WO2019189220A1 - Film sec, produit durci et carte imprimée - Google Patents

Film sec, produit durci et carte imprimée Download PDF

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Publication number
WO2019189220A1
WO2019189220A1 PCT/JP2019/012934 JP2019012934W WO2019189220A1 WO 2019189220 A1 WO2019189220 A1 WO 2019189220A1 JP 2019012934 W JP2019012934 W JP 2019012934W WO 2019189220 A1 WO2019189220 A1 WO 2019189220A1
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WIPO (PCT)
Prior art keywords
film
resin
mass
spherical silica
resin layer
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PCT/JP2019/012934
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English (en)
Japanese (ja)
Inventor
太郎 北村
健志 依田
克起 岡安
庸二 滝井
信人 伊藤
Original Assignee
太陽インキ製造株式会社
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Publication of WO2019189220A1 publication Critical patent/WO2019189220A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C08L101/08—Carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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 dry film, a cured product, and a printed wiring board.
  • the curable resin composition for forming such a solder resist for a package substrate is classified into a liquid type and a dry film type, and in particular, a dry film type curable resin composition (hereinafter also simply referred to as “dry film”). ) Has superiority such as high smoothness and high film thickness accuracy, and less foreign matter is mixed into the film, and the amount used is increasing.
  • This dry film generally comprises a support (carrier) film and a dried resin layer comprising a curable resin composition on the support film, and further a protective (cover) that can be peeled off on the surface of the dried resin layer.
  • Films are laminated, cut into a predetermined size (hereinafter also referred to as slit processing), and provided as a roll or sheet.
  • a dry film usually peels off the protective film, arranges the dried resin layer in contact with the substrate, and heats and pressurizes the dry film under vacuum using a vacuum laminator.
  • a constituent resin layer is melted and fluidized and attached to the substrate (hereinafter referred to as “laminate”). Therefore, in the case of a dry film, the resin layer needs to be melted and flowable under lamination conditions so that bubbles remain in the coating and poor adhesion to the substrate does not occur.
  • a property such as rigidity is generally improved by, for example, highly filling an inorganic filler in the composition.
  • inorganic fillers especially spherical silica is widely used for improving the properties of solder resists because of its excellent filling properties and low coefficient of thermal expansion (CTE) (see Patent Document 1).
  • an object of the present invention is to provide a dry film, a cured product, and a printed wiring board that are excellent in slit processability and handleability and have an excellent laminating property while realizing excellent reliability as a cured product. is there.
  • the inventors of the present invention focused on the epoxy resin component contained in the resin layer of the dry film for the photosensitive dry film highly filled with spherical silica, and conducted intensive studies to achieve the above object. As a result, it has been found that the above problem can be solved by blending at least 20% by mass or more of an epoxy resin component that is liquid at room temperature into the epoxy resin component, and the present invention has been completed.
  • the dry film of the present invention is a dry film having a support film, a protective film, and a dried resin layer sandwiched between the support film and the protective film, wherein the resin layer is (A) It contains a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) spherical silica, and (D) an epoxy resin, and the content of the (C) spherical silica is based on the total amount of nonvolatile components in the resin layer.
  • the (D) epoxy resin contains an epoxy resin that is liquid at room temperature in a proportion of at least 20 mass% with respect to the total amount of the epoxy resin.
  • the cured product of the present invention is obtained by curing the resin layer of the dry film.
  • the printed wiring board of the present invention is characterized by having the above cured product.
  • the present invention it is possible to provide a dry film with improved adhesion between the resin layer constituting the dry film and the film, excellent slit processability and handling properties, and excellent laminating properties. As a result, excellent reliability such as high rigidity as a cured product and thermal dimensional stability can be realized, and a printed wiring board having excellent reliability can be provided.
  • the photosensitive dry film according to the present invention is a dry film having a support film, a protective film, and a dried resin layer sandwiched between the support film and the protective film, wherein the resin layer is ( A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) spherical silica, and (D) an epoxy resin, and the content of the (C) spherical silica is the total amount of nonvolatile components in the resin layer.
  • the (D) epoxy resin contains an epoxy resin that is liquid at room temperature in a proportion of at least 20 mass% with respect to the total amount of the epoxy resin.
