WO2019163292A1 - 積層型電子部品用樹脂組成物、ドライフィルム、硬化物、積層型電子部品、および、プリント配線板 - Google Patents

積層型電子部品用樹脂組成物、ドライフィルム、硬化物、積層型電子部品、および、プリント配線板 Download PDF

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WO2019163292A1
WO2019163292A1 PCT/JP2018/048327 JP2018048327W WO2019163292A1 WO 2019163292 A1 WO2019163292 A1 WO 2019163292A1 JP 2018048327 W JP2018048327 W JP 2018048327W WO 2019163292 A1 WO2019163292 A1 WO 2019163292A1
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Prior art keywords
resin
multilayer electronic
resin composition
electronic component
electronic components
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PCT/JP2018/048327
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English (en)
French (fr)
Japanese (ja)
Inventor
諭 興津
貴幸 中条
良朋 青山
遠藤　新
衆 管
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太陽インキ製造株式会社
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Priority to JP2019568421A priority Critical patent/JPWO2019163292A1/ja
Priority to CN201880089860.3A priority patent/CN111742014A/zh
Priority to KR1020207026871A priority patent/KR20200124700A/ko
Publication of WO2019163292A1 publication Critical patent/WO2019163292A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F17/00—Fixed inductances of the signal type 
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G2/00—Details of capacitors not covered by a single one of groups H01G4/00-H01G11/00
    • H01G2/24—Distinguishing marks, e.g. colour coding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/224—Housing; Encapsulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors

Definitions

  • the present invention relates to a resin composition for laminated electronic components, a dry film, a cured product, a laminated electronic component, and a printed wiring board.
  • Patent Document 1 describes an inductor manufactured by laminating an insulating layer made of an organic material and a layer made of a copper plating electrode.
  • an object of the present invention is to solve such a problem, and a resin composition for a multilayer electronic component suitable for the manufacture of a small multilayer electronic component excellent in distinguishability in appearance inspection is obtained from the composition.
  • the resin composition for multilayer electronic components of the present invention is a resin used for the protective layer of a multilayer electronic component in which electrode layers and insulating layers are alternately stacked and protective layers are provided on both end surfaces in the stacking direction.
  • a composition comprising a curable resin, an inorganic filler, and a colorant.
  • the resin composition for multilayer electronic components of the present invention preferably contains two or more inorganic fillers having different average particle diameters as the inorganic filler.
  • the resin composition for multilayer electronic components of the present invention preferably contains silica as the inorganic filler.
  • the colorant is preferably a white colorant.
  • the white colorant is preferably titanium oxide.
  • the blending amount of the titanium oxide is preferably 10% by mass or less based on the total solid content of the composition.
  • the dry film of the present invention is characterized in that it has a resin layer obtained by applying and drying the resin composition for laminated electronic components on a film.
  • the cured product of the present invention is obtained by curing the resin composition for laminated electronic parts or the resin layer of the dry film.
  • the multilayer electronic component of the present invention is characterized in that electrode layers and insulating layers are alternately stacked, and protective layers containing the cured product are provided on both end faces in the stacking direction.
  • the insulating layer is made of an alkali developing resin composition containing an alkali-soluble resin, a photopolymerization initiator, and an inorganic filler.
  • the multilayer electronic component of the present invention is preferably an inductor.
  • the printed wiring board of the present invention is characterized in that the multilayer electronic component is mounted on at least one of the surface and the inside.
  • stacked electronic components suitable for manufacture of the small laminated electronic component excellent in the discrimination property in an external appearance test
  • a cured product of the resin layer of the dry film, a multilayer electronic component provided with a protective layer containing the cured product, and a printed wiring board having the multilayer electronic component can be provided.
  • the resin composition for laminated electronic components of the present invention is a resin composition used for the protective layer of a laminated electronic component in which electrode layers and insulating layers are alternately laminated and protective layers are provided on both end faces in the laminating direction. And it is characterized by including curable resin, an inorganic filler, and a coloring agent.
  • the present inventors have found that by providing a protective layer containing a colorant on both end faces in the stacking direction, the distinction of the orientation of stacked electronic components in appearance inspection can be greatly improved, and oversight of defective products can be reduced. It was. Such an improvement in distinguishability in the appearance inspection is particularly remarkable in a small multilayer electronic component whose one side is less than 1 mm.
  • a protective layer containing an inorganic filler can be provided at both ends in the stacking direction of the multilayer electronic component, so that the electrode layer and the insulating layer are effectively protected. This has the effect of improving the handleability of the multilayer electronic component.
  • the resin composition for multilayer electronic components of the present invention it can serve not only as an identification layer of the multilayer electronic component but also as a protection of the electrode layer and the insulating layer.
  • the colorant is preferably a white colorant, which is further excellent in distinguishability.
  • titanium oxide is preferable.
  • the concealability of the electrode layer pattern can be maintained and the dielectric constant and dielectric loss tangent can be reduced. It becomes possible.
  • the resin composition for multilayer electronic components of the present invention preferably contains a large amount of inorganic filler, and the inorganic filler is 50% by mass or more based on the total solid content of the composition. It is preferable to contain. Moreover, it is preferable that 2 or more types of inorganic fillers from which an average particle diameter differs are included as an inorganic filler from a viewpoint of the high filling of such an inorganic filler and high elasticity.
  • the curable resin constituting the resin composition for laminated electronic components of the present invention may be either a thermosetting resin or a photocurable resin, or a mixture thereof.
  • a thermosetting resin or a photocurable resin, or a mixture thereof.
