of 350 to 450 nm.
• the exposure amount for image formation varies depending on the film thickness, etc., but can generally be in the range of 10 to 1000 mJ/cm 2 , preferably 20 to 800 mJ/cm 2 .
• Development methods include dipping, showering, spraying, brushing, etc.
• Developers include potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, and ammonia.
• An alkaline aqueous solution of amines or the like can be used.
• further curing may be promoted by irradiating ultraviolet rays after the above-mentioned exposure and development with active energy ray irradiation (post-UV), or heating. It is also possible to accelerate heat curing (post-cure).
• post-UV and post-cure treatments various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties of the cured product of the photosensitive resin composition can be further improved.
• a polymerization inhibitor hydroquinone
• a reaction catalyst triphenylphosphine
• the resulting mixture was heated to 95-105°C, 72 parts of acrylic acid was gradually added dropwise, and the mixture was allowed to react for 16 hours.
• the obtained reaction product was cooled to 80 to 90°C, 91.2 parts of tetrahydrophthalic anhydride was added, and the reaction product was reacted for 8 hours.
• a polymer was obtained.
• the resulting photosensitive prepolymer had a nonvolatile content of 65% and a solid acid value of 87.8 mgKOH/g.
• each component shown in Table 1 below was mixed in the amount shown in the same table (solid content, the amount of organic solvent listed in the table was blended at the time of preparing the photosensitive resin composition), and the mixture was mixed with a stirrer. After preliminary mixing using a three-roll mill, the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 2 were prepared. The details of each component in Table 1 are as follows.
• Thermosetting component 1 Phenol novolac type epoxy resin (RE-306-SA9, manufactured by Nippon Kayaku Co., Ltd.)
• Thermosetting component 2 Alicyclic epoxy resin (Epolead (registered trademark) PB3600, manufactured by Daicel Corporation)
• Thermosetting component 3 Biphenol type epoxy resin (YX-4000, manufactured by Mitsubishi Chemical Corporation) Photopolymerizable monomer: Dipentaerythritol hexaacrylate
• Other additive components 1 Antifoaming agent (KS-66, manufactured by Shin-Etsu Chemical Co., Ltd.)
• Other additive components 2 Thickener (ORBEN-MF, manufactured by Shiraishi Kogyo Co., Ltd.)
• Other additive components 3 Blue pigment
• Other additive components 4 Yellow pigment
• Thermosetting catalyst Melamine Filler: Surface treatment barium sulfate (B-30, manufactured by Nippon Kayaku Co., Ltd.)
• Crystal generation of each of the photosensitive resin compositions of Examples and Comparative Examples due to cooling and heating cycles was evaluated according to the following procedure. Weighed out 50 g of each photosensitive resin composition of Examples and Comparative Examples, left it for one day at room temperature, and then left it for another day at 4°C or less, one cycle, and after each cycle 1 to 3 times. A photosensitive resin composition was produced.
• the resulting photosensitive resin composition after each cycle was applied to a glass substrate and dried at 80° C. for 20 minutes.
• a substrate for evaluation of crystal generation due to cooling and heating cycles was prepared. Each evaluation substrate was visually observed to confirm the presence or absence of crystals on each evaluation substrate, and the generation of crystals due to cooling/heating cycles in each photosensitive resin composition was evaluated according to the following evaluation criteria. The results are shown in Table 1.
• ⁇ Crystals with a maximum diameter of 200 ⁇ m or less are not observed.
• Good One or more and two or less crystals with a maximum diameter of 200 ⁇ m or less are observed.
• ⁇ Three or more crystals with a maximum diameter of 200 ⁇ m or less are observed.
• Each board for evaluating drying control width was developed for 60 seconds in a printed wiring board developer using a 1% by mass aqueous sodium carbonate solution at a liquid temperature of 30°C as a developer. After development, each substrate for evaluation of drying control width was visually observed to confirm the presence or absence of a dried coating film (residue from development), and the drying control width of each photosensitive resin composition was evaluated according to the following evaluation criteria. The results are shown in Table 1.
• ⁇ No development residue was left on any of the drying control width evaluation substrates dried at 80° C. for 60 minutes, 65 minutes, and 70 minutes.
• ⁇ Remains of development occur on one of the drying control width evaluation substrates dried at 80° C. for 60 minutes, 65 minutes, and 70 minutes.
• x Out of the drying control width evaluation substrates dried at 80° C. for 60 minutes, 65 minutes, and 70 minutes, at least two of the drying control width evaluation substrates have development residues.
• the sagging properties of each photosensitive resin composition were evaluated according to the following evaluation criteria. The results are shown in Table 1. ⁇ : The length of the droop is within 1 cm. ⁇ : The length of the droop is more than 1 cm and less than 2 cm. ⁇ : The length of the droop is more than 2 cm.
• the photosensitive resin compositions of each example sufficiently suppressed the generation of crystals due to cooling and heating cycles, and even when used after cooling and heating cycles, the photosensitive resin compositions exhibited good performance required for printed wiring board manufacturing. It can be seen that various characteristics (drying control width, sagging properties, and printability) are exhibited. That is, in a photosensitive resin composition containing a carboxyl group-containing resin, a photopolymerization initiator, and an organic solvent, an ⁇ -aminoacetophenone photopolymerization initiator is blended as the photopolymerization initiator, and a petroleum-based solvent is used as the organic solvent.

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