  • a curable resin composition containing (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) spherical silica, and (D) an epoxy resin. Is used.
  • carboxyl group-containing resin various conventionally known carboxyl group-containing resins having a carboxyl group in the molecule can be used.
  • a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable from the viewpoint of photocurability and development resistance.
  • the ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof.
  • carboxyl group-containing resin having no ethylenically unsaturated double bond
  • Specific examples of the carboxyl group-containing resin include the following compounds (any of oligomers and polymers).
  • a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
  • Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers
  • carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
  • Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
  • bisphenol A type epoxy resin hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
  • one isocyanate group and one or more (meth) acryloyl groups are added in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.
  • a carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal (meth) acrylate.
  • a carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group present in the side chain.
  • Two bases such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are reacted with a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid by reacting the bifunctional oxetane resin.
  • An epoxy compound having a plurality of 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) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as an acid.
  • Reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with an 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 compound having a plurality of phenolic hydroxyl groups in one molecule with a reaction product obtained by reacting 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).
  • (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
  • the acid value of the carboxyl group-containing resin is suitably in the range of 30 to 150 mgKOH / g, more preferably in the range of 50 to 120 mgKOH / g.
  • the acid value of the carboxyl group-containing resin is 30 mgKOH / g or more, alkali development is facilitated.
  • the acid value is 150 mgKOH / g or less, sufficient resistance to the developer in the exposed area is obtained, and a normal resist pattern is obtained. Can be reliably drawn, which is preferable.
  • the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000.
  • the weight average molecular weight is 2,000 or more, the development resistance of the film in the exposed area is improved and the resolution is excellent.
  • the weight average molecular weight is 150,000 or less, the solubility of the unexposed part is good and the resolution is excellent, and the storage stability may be improved.
  • the weight average molecular weight can be measured by gel permeation chromatography.
  • carboxyl group-containing resins are not limited to those listed above, and one kind may be used alone, or a plurality of kinds may be mixed and used. Of these, carboxyl group-containing resins synthesized using a phenol compound as a starting material, such as the carboxyl group-containing resins (10) and (11), are excellent in B-HAST resistance and PCT resistance, and can be suitably used.
  • photopolymerization initiator Any known photopolymerization initiator can be used.
  • a photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.
  • photopolymerization initiator examples include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide and bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine.
  • photobleaching is also called photobleaching or photobleaching, and is a reaction that occurs because a fluorescent substance in an excited state is chemically activated and becomes unstable compared to the ground state.
  • a compound that acts as a photopolymerization initiator absorbs light in a specific wavelength region to generate radicals, the structure of the compound changes due to the generation of radicals, and light in that wavelength region changes. It means that it will not absorb. Thereby, since it becomes easy to let the light in the wavelength range pass, it becomes easy to photocure to a deep part.
  • 2,4,6-trimethylbenzoyl-diphenylphosphine oxide IGM, Omnirad TPO
  • bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide BASF Japan, IRGACURE819
  • phenyl ( 2,4,6-trimethylbenzoyl) ethyl phosphinate IRGACURE TPO-L manufactured by BASF Japan Ltd.
  • the blending amount of the photopolymerization initiator excluding the oxime ester photopolymerization initiator is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin in terms of nonvolatile components.
  • the content is 0.1 parts by mass or more, the photocurability of the resin composition is good, the film is hardly peeled off, and the film properties such as chemical resistance are also good.
  • 30 parts by mass or less an effect of reducing outgas is obtained, and light absorption on the surface of the solder resist coating film is good, and the deep curability is hardly lowered. More preferably, it is 0.5 to 15 parts by mass.
  • the blending amount of the oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin in terms of nonvolatile components.
  • the amount is 0.01 parts by mass or more, the photocurability of the resin composition becomes good, and the film properties such as heat resistance and chemical resistance become good.
  • the light absorption of the solder resist film becomes good, and the deep part curability is hardly lowered. More preferably, it is 0.5 to 3 parts by mass.
  • any spherical silica can be used as long as it can be used as a filler for electronic materials.
  • One kind may be used alone, or two or more kinds may be used in combination.
  • the shape of (C) spherical silica should just be spherical shape, and is not limited to a true spherical thing.
  • Suitable (C) spherical silica includes, for example, those having a sphericity measured as follows of 0.8 or more, but are not limited thereto.