  • Colorant a conventionally known colorant can be used, and any of a pigment, a dye, and a pigment may be used. Colorants such as green, yellow, red, black, blue, orange, purple, brown, and white can be used, with white colorants being preferred.
  • a coloring agent can be used 1 type or in combination of 2 or more types. Specific examples include those with the following color index numbers (CI; issued by The Society of Dyers and Colorists). However, it is more preferable not to contain halogen from the viewpoint of reducing the environmental burden and affecting the human body.
  • a white colorant, a blue colorant, and a black colorant are preferable because of excellent discrimination between the protective layer of the multilayer electronic component and the inner insulating layer, and more preferably a white colorant. It is.
  • white colorants examples include titanium oxide, zinc oxide, basic lead carbonate, basic lead sulfate, lead sulfate, zinc sulfide, and antimony oxide.
  • the white colorant is preferably titanium oxide.
  • titanium oxide By including titanium oxide, the reflectivity is increased, which is advantageous for improving the discriminability, and the reflectivity is good even after reflow, so that the discriminability in the appearance inspection can be maintained well.
  • TR-600, TR-700, TR-750, TR-840 manufactured by Fuji Titanium Industry Co., Ltd., R-550, R-580, R-630, R-820, CR-50 manufactured by Ishihara Sangyo Co., Ltd., CR-58, CR-60, CR-90, CR-97, CR-953, KR-270, KR-310, KR-380 manufactured by Titanium Industry Co., Ltd. can be used.
  • the cured product formed from the composition containing titanium oxide preferably has a Y value of 15 or more, more preferably 18 or more, and the upper limit of the Y value is preferably 45 or less.
  • the difference in reflectance between the protective layer and the inner insulating layer is preferably 10% or more at a wavelength of 450 nm, more preferably 20% or more. Further, it is more preferable that the distance is 40% or more.
  • the inner layer means a layer formed between the outermost protective layers and forming a circuit of the multilayer electronic component.
  • Coloring agents may be used alone or in combination of two or more.
  • the blending amount of the colorant is preferably 10% by mass or less based on the total solid content of the composition.
  • the white colorant is titanium oxide
  • it is preferably blended at 10% by mass or less with respect to the total solid content of the composition as described above. More preferably, it is 8 mass% or less, More preferably, it is 5 mass% or less.
  • the compounding quantity of a titanium oxide is 2 mass% or more.
  • the inorganic filler By blending the inorganic filler, the physical strength and the like of the obtained cured product can be increased. Further, the inorganic filler can prevent the protective layer from being peeled off or damaged by suppressing curing shrinkage of the protective layer and contributing to improvement in properties such as adhesion and hardness.
  • the inorganic filler conventionally known inorganic fillers can be used, and are not limited to specific ones.
  • the inorganic filler is preferably spherical particles.
  • the average particle diameter (median diameter, D50) of the inorganic filler is preferably 0.01 to 10 ⁇ m.
  • the average particle size of the inorganic filler is an average particle size including not only the primary particle size but also the secondary particle (aggregate) particle size.
  • the average particle size can be determined by a laser diffraction particle size distribution measuring device.
  • An example of a measuring apparatus using the laser diffraction method is Nanotrac wave manufactured by Nikkiso Co., Ltd.
  • the inorganic filler may be surface-treated.
  • a surface treatment that does not introduce an organic group such as a surface treatment with a coupling agent or an alumina treatment may be performed.
  • the surface treatment method of the inorganic filler 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. What is necessary is just to process the surface.
  • the surface treatment of the inorganic filler is preferably a surface treatment with a coupling agent.
  • a coupling agent such as silane, titanate, aluminate and zircoaluminate can be used. Of these, silane coupling agents are preferred. Examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-amino.
  • silane coupling agents are preferably immobilized in advance on the surface of the inorganic filler by adsorption or reaction.
  • the treatment amount of the coupling agent with respect to 100 parts by mass of the inorganic filler is preferably 0.5 to 10 parts by mass.
  • 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 inorganic filler should just be contained in the composition of this invention in the surface-treated state, mix
  • it may be surface-treated it is preferable to blend an inorganic filler that has been surface-treated in advance.
  • By blending the inorganic filler that has been surface-treated in advance it is possible to prevent a decrease in crack resistance or the like due to the surface treatment agent that has not been consumed by the surface treatment that may remain when blended separately.
  • the surface treatment is performed in advance, it is preferable to blend a pre-dispersion liquid in which an inorganic filler is pre-dispersed in a solvent or a curable resin.
  • the pre-dispersion of the surface-treated inorganic filler is pre-dispersed in a solvent, and the pre-dispersion liquid is blended in the composition.
  • the pre-dispersed liquid is blended in the composition after sufficiently surface-treating when the surface-untreated inorganic filler is pre-dispersed in the solvent.
  • the inorganic filler may be blended with a curable resin or the like in a powder or solid state, or may be blended with a curable resin or the like after being mixed with a solvent or a dispersant to form a slurry.
  • the inorganic filler may be used alone or as a mixture of two or more.
  • the blending amount of the inorganic filler is preferably 50 to 90% by mass, more preferably 60 to 90% by mass, and still more preferably 70 to 90% by mass with respect to the total solid content of the composition. .
  • the inorganic filler When two or more kinds of mixtures are used as the inorganic filler, two kinds of inorganic fillers having different average particle diameters (hereinafter referred to as (B-1) inorganic filler and (B-2) inorganic filler) are blended. It is preferable. The larger the difference in the average particle size between (B-1) inorganic filler and (B-2) inorganic filler, the better.