  • spherical silica having an average particle size of 300 nm to 1000 nm is preferably used, and more preferably, the average particle size is set to 500 nm to 900 nm.
  • the average particle diameter of (C) spherical silica is not only the particle diameter of primary particles but also the average particle diameter (D50) including the particle diameter of secondary particles (aggregates).
  • D50 value measured by laser diffraction method is measured by laser diffraction method.
  • An example of a measuring apparatus using a laser diffraction method is Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. Note that the maximum particle size (D100) and the particle size (D10) can be measured in the same manner using the above-described apparatus.
  • the (C) spherical silica two kinds of spherical silicas having different average particle diameters can be used. That is, in addition to spherical silica (C1) having an average particle diameter of 300 nm to 1000 nm, spherical silica (C2) having an average particle diameter of 1 nm or more and less than 300 nm can be used in combination. By using together, since the spherical silica (C2) is filled in the gaps between the spherical silica (C1), the gap amount can be reduced. Thereby, (C) spherical silica can be highly filled in the composition, and a curable resin composition having a low resin content, that is, a high ratio of filler mass in the total mass can be obtained.
  • the particle size originally varies by 2 to 3 times, but since the fine particles do not effectively enter the gap at that ratio, spherical silica (C1) and spherical silica (The difference in the average particle diameter of C2) is preferably 5 times or more.
  • the difference in the average particle diameter is preferably as large as possible, more preferably 8 times or more, and even more preferably 10 times or more.
  • the maximum particle size (D100) of the spherical silica (C1) is preferably 5 ⁇ m or less.
  • the maximum particle size varies depending on the use of the curable resin composition, and is preferably 5 ⁇ m or less for use in forming a cured film on a package substrate, for example.
  • the particle diameter (D10) of the spherical silica (C1) is preferably 5 times or more the average particle diameter (D50) of the spherical silica (C2).
  • the method for producing spherical silica is not particularly limited, and methods known to those skilled in the art can be applied.
  • it can be manufactured by burning silicon powder by a VMC (Vaporized Metal Combustion) method.
  • VMC Vehicleized Metal Combustion
  • a chemical flame is formed by a burner in an oxygen-containing atmosphere, and metal powder that constitutes part of the target oxide particles is introduced into the chemical flame in such an amount that a dust cloud is formed.
  • deflagration is caused to obtain oxide particles.
  • spherical silica (C1) commercially available, for example, Admafine SO-C2, SO-E2, SO-E3 manufactured by Admatechs Co., Ltd., SFP- manufactured by Denka Co., Ltd.
  • spherical silica (C2) include Admanano (manufactured by Admatechs), SO-E1, UFP-30 (manufactured by Denka Co., Ltd.), and Nippon Shokubai Co., Ltd.
  • Examples include the Sea Hoster series, the Sciqas series manufactured by Sakai Chemical Industry Co., Ltd., and SG-SO100 manufactured by Kyoritsu Material Co., Ltd.
  • the presence or absence of surface treatment of (C) spherical silica is not particularly limited, but the curable resin composition of the present invention is highly filled with (C) spherical silica and has a relatively low resin content.
  • Silica is preferably subjected to a surface treatment for improving dispersibility. Aggregation can be suppressed by using a filler that has been surface-treated.
  • (C) spherical silica (C1) and spherical silica (C2) are used in combination as spherical silica, only one of them may be surface treated, or both may be surface treated.
  • the surface treatment method of the spherical silica is not particularly limited, and a known and commonly used method may be used.
  • a surface treatment agent having a curable reactive group for example, a coupling agent having a curable reactive group as an organic group, etc. It is preferable to treat the surface of the inorganic filler.
  • silane, titanate, aluminate and zircoaluminate coupling agents can be used as the coupling agent.
  • silane coupling agents are preferred.
  • examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-amino.
  • the treatment amount of the coupling agent with respect to 100 parts by mass of (C) spherical silica is preferably 0.5 to 10 parts by mass.
  • (C) the reactive functional group derived from the coupling agent applied to the spherical silica is not included in the compound having a photocurable reactive group or a thermosetting functional group.
  • Examples of the photocurable reactive group include ethylenically unsaturated groups such as vinyl group, styryl group, methacryl group, and acrylic group. Among these, at least one of a vinyl group and a (meth) acryl group is preferable.
  • thermosetting reactive groups include hydroxyl groups, carboxyl groups, isocyanate groups, amino groups, imino groups, epoxy groups, oxetanyl groups, mercapto groups, methoxymethyl groups, methoxyethyl groups, ethoxymethyl groups, ethoxyethyl groups, oxazoline groups, etc. Is mentioned. Among these, at least one of an amino group and an epoxy group is preferable.
  • the surface-treated (C) spherical silica may be contained in the curable resin composition of the present invention in a surface-treated state, and the surface-untreated (C) spherical silica, the surface treatment agent,
  • the (C) spherical silica may be surface-treated in the composition by separately blending, but it is preferable to blend the (C) spherical silica that has been surface-treated in advance. By blending the (C) spherical silica that has been surface-treated in advance, it is possible to suppress a decrease in crack resistance or the like due to the surface treatment agent that has not been consumed by the surface treatment that can remain when blended separately.
  • a predispersion liquid in which (C) spherical silica is predispersed in a solvent or a curable component, and the surface-treated (C) spherical silica is predispersed in a solvent, and this predispersion More preferably, the liquid is mixed into the composition, or after sufficiently surface-treating the surface-untreated (C) spherical silica in the solvent, the pre-dispersed liquid is mixed into the composition.
  • (C) Spherical silica may be blended with the component (A) in a powder or solid state depending on the use mode of the curable resin composition of the present invention, and after mixing with a solvent or a dispersant to form a slurry. And may be blended with the component (A).
  • the content of (C) spherical silica needs to be 50% by mass or more in the nonvolatile component of the composition, preferably 50% by mass to 80% by mass, more preferably 60% by mass to 80% by mass, It is.
  • (C) By setting the content of spherical silica to 50% by mass or more in the nonvolatile component of the curable resin composition used in the resin layer, the cured product has high strength and high rigidity, and the linear expansion coefficient (CTE) is It can be lowered, which is preferable.
  • the epoxy resin (D) As this epoxy resin (D), a publicly known one can be used, and the epoxy resin that is liquid at least at room temperature is contained in the resin layer constituting the dry film at a ratio of 20% by mass or more with respect to the total amount of the epoxy resin. Thus, it is preferable to mix
  • the dry film of this invention will contain a liquid epoxy resin at normal temperature in the ratio of 20 mass% or more as (D) epoxy resin of a resin layer, and curable resin composition is used.
  • the resin layer and the protective film can be used even if the resin layer is highly filled with (C) spherical silica for the purpose of high rigidity and low CTE. Excellent adhesion to the film can be obtained.
  • liquidity of the resin layer of a dry film is provided in the case of a lamination by containing 20 mass% or more of liquid epoxy resins in the epoxy resin of this (D) component.
  • liquid at normal temperature means liquid at 15 ° C.
  • the determination of liquidity can be made in accordance with the second “liquid confirmation method” of the ministerial ordinance on the test and properties of hazardous materials (Ministry of Local Government Ordinance No. 1 of 1989).
  • epoxy resin that is liquid at room temperature in this component (D) bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (jER807 manufactured by Mitsubishi Chemical Corporation), bisphenol AF type epoxy resin Phenol novolac type epoxy resin (N-730 manufactured by DIC Corporation), tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, aminophenol type epoxy resin, alicyclic epoxy resin and the like.
  • the epoxy resin other than the epoxy resin that is liquid at room temperature in the component (D) a known and commonly used polyfunctional epoxy resin having at least two epoxy groups in one molecule can be used.
  • the other epoxy resin may be solid or semi-solid.
  • naphthalene type epoxy resin manufactured by DIC Corporation, HP-4700
  • naphthalene skeleton-containing polyfunctional solid epoxy resin manufactured by Nippon Kayaku Co., Ltd., NC-7000
  • trisphenol epoxy resin manufactured by Nippon Kayaku Co., Ltd.
  • EPPN-502H dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin
  • Epiclon HP-7200 manufactured by DIC Corporation biphenyl type epoxy resin (Mitsubishi Chemical Corporation YX-4000), biphenyl skeleton-containing polyfunctional solid epoxy resin (Nippon Kayaku Co., Ltd.