  • (B-1) The average particle size of the inorganic filler is (B-2) The average particle size of the inorganic filler. Is preferably 5 times or more, more preferably 8 times or more, and even more preferably 10 times or more.
  • a resin composition having a high mass ratio can be obtained. In this case, it is more effective when it contains 50 mass% or more of the total mass of the solid content of the composition, and it is effective when it is 60 mass% or more and 70 mass% or more.
  • a cured product having excellent strength, high storage elastic modulus, and low linear expansion coefficient (CTE) can be formed. In the case of a dry film, the laminate property to the electrode layer and the insulating layer is also excellent.
  • the average particle size of the inorganic filler is preferably 5 ⁇ m or less.
  • the maximum particle size of (B-2) inorganic filler is preferably 500 nm or less.
  • the presence or absence of surface treatment of the inorganic filler is not particularly limited. However, as described above, since the curable composition of the present invention has a low resin content, the (B-1) and (B-2) inorganic fillers may be subjected to a surface treatment for improving dispersibility. preferable.
  • the curable resin composition of the present invention contains a curable resin.
  • the curable resin used in the present invention may be either a thermosetting resin or a photocurable resin, or a mixture thereof.
  • thermosetting resin is a resin having a functional group that can be cured by heat.
  • the thermosetting resin is not particularly limited, and is an epoxy compound, an oxetane compound, a compound having two or more thioether groups in the molecule, that is, an amino resin such as an episulfide resin, a melamine resin, a benzoguanamine resin, a melamine derivative, or a benzoguanamine derivative.
  • Block isocyanate compounds, cyclocarbonate compounds, bismaleimides, carbodiimides, and the like can be used.
  • the epoxy compound is a compound having an epoxy group, and any conventionally known one can be used.
  • a bifunctional epoxy compound having two epoxy groups in the molecule a polyfunctional epoxy compound having many epoxy groups in the molecule. Etc.
  • a hydrogenated bifunctional epoxy compound may be used.
  • epoxy compound examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, and phenol novolac type.
  • the epoxy compound may be a solid epoxy resin, a semi-solid epoxy resin, or a liquid epoxy resin.
  • solid epoxy resin refers to an epoxy resin that is solid at 40 ° C.
  • semi-solid epoxy resin refers to an epoxy resin that is solid at 20 ° C. and liquid at 40 ° C.
  • the liquid epoxy resin refers to an epoxy resin that is liquid at 20 ° C.
  • the determination of the liquid state can be performed 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). For example, the method described in paragraphs 23 to 25 of JP-A-2016-079384 is performed.
  • Solid epoxy resins include HP-4700 (naphthalene type epoxy resin) manufactured by DIC, EXA4700 (tetrafunctional naphthalene type epoxy resin) manufactured by DIC, and NC-7000 (polyfunctional solid epoxy resin containing naphthalene skeleton) manufactured by Nippon Kayaku Co., Ltd.
  • Naphthalene type epoxy resin such as EPPN-502H (Trisphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd.
  • Epoxy product of a condensate of phenols and aromatic aldehyde having a phenolic hydroxyl group (Trisphenol type epoxy resin); DIC Dicyclopentadiene aralkyl epoxy resin such as Epicron HP-7200H (dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin) manufactured by Nihon Kayaku Co., Ltd .; biphenyl aralkyl such as NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin) Type epoch Biphenyl / phenol novolak type epoxy resin such as NC-3000L manufactured by Nippon Kayaku; Novolak type epoxy resin such as Epicron N660 and Epicron N690 manufactured by DIC, EOCN-104S manufactured by Nippon Kayaku; YX manufactured by Mitsubishi Chemical Biphenyl type epoxy resin such as ⁇ 4000; phosphorus-containing epoxy resin such as TX0712 manufactured by Nippon Steel & Sumikin Chemical Co .; tris (2,3
  • Semi-solid epoxy resins include DIC's Epicron 860, Epicron 900-IM, Epicron EXA-4816, Epicron EXA-4822, Asahi Ciba's Araldite AER280, Toto Kasei's Epoto YD-134, Mitsubishi Chemical's jER834, jER872, bisphenol A type epoxy resin such as ELA-134 manufactured by Sumitomo Chemical Co., Ltd .; naphthalene type epoxy resin such as Epicron HP-4032 manufactured by DIC; phenol novolac type epoxy resin such as Epicron N-740 manufactured by DIC .
  • Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin Aminophenol type epoxy resin, alicyclic epoxy resin and the like.
  • oxetane compounds include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl)
  • polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene), card
  • (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
  • episulfide resin examples include bisphenol A type episulfide resin.
  • an episulfide resin or the like in which the oxygen atom of the epoxy group of the epoxy resin is replaced with a sulfur atom can be used by using a similar synthesis method.
  • an epoxy compound as the thermosetting resin.
  • Thermosetting resins can be used singly or in combination of two or more.
  • the blending amount of the thermosetting resin is preferably 5 to 40%, more preferably 10 to 30%, and even more preferably 15 to 20% with respect to the total solid content of the composition.
  • Photocuring resin As a photocurable resin, what is necessary is just a resin which hardens
  • a photocurable resin can be used individually by 1 type or in combination of 2 or more types.
  • photopolymerizable oligomers As the compound having an ethylenically unsaturated bond, known and commonly used photopolymerizable oligomers, photopolymerizable vinyl monomers, and the like are used.
  • examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers.
  • Examples of (meth) acrylate oligomers include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, epoxy (meth) acrylates such as bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meta ) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like.