  • the compounding ratio amount of the epoxy resin is preferably 0.5 to 2.5 mol, more preferably the functional group number of the thermosetting component to react with respect to 1 mol of the carboxyl group contained in the (A) carboxyl group-containing photosensitive resin. Is 0.8 to 2.0 mol.
  • the curable resin composition described above can be blended with a photopolymerizable monomer, a thermosetting catalyst, a colorant, an organic solvent, other additive components, and the like.
  • a photopolymerizable monomer can be blended in the curable composition used for the resin layer of the dry film of the present invention.
  • the photopolymerizable monomer is a compound having an ethylenically unsaturated double bond.
  • photopolymerizable monomers examples include alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Hydroxyalkyl (meth) acrylates such as acrylates; Mono- or di (meth) acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane , Dipentaerythritol, trishydroxyethyl isocyanurate and other polyhydric alcohols or their addition of ethylene oxide or propylene oxide Polyhydric (meth) acrylates; Phenoxyethyl (meth) acrylate, (meth) acrylates of ethylene
  • the photopolymerizable monomer can be used alone or in combination of two or more.
  • the content of the photopolymerizable monomer is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin in terms of nonvolatile components.
  • the blending amount is 0.5 parts by mass or more, the photocurability is good, and pattern formation is easy in alkali development after irradiation with active energy rays.
  • 30 parts by mass or less halation does not easily occur and good resolution is obtained.
  • thermosetting catalyst can be blended in the curable resin composition used for the resin layer of the dry film of the present invention.
  • thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzyl Examples include amines, amine compounds such as 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide;
  • thermosetting catalyst can be used singly or in combination of two or more.
  • the blending amount of the thermosetting catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the nonvolatile component (A) carboxyl group-containing resin. .
  • 0.1 mass part or more it is excellent in heat resistance.
  • 10 parts by mass or less the storage stability is improved.
  • the curable resin composition used for the resin layer of the dry film of the present invention may contain a colorant.
  • a colorant conventionally known colorants such as red, blue, green, yellow, white, and black can be used, and any of pigments, dyes, and pigments may be used.
  • CI the Society of Dyer's and Colorists (issued by The Society of Dyers and Colorists) number.
  • red colorant examples include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone.
  • blue colorant there are phthalocyanine series, anthraquinone series, and the like, and as the pigment series, a compound classified as Pigment can be used. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
  • the green colorant includes phthalocyanine, anthraquinone and perylene. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
  • Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone.
  • Examples of the white colorant include rutile type or anatase type titanium oxide.
  • Black colorants include carbon black, graphite, iron oxide, titanium black, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, aniline, and sulfide. There are molybdenum and bismuth sulfide.
  • a colorant such as purple, orange or brown may be added for the purpose of adjusting the color tone.
  • the content of the colorant is preferably 0.18 to 0.50% by mass in terms of nonvolatile components per total amount of the curable resin composition used in the resin layer.
  • the circuit concealing property is excellent, and when it is 0.50% by mass or less, the resolution is more excellent. More preferably, it is 0.20 mass% to 0.40 mass%.
  • a coloring agent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the curable resin composition used for the resin layer of the dry film of the present invention can contain an organic solvent for the purpose of preparing the composition and adjusting the viscosity when applied to the support film.
  • organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate,
  • the curable resin composition used for the resin layer of the dry film of the present invention may further include a photoinitiator aid, a cyanate compound, an elastomer, a mercapto compound, a urethanization catalyst, a thixotropic agent, an adhesion promoter, if necessary.
  • a photoinitiator aid e.g., a cyanate compound, an elastomer, a mercapto compound, a urethanization catalyst, a thixotropic agent, an adhesion promoter, if necessary.
  • Components such as antifoaming agents and / or leveling agents, silane coupling agents such as imidazole, thiazole, and triazole, flame retardants such as phosphinates, phosphate derivatives, phosphorous compounds such as phosphazene compounds, etc. it can. As these, those known in the field of electronic materials can be used.
  • the curable resin composition used for the resin layer of the dry film of the present invention may be used as a liquid instead of being used as a dry film. When used as a liquid, it may be one-component or two-component or more.