  • photopolymerizable vinyl monomer known and commonly used monomers, for example, styrene derivatives such as styrene, chlorostyrene and ⁇ -methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide (Meth) acrylamides such as rilamide and N-butoxymethylacrylamide; allyl compounds such as triallyl isocyan
  • the resin composition of the present invention is an alkali development type photosensitive resin composition
  • a carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group, and may or may not have an aromatic ring.
  • a resin having an epoxy resin as a starting material a resin having a phenol compound as a starting material, a resin having a urethane structure, a resin having a copolymer structure, and a resin having an imide structure are preferable.
  • a phenolic hydroxyl group-containing resin may be used as the curable resin.
  • 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 compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems
  • a terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
  • Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin (Photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its modified partial anhydride, carboxyl group-containing dialcohol compound and diol compound.
  • one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.
  • the carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.
  • Photosensitivity obtained by reacting polyfunctional epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride to the hydroxyl group present in the side chain Carboxyl group-containing resin.
  • a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride
  • a photosensitive carboxyl group obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin and adding a dibasic acid anhydride to the resulting hydroxyl group Containing resin.
  • a carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
  • 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.
  • 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 photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid.
  • One epoxy group and one or more (meth) acryloyl groups in the molecule such as glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate and the like in any one of the resins (1) to (12) above
  • a photosensitive carboxyl group-containing resin obtained by adding a compound having a group.
  • the carboxyl group-containing resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
  • the acid value of the carboxyl group-containing resin is preferably in the range of 20 to 2000 mgKOH / g, more preferably in the range of 40 to 1800 mgKOH / g.
  • adhesion of the coating film can be obtained, alkali development is facilitated, dissolution of the exposed area by the developer is suppressed, and the line does not fade more than necessary. This is preferable because the resist pattern can be easily drawn.
  • the weight average molecular weight of the carboxyl group-containing resin used in the present invention varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000. Within this range, tack-free performance is good, the moisture resistance of the coated film after exposure is good, and film loss is less likely to occur during development. Further, when the weight average molecular weight is within the above range, the resolution is improved, the developability is good, and the storage stability is improved. More preferably, it is 5,000 to 100,000.
  • the weight average molecular weight can be measured by gel permeation chromatography.
  • the resin composition of the present invention contains a thermosetting resin, it preferably contains a curing agent.
  • the curing agent include compounds having a phenolic hydroxyl group, polycarboxylic acids and acid anhydrides thereof, compounds having a cyanate ester group, compounds having an active ester group, compounds having a maleimide group, alicyclic olefin polymers, and the like. It is done.
  • curing agent can be used individually by 1 type or in combination of 2 or more types.
  • the dielectric loss tangent after humidification can be lowered by using at least a compound having a cyanate ester group or a compound having an active ester group.
  • the crack tolerance at the time of the thermal cycle after reflow improves by using the compound which has a cyanate ester group or the compound which has a maleimide group at least.
  • Examples of the compound having a phenolic hydroxyl group include phenol novolac resin, alkylphenol novolak resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, cresol / naphthol resin, polyvinylphenols, phenol Conventionally known resins such as naphthol resin, ⁇ -naphthol skeleton-containing phenol resin, triazine skeleton-containing cresol novolak resin, biphenyl aralkyl type phenol resin, and zylock type phenol novolak resin can be used.
  • the hydroxyl group equivalent is 100 g / eq.
  • the above is preferable.
  • Hydroxyl equivalent weight is 100 g / eq.
  • the compound having a phenolic hydroxyl group include a dicyclopentadiene skeleton phenol novolak resin (GDP series, manufactured by Gunei Chemical Co., Ltd.), a zylock type phenol novolak resin (MEH-7800, manufactured by Meiwa Kasei Co., Ltd.), and a biphenyl aralkyl type.
  • Novolak resin MEH-7785, manufactured by Meiwa Kasei Co., Ltd.
  • naphthol aralkyl type curing agent SN series, manufactured by Nippon Steel & Sumikin Co., Ltd.
  • triazine skeleton-containing cresol novolac resin LA-3018-50P, manufactured by DIC
  • the compound having a cyanate ester group is a compound having two or more cyanate ester groups (—OCN) in one molecule.
  • any conventionally known compounds can be used.
  • the compound having a cyanate ester group include a phenol novolak type cyanate ester resin, an alkylphenol novolak type cyanate ester resin, a dicyclopentadiene type cyanate ester resin, a bisphenol A type cyanate ester resin, a bisphenol F type cyanate ester resin, and a bisphenol S type.
  • Examples include cyanate ester resins. Further, it may be a prepolymer partially triazine.
  • the compound having an active ester group is a compound having two or more active ester groups in one molecule.
  • a compound having an active ester group can generally be obtained by a condensation reaction between a carboxylic acid compound and a hydroxy compound.
  • the compound which has an active ester group obtained using a phenol compound or a naphthol compound as a hydroxy compound is preferable.
  • phenol compound or naphthol compound examples include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like.
  • the compound having an active ester group may be naphthalenediol alkyl / benzoic acid type.
  • the compound having a maleimide group is a compound having a maleimide skeleton, and any conventionally known compound can be used.
  • the compound having a maleimide group preferably has two or more maleimide skeletons.
  • the blending amount of the curing agent is preferably 2 to 30%, more preferably 3 to 20%, and even more preferably 3 to 10% with respect to the total solid content of the composition.
  • the ratio of the functional group capable of thermosetting reaction such as epoxy group of the thermosetting resin and the functional group in the curing agent that reacts with the functional group is the functional group of the curing agent / thermosetting reaction.
  • the functional group (equivalent ratio) is preferably in a ratio of 0.2 to 2.