  • the said curable resin composition is used for the dry film of this invention provided with the support film, the dry resin layer which consists of the said curable resin composition formed on this support film, and a protective film.
  • the dry film of the present invention has good laminating properties.
  • the curable resin composition is diluted with the above organic solvent to adjust to an appropriate viscosity, and a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure
  • a film can be obtained by applying a uniform thickness on a support film with a coater, spray coater or the like, and drying usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes.
  • the coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 1 to 150 ⁇ m, preferably 10 to 60 ⁇ m.
  • a plastic film is used, and it is preferable to use a polyester film such as polyethylene terephthalate (PET), a plastic film such as a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film.
  • PET polyethylene terephthalate
  • the thickness of the support film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 ⁇ m.
  • a protective film that can be peeled off on the surface of the resin layer is further provided for the purpose of preventing dust from adhering to the surface of the resin layer.
  • Laminate for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used. As long as the adhesive strength between the resin layer and the protective film is smaller. Among these, a biaxially stretched polypropylene film (OPP) is suitable from the viewpoint of mechanical properties (strength and rigidity) and economy.
  • the thickness of the protective film is not particularly limited, but is generally appropriately selected within the range of 5 to 150 ⁇ m.
  • a curable resin composition used for the dry film of the present invention is applied on the protective film and dried to form a resin layer, and a support film is laminated on the surface. May be. That is, when manufacturing a dry film in this invention, as a film which apply
  • the dry film of the present invention is useful for forming a pattern layer as a permanent film of a printed wiring board such as a solder resist, a coverlay, and an interlayer insulating layer, and is particularly useful for forming a solder resist.
  • the dry film of the present invention can form a cured product having excellent film strength even with a thin film, the pattern layer of a printed wiring board that is required to be thin, such as a package substrate (printed wiring board used for a semiconductor package). It can also be suitably used for formation.
  • the cured product obtained from the dry film of the present invention can be suitably used for the formation of a pattern layer on a package substrate having a thin total thickness and insufficient rigidity, even in terms of high modulus and low CTE. is there.
  • the cured product of the present invention is obtained by curing the curable resin composition of the present invention or the resin layer of the dry film of the present invention, and has high rigidity and thermal dimensional stability.
  • the printed wiring board of the present invention has a cured product obtained from the resin layer of the dry film of the present invention.
  • the present invention is based on a method of peeling a support film after laminating a dry film on a substrate with a laminator or the like so that the resin layer is in contact with the substrate.
  • a resin layer is formed on the material, but the curable resin composition used for the resin layer of the dry film of the present invention is adjusted to a viscosity suitable for the coating method using the organic solvent, and on the substrate, After applying by dip coating method, flow coating method, roll coating method, bar coater method, screen printing method, curtain coating method, etc., the organic solvent contained in the composition is evaporated and dried at a temperature of 60 to 100 ° C. ( A tack-free resin layer may be formed by temporary drying.
  • Examples of the base material include printed wiring boards and flexible printed wiring boards that have been previously formed with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy.
  • copper-clad laminates for high-frequency circuits using synthetic fiber epoxy, fluororesin / polyethylene / polyphenylene ether, polyphenylene oxide / cyanate, etc., all grades (FR-4 etc.) copper-clad laminates examples thereof include a plate, a metal substrate, a polyimide film, a polyethylene terephthalate film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, and a wafer plate.
  • a hot-air circulating drying furnace an IR furnace, a hot plate, a convection oven, etc. (air heating method using steam) And a method in which hot air in the dryer is brought into countercurrent contact with a device provided with a heat source and a method in which a nozzle is blown onto a support).
  • the resin layer is formed on the substrate, it is selectively exposed with active energy rays through a photomask having a predetermined pattern, and the unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 to 3 mass% sodium carbonate aqueous solution).
  • a dilute alkaline aqueous solution for example, 0.3 to 3 mass% sodium carbonate aqueous solution.
  • the cured product is irradiated with active energy rays and then heat-cured (for example, 100 to 220 ° C.), irradiated with active energy rays after heat-curing, or subjected to final finish curing (main curing) only by heat-curing.
  • a cured film having excellent properties such as properties and hardness is formed.
  • the exposure apparatus used for the active energy ray irradiation may be any apparatus that irradiates ultraviolet rays in the range of 350 to 450 nm, equipped with a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc.