  • thermosetting resin when a thermosetting resin is used, a curing accelerator can be blended together with the above curing agent or alone.
  • the curing accelerator is for accelerating the thermosetting reaction, and is used for further improving properties such as adhesion, chemical resistance, and heat resistance.
  • curing accelerators include imidazole and derivatives thereof; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, Polyamines such as melamine and polybasic hydrazides; organic acid salts and / or epoxy adducts thereof; boron trifluoride amine complexes; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4- Triazine derivatives such as diamino-6-xylyl-S-triazine; trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, he
  • a curing accelerator is not essential, but particularly when it is desired to accelerate the curing, it is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the thermosetting resin. It can be used in the range.
  • the amount is preferably 10 to 550 ppm, more preferably 25 to 200 ppm in terms of metal with respect to 100 parts by mass of the thermosetting resin.
  • Photopolymerization initiator In the resin composition of the present invention, when a photocurable resin is used, it is preferable to further add a photopolymerization initiator. Any photopolymerization initiator can be used as long as it is a known photopolymerization initiator as a photopolymerization initiator or a photoradical generator.
  • photopolymerization initiator examples include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) -phenylphosphine oxide Bisacylphosphine oxides such as 2,6
  • Anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone; acetophenone dimethyl ketal, benzyldimethyl Ketals such as ketals; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate, and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1- [4- ( Phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-c
  • the blending amount of the photopolymerization initiator is preferably 0.01 to 30 parts by mass and more preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the photocurable resin in terms of solid content.
  • the resin composition of the present invention can further contain a thermoplastic resin in order to improve the mechanical strength of the resulting cured film.
  • the thermoplastic resin is preferably soluble in a solvent. When it is soluble in the solvent, the flexibility of the dry film is improved, and the generation of cracks and powder falling can be suppressed.
  • the thermoplastic resin use is made of thermoplastic polyhydroxy polyether resin, phenoxy resin that is a condensate of epichlorohydrin and various bifunctional phenolic compounds, or hydroxyl group of hydroxy ether part present in the skeleton of various acid anhydrides and acid chlorides. And esterified phenoxy resin, polyvinyl acetal resin, polyamide resin, polyamideimide resin, block copolymer and the like.
  • a thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the blending amount of the thermoplastic resin is preferably 1 to 10%, more preferably 1 to 5%, and even more preferably 1.5 to 5% with respect to the total solid content of the composition.
  • the resin composition of the present invention can contain rubber-like particles as necessary.
  • rubber-like particles include polybutadiene rubber, polyisopropylene rubber, urethane-modified polybutadiene rubber, epoxy-modified polybutadiene rubber, acrylonitrile-modified polybutadiene rubber, carboxyl group-modified polybutadiene rubber, acrylonitrile butadiene rubber modified with a carboxyl group or a hydroxyl group, and
  • These crosslinked rubber particles, core-shell type rubber particles, and the like can be mentioned, and one kind can be used alone or two or more kinds can be used in combination.
  • These rubber-like particles are added in order to improve the flexibility of the resulting cured film and to improve crack resistance.
  • the average particle size of the rubber-like particles is preferably in the range of 0.005 to 1 ⁇ m, more preferably in the range of 0.2 to 1 ⁇ m.
  • the average particle size of the rubber-like particles in the present invention can be determined by a laser diffraction particle size distribution measuring device. For example, rubber-like particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and a particle size distribution of the rubber-like particles is created on a mass basis using Nanotrac wave manufactured by Nikkiso Co., Ltd. It can be measured by doing.
  • the blending amount of the rubber-like particles is preferably 1 to 10%, more preferably 1 to 5%, based on the total solid content of the composition. Within the above range, the flexibility and crack resistance of the cured film can be improved while maintaining a high glass transition temperature (Tg).
  • Organic solvent is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. it can.
  • ketones such as methyl ethyl ketone, cyclohexanone, methyl butyl ketone, and methyl isobutyl ketone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methylcarbitol Glycol ethers such as butyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, di Esters such as propylene glycol methyl ether acetate, but
  • the resin composition of the present invention may further contain other conventionally known additives.
  • additives include, for example, conventionally known thickeners such as asbestos, olben, benton, fine silica, etc., defoamers and / or leveling agents such as silicones, fluorines and polymers, thiazoles, Examples thereof include adhesion imparting agents such as triazoles and silane coupling agents, fine powders such as cellulose nanofibers, antioxidants such as hindered phenols, flame retardants, titanates, and aluminum additives. .
  • the resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more.
  • the dry film of the present invention can be produced by applying the resin composition of the present invention on a carrier film and drying to form a resin layer. In addition, you may bond a protective film on a resin layer as needed.
  • the carrier film has a role of supporting the resin layer of the dry film, and is a film to which the resin composition is applied when the resin layer is formed.
  • the carrier film for example, a polyester film such as polyethylene terephthalate or polyethylene naphthalate, a polyimide film, a polyamideimide film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a film made of a thermoplastic resin such as a polystyrene film, and
  • a polyester film can be used suitably from viewpoints, such as heat resistance, mechanical strength, and handleability.
  • the thickness of the carrier film is not particularly limited, but is appropriately selected depending on the intended use within a range of about 10 to 150 ⁇ m.
  • the surface on which the resin layer of the carrier film is provided may be subjected to release treatment.
  • the protective film is provided on the surface opposite to the carrier film of the resin layer for the purpose of preventing dust and the like from adhering to the surface of the resin layer of the dry film and improving the handleability.
  • a film made of a thermoplastic resin exemplified for the carrier film, surface-treated paper, and the like can be used.
  • a polyester film, a polyethylene film, and a polypropylene film are preferable.
  • the thickness of the protective film is not particularly limited, but is appropriately selected depending on the intended use within a range of about 10 to 150 ⁇ m.
  • the surface on which the resin layer of the protective film is provided may be subjected to a mold release treatment.
  • the amount of residual solvent in the resin layer of the dry film is preferably 0.1 to 5.0% by mass, more preferably 0.1 to 3.0% by mass, and 0.5 to 2.0%. Even more preferably, it is by mass.
  • the residual solvent is 5.0% by mass or less, bumping at the time of thermosetting is suppressed, and the flatness of the surface becomes better. Moreover, it can suppress that melt viscosity falls too much and resin flows, and flatness becomes favorable.
  • the residual solvent is 0.1% by mass or more, the fluidity during lamination is good, and the flatness and embedding are better. Further, when the residual solvent is 0.5 to 2.0% by mass, the handling property and the coating film characteristics of the dry film are excellent.
  • a coating method of the resin composition a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain coating method, or the like can be used.
  • a hot air circulation drying furnace an IR (infrared) furnace, a hot plate, a convection oven, or the like equipped with a heat source of an air heating method using steam can be used.
  • a method for forming a protective layer of a multilayer electronic component using the resin composition of the present invention when a liquid curable resin composition is used, a roll coating method, a bar coater method, a screen printing method, a curtain coating method, etc. After the application of the liquid curable resin composition, the solvent is evaporated by temporary drying at a low temperature of 50 to 100 ° C. for 20 to 60 minutes, and then the temperature of 150 to 250 ° C. Heat cure at a temperature of 30-90 minutes. When used as a dry film, methods such as laminating and pressing can be used. After the dry film is laminated, it is protected by thermosetting at a temperature of 150 to 250 ° C. for 30 to 90 minutes. A layer can be formed.
  • the multilayer electronic component of the present invention is characterized in that electrode layers and insulating layers are alternately laminated, and protective layers containing a cured product of the composition of the present invention are provided on both end faces in the lamination direction. .
  • the multilayer electronic component of the present invention is useful in multilayer electronic components used in various electronic devices such as digital devices, AV devices, and information communication terminals.
  • the multilayer electronic component of the present invention is, for example, a passive component such as an inductor or an active component.
  • the multilayer electronic component is preferably an inductor.
  • FIG. 1 schematically shows a schematic cross-sectional view of one embodiment of the multilayer electronic component of the present invention, but the present invention is not limited to this.
  • the inductor which is the multilayer electronic component 11 is connected to the external electrodes 15a and 15b.
  • the electrode layers 12a to 12f are alternately stacked with the insulating layers 13a to 13f, and protective layers 14a and 14b are provided on both end surfaces in the stacking direction.
  • the electrode layers 12a to 12f are formed in a coil shape as a whole.
  • the size of the multilayer electronic component of the present invention is not particularly limited, even if one side is 1 mm or less, each side is 1 mm or less, each side is 500 ⁇ m or less, or even Even if each side is 200 ⁇ m or less, the discrimination power at the time of appearance inspection is excellent.
  • the protective layer is a cured product of the laminated electronic component composition of the present invention.
  • the thickness of the protective layer is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and even more preferably 30 ⁇ m or less.
  • the protective layer preferably has a coefficient of thermal expansion (CTE ( ⁇ 1)) of less than 25 ppm, and preferably has a storage elastic modulus (E ′) of 15 GPa or more, more preferably 16 GPa or more.
  • the electrode layer preferably has a thickness of 50 ⁇ m or less, and more preferably 15 ⁇ m or less.
  • the electrode layer is not particularly limited as long as it has conductivity such as a silver (Ag) material or a copper (Cu) material, but it is more preferable to use a circuit formed of copper.
  • a paste such as a copper paste or a silver paste, it is formed by a screen printing method or the like, and other methods include a method of forming by copper foil etching, copper plating, coil conductors, etc., and an embodiment of the present invention. Then, any method may be used and is not particularly limited.
  • an organic insulating layer can be suitably used.
  • An insulating layer made of the composition may be used.
  • a cured film of a conventional printed wiring board for example, a cured product of a curable resin composition for forming a solder resist or the like can be used.
  • the insulating layer is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and even more preferably 20 ⁇ m or less.
  • liquid resin composition When the liquid resin composition is used for the insulating layer, methods such as a roll coating method, a bar coater method, a screen printing method, and a curtain coating method can be used. Moreover, when using as a dry film, methods, such as a lamination method and a press method, can be used.
  • the insulating layer is obtained by curing an alkali developing resin composition containing an alkali-soluble resin, a photopolymerization initiator, and an inorganic filler, depending on the amount of the inorganic filler (for example, And 20 to 70% by mass relative to the total solid content of the composition), the storage elastic modulus of the insulating layer is lowered, and the strength of the multilayer electronic component as a whole may be reduced.
  • the strength of the entire multilayer electronic component can be ensured by forming protective layers obtained by curing the resin composition of the present invention on both end faces of the multilayer electronic component.
  • the resin composition of the present invention can exhibit the above effects well when the blending amount of the inorganic filler is 50 to 90% by mass with respect to the total solid content of the composition.
  • alkali-soluble resin used for an insulating layer the carboxyl group containing resin mentioned above, phenolic hydroxyl group containing resin, etc. can be used as a component which the resin composition of this invention contains.
  • photoinitiator and inorganic filler which are used for an insulating layer the photoinitiator and inorganic filler which were mentioned above as a component which the resin composition of this invention contains, respectively can be used.