  • a direct drawing apparatus for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer
  • 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 and the like, but can be generally in the range of 10 to 1000 mJ / cm 2 , preferably 20 to 800 mJ / cm 2 .
  • the developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.
  • the curable resin composition used for the dry film and the resin layer of the dry film of the present invention is not only used for forming a cured film pattern with a developer as described above, but also used for forming a pattern, such as a mold ( It may be used for sealing applications.
  • spherical silica B-1 70 parts of spherical silica (SFP-30M manufactured by Denka Co., Ltd., average particle size: 600 nm), 28 parts of PMA (propylene glycol monomethyl ether acetate) as a solvent, and a silane coupling agent having a methacryl group (Shin-Etsu Chemical Co., Ltd.) And 2 parts of KBM-503 (3-methacryloxypropyltrimethoxysilane) manufactured by) were uniformly dispersed to obtain a silica solvent-dispersed product having a nonvolatile content of 70% by mass.
  • SFP-30M manufactured by Denka Co., Ltd., average particle size: 600 nm
  • PMA propylene glycol monomethyl ether acetate
  • silane coupling agent having a methacryl group Shin-Etsu Chemical Co., Ltd.
  • KBM-503 3-methacryloxypropyltrimethoxysilane
  • the measurement was performed using a TMA measuring apparatus (TMA / SS6000 manufactured by Shimadzu Corporation), and CTE ⁇ 1 (0-50 ° C.) was performed. Judgment criteria are as follows. ⁇ ... less than 30ppm ⁇ ... 30ppm or more
  • ⁇ Adhesion between resin layer and protective film> On a support film (Toray Industries, Ltd., Lumirror T60, thickness 16 ⁇ m), a curable resin composition was applied to a uniform thickness, dried, and allowed to cool to room temperature to obtain a resin layer (thickness). 20 ⁇ m) was formed. A dry film was prepared by sandwiching the obtained resin layer with a protective film (manufactured by Oji F-Tex Co., Ltd., MA-411, thickness: 15 ⁇ m) from the opposite side of the support film, and this dry film was protected against the resin layer. The degree of adhesion was visually determined. ⁇ : Good adhesion is obtained without peeling if no load is applied. (Triangle

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  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un film sec, un produit durci et une carte imprimée qui présentent une excellente fiabilité en tant que produits durcis, tout en présentant une excellente aptitude au traitement des entailles et une excellente maniabilité et d'excellentes propriétés de stratification. Ce film sec comprend un film de support, un film protecteur et une couche de résine, maintenue entre le film de support et le film protecteur. La couche de résine contient (A) une résine contenant un groupe carboxyle, (B) un initiateur de photopolymérisation, (C) une silice sphérique et (D) une résine époxy. La teneur en silice sphérique (C) est supérieure ou égale à 50 % en masse par rapport au contenu solide dans une composition de résine durcissable utilisée dans la couche de résine. La quantité totale d'au moins une résine époxy mélangée sous forme liquide à la résine époxy (D) est supérieure ou égale à 20 % en masse de la quantité globale de la résine époxy (D).
PCT/JP2019/012934 2018-03-30 2019-03-26 Film sec, produit durci et carte imprimée WO2019189220A1 (fr)

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JP2018070147A JP2019179223A (ja) 2018-03-30 2018-03-30 ドライフィルム、硬化物およびプリント配線板
JP2018-070147 2018-03-30

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015002071A1 (fr) * 2013-07-04 2015-01-08 味の素株式会社 Composition de résine photosensible
JP2016194669A (ja) * 2015-03-31 2016-11-17 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板
JP2017181848A (ja) * 2016-03-31 2017-10-05 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板
JP2017198746A (ja) * 2016-04-25 2017-11-02 太陽インキ製造株式会社 ドライフィルム、硬化物およびプリント配線板

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015002071A1 (fr) * 2013-07-04 2015-01-08 味の素株式会社 Composition de résine photosensible
JP2016194669A (ja) * 2015-03-31 2016-11-17 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板
JP2017181848A (ja) * 2016-03-31 2017-10-05 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板
JP2017198746A (ja) * 2016-04-25 2017-11-02 太陽インキ製造株式会社 ドライフィルム、硬化物およびプリント配線板

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