  • the blending amount of the alkali-soluble resin used for the insulating layer is preferably 5 to 60% by mass with respect to the total solid content of the composition.
  • the blending amount of the photopolymerization initiator used for the insulating layer is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.
  • the printed wiring board of the present invention is characterized in that the multilayer electronic component of the present invention is mounted on at least one of the surface and the inside. In the present invention, the printed wiring board is not included in the concept of “multilayer electronic component”.
  • the water produced by the reaction was distilled as an azeotrope with toluene and was 12.6 g. Thereafter, the resulting reaction solution was cooled to room temperature, neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution.
  • Irgacure OXE02 Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), manufactured by BASF Japan * 2 )
  • JER828 bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 184 to 194 g / eq, liquid * 3)
  • DPHA dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd. * 4)
  • thermosetting resin composition layer and the thermosetting resin layer were formed on a carrier film.
  • a protective film polypropylene film
  • etching process corresponding to 0.5 ⁇ m was performed as a pretreatment on a substrate (500 mm ⁇ 600 mm ⁇ 0.4 mmt (thickness)) on which a copper circuit was formed as an electrode layer by a CZ-8101 process manufactured by MEC.
  • the dry film protective film of the photo / thermosetting resin composition of Table 1 prepared above was peeled off and bonded so that the resin layer side was in contact with the substrate surface, and a batch type vacuum pressure laminator MVLP-500 (name Was used for heat lamination under the conditions of pressure: 0.5 MPa, 80 ° C., 1 minute, and vacuum: 133.3 Pa to obtain a substrate having a resin layer.
  • a batch type vacuum pressure laminator MVLP-500 name Was used for heat lamination under the conditions of pressure: 0.5 MPa, 80 ° C., 1 minute, and vacuum: 133.3 Pa to obtain a substrate having a resin layer.
  • the exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp) the resin layer was exposed from the carrier film, and then the carrier film was peeled off. Thereafter, development was performed for 60 seconds with a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. under a spray pressure of 2 kg / cm 2 .
  • thermosetting resin composition ⁇ Preparation of a substrate having an insulating layer protected by a protective layer made of a thermosetting resin composition>
  • the protective film for the dry film of the thermosetting resin composition of Tables 2 to 5 prepared above on the substrate prepared by the method described in ⁇ Preparation of substrate having insulating layer made of photo / thermosetting resin composition> Are laminated so that the thermosetting resin layer side is in contact with the insulating layer, and using a batch type vacuum pressure laminator MVLP-500 (manufactured by Meiki Co., Ltd.), the degree of pressure is 0.5 MPa, 90 ° C., Heat lamination was performed for 1 minute under a vacuum degree of 133.3 Pa to obtain a substrate having a thermosetting resin layer on the insulating layer.
  • MVLP-500 manufactured by Meiki Co., Ltd.
  • the carrier film is peeled off, heated at 100 ° C. for 30 minutes in a hot-air circulating drying furnace, then heated at 180 ° C. for 60 minutes, and on the light / thermosetting cured film as the insulating layer, as a protective layer A laminated cured product in which a thermosetting cured film was laminated was obtained.
  • the softness of the dry film was evaluated from the minimum diameter of the mandrel that began to crack and peel off from the carrier film.
  • the evaluation criteria are as follows. When the flexibility of the dry film is good, the flexibility of the resin layer is high and cracking and powder falling can be suppressed. A: The diameter was ⁇ 2 mm or less, and there was no occurrence of cracking of the resin layer, powder falling, or peeling of the carrier film.
  • ⁇ In the range of more than ⁇ 2 mm and less than 5 mm, there was no occurrence of cracking of the resin layer, powder falling, or peeling of the carrier film.
  • X Cracking of resin layer, powder falling, and peeling of carrier film occurred at a diameter of ⁇ 5 mm or more.
  • melt viscosity was measured using an Rheo Stress RS-6000 (manufactured by HAAKE) under conditions of an oscillation mode, a strain of 2%, a heating rate of 3 ° C./min, a gap of 300 ⁇ m, and a frequency of 1 Hz. .
  • ⁇ The melt viscosity is 10,000 dPa ⁇ s or more and less than 50,000 dPa ⁇ s.
  • X Melt viscosity is less than 10,000 dPa ⁇ s or 500,000 dPa ⁇ s or more.
  • thermosetting resin composition prepared by the method described in ⁇ Preparation of Dry Film> on the glossy surface side (copper foil) of copper foil F2 (Furukawa Sangyo Co., Ltd.).
  • a film is attached, and a batch type vacuum pressure laminator MVLP-500 (manufactured by Meiki Co., Ltd.) is used on a copper foil under the conditions of pressure: 0.5 MPa, 90 ° C., 1 minute, vacuum: 133.3 Pa. Heat laminated. Next, after heating at 110 ° C.
  • the resin layer was cured at 180 ° C. for 60 minutes, and then the carrier film was peeled off to obtain a cured product. Then, after peeling hardened
  • the test weight was 5 g, and the sample was heated from room temperature at a heating rate of 10 ° C./min, and was measured twice continuously.
  • the intersection of two tangents having different thermal expansion coefficients in the second round was evaluated as CTE ( ⁇ 1), which is a thermal expansion coefficient between 30 ° C. and 100 ° C. of glass transition temperature (Tg).
  • Tg glass transition temperature
  • CTE ( ⁇ 1) thermal expansion coefficient
  • Tg glass transition temperature
  • Evaluation of storage elastic modulus E ′ 18 GPa or more. ⁇ : 15 GPa or more and less than 18 GPa. ⁇ : 10 GPa or more and less than 15 GPa. X: Less than 10 GPa.
  • ⁇ Measurement of dielectric constant (Dk) and dielectric loss tangent (Df)> The cured product prepared by the method described in ⁇ Measurement of glass transition temperature (Tg) and coefficient of thermal expansion (CTE ( ⁇ 1)) by TMA> is SPDR dielectric resonator and network analyzer (both manufactured by Agilent). The dielectric constant (Dk) and dielectric loss tangent (Df) of 10 GHz at 23 ° C. were measured. Judgment criteria are as follows.
  • Dk dielectric constant
  • ⁇ Circuit concealment> The substrate prepared by the method described in ⁇ Preparation of substrate having insulating layer protected by protective layer made of thermosetting resin composition> was visually checked for discoloration of the copper circuit from the cured film, and the circuit The concealment property was evaluated. A: When discoloration is not confirmed. A: When slight discoloration is confirmed. X: When discoloration is confirmed.
  • CM-2600d manufactured by Konica Minolta Sensing Co., Ltd.
  • the reflectance at a wavelength of 360 to 740 nm was measured, and the reflectance of the insulating layer at a wavelength of 450 nm was measured.
  • Reflectance difference (%) Protective layer reflectance (%)-Insulating layer reflectance (%) Judgment criteria are as follows. A: Very excellent in distinguishability (difference in reflectance is 20% or more) ⁇ : Excellent discrimination (difference in reflectance is 10% or more and less than 20%) X: Inferior in discrimination (difference in reflectance is less than 10%)
  • the protective layer and the insulating layer have a difference in reflectance of 10% or more at a wavelength of 450 nm
  • an AOI inspection machine manufactured by Orbotech
  • one side is 1 mm.
  • a visual inspection can be performed without misidentifying the upper and lower sides of the protective layer and the side surface of the inner layer material.
  • ⁇ Reflow resistance (reflectance after heating and before heating)> The method according to ⁇ Preparation of substrate having insulating layer protected by protective layer made of thermosetting resin composition> used in ⁇ discrimination (difference in reflectance (protective layer and insulating layer))>
  • the reflow treatment was performed five times at a heating temperature of 260 ° C., and the coating film surface after the reflow treatment was subjected to a spectrocolorimeter (CM- 2600d, manufactured by Konica Minolta Sensing Co., Ltd.), the reflectance at a wavelength of 360 to 740 nm was measured, the reflectance at a wavelength of 450 nm was measured, and the difference between the reflectance after heating and before heating was evaluated.
  • CM- 2600d manufactured by Konica Minolta Sensing Co., Ltd.
  • the reflow treatment 5 times means that the operation of passing through an infrared furnace at 260 ° C. for 10 seconds and returning to normal temperature was repeated 5 times.
  • the dry film protective film of the thermosetting resin composition prepared in ⁇ Preparation of Dry Film> is peeled off and bonded so that the thermosetting resin layer side is in contact with the substrate surface, and the batch type vacuum pressure laminator MVLP -500 (manufactured by Meiki Co., Ltd.) and heat laminated under the conditions of pressure: 0.5 MPa, 90 ° C., 1 minute, vacuum: 133.3 Pa to obtain a substrate having a thermosetting resin layer. It was.
  • the carrier film was peeled off and heated at 100 ° C. for 30 minutes in a hot-air circulating drying furnace, and then heated at 180 ° C. for 60 minutes to obtain a thermosetting film. After thermosetting, air entered the boundary part between the line and the space, and evaluated whether 100 bubbles were generated. A: No void was confirmed. ⁇ : 1 to 3 voids were confirmed. X: Four or more voids were confirmed.
  • ⁇ Cross cut test> The substrate prepared in ⁇ Preparation of substrate having an insulating layer protected by a protective layer comprising a thermosetting resin composition> is cross-cut in a grid pattern according to the test method of JIS D 0202, and peeled with an adhesive tape A test was conducted to evaluate the peeling of the protective layer. Judgment criteria are as follows. ⁇ : No peeling at all. X: The protective layer has peeling.
  • EPOX-MK R710 Bisphenol E type epoxy resin, manufactured by Printec, epoxy equivalent 160-180 g / eq, liquid * 8)
  • jER828 Bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical, epoxy equivalent 184-194 g / eq, liquid * 9)
  • jER807 bisphenol F type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 160-175 g / eq, liquid * 10)
  • HP-7200L dicyclopentadiene type epoxy resin, manufactured by DIC, epoxy equivalent 250- 280 g / eq, softening point 57-68 ° C * 11)
  • HP-4032 Naphthalene type epoxy resin, manufactured by DIC, epoxy equivalent of 135 to 165 g / eq, semi-solid * 12)
  • HF-1M Phenol novolac resin, manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent of 104 to 108 g / eq, Softening point
  • BiNFi-s Extra fine fiber biomass nanofiber, manufactured by Sugino Machine Co., Ltd. * 21) KBM-602: N-2- (aminoethyl) -3-amino propyl methyl dimethoxy silane, manufactured by Shin-Etsu chemical Co., Ltd.
  • IRGANOX 1076 polymeric heat-resistant stabilizer, BASF Japan Ltd., hindered phenol antioxidant * 23)
  • SO-C2 silica SiO 2
  • Admatechs Co., D50 0.5 ⁇ m * 24
  • YA050C silica SiO 2
  • Admatechs Co., Ltd., D50 50nm * 25)
  • Taipei CR-953 TiO 2 manufactured by Ishihara Sangyo Co., Ltd. * 26) Cyclohexanone: Solvent * 27) Toluene: Solvent * 28)
  • MEK Methyl ethyl ketone, solvent

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