WO2019187588A1 - Composition de résine durcissable, film sec, objet durci et composant électronique - Google Patents

Composition de résine durcissable, film sec, objet durci et composant électronique Download PDF

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Publication number
WO2019187588A1
WO2019187588A1 PCT/JP2019/002809 JP2019002809W WO2019187588A1 WO 2019187588 A1 WO2019187588 A1 WO 2019187588A1 JP 2019002809 W JP2019002809 W JP 2019002809W WO 2019187588 A1 WO2019187588 A1 WO 2019187588A1
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Prior art keywords
compound
resin
group
resin composition
silica particles
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PCT/JP2019/002809
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English (en)
Japanese (ja)
Inventor
千穂 植田
岡田　和也
沙和子 嶋田
知哉 工藤
Original Assignee
太陽インキ製造株式会社
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Application filed by 太陽インキ製造株式会社 filed Critical 太陽インキ製造株式会社
Priority to CN201980023562.9A priority Critical patent/CN111936575B/zh
Priority to KR1020207029607A priority patent/KR20200140289A/ko
Publication of WO2019187588A1 publication Critical patent/WO2019187588A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • 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 curable resin composition, a dry film, a cured product, and an electronic component.
  • the main component is a curable resin such as a carboxyl group-containing resin or an epoxy resin for an interlayer insulating material or a solder resist material.
  • resin compositions containing additive components such as fillers are widely used.
  • the surface of the resin insulation layer such as an interlayer insulation material is usually roughened by a conductor layer formation process (copper foil rough surface transfer or chemical treatment before copper plating), and is in close contact with the solder resist material. Improves sex.
  • the cured product made of the conventional resin composition used as such an interlayer insulating material there is a problem that delay and loss of electric signals are unavoidable when communicating in a high frequency region.
  • the surface of an interlayer insulating material tends to become a roughening-free or low-roughening surface (so-called low profile substrate), and the material includes a low-polarity insulating material containing an active ester, etc.
  • the low dielectric loss material has come to be used.
  • thermophysical properties for example, by highly filling the composition with an inorganic filler.
  • silica is particularly excellent in filling properties, has a low coefficient of thermal expansion (CTE), and can be easily introduced with a curable reactive group, and has been widely used to improve the properties of solder resists. (See Patent Document 1).
  • an interlayer insulating material used as a material for a low profile substrate that solves the problem of transmission loss is blended with components for reducing polarity such as active esters as described above in order to reduce the dielectric loss tangent.
  • components for reducing polarity such as active esters as described above in order to reduce the dielectric loss tangent.
  • the adhesion with the conductor layer or the solder resist decreases.
  • the solder resist material described above when silica is highly filled as an inorganic filler from the viewpoint of CTE mismatch or low dielectric loss tangent with a semiconductor chip, the ratio of the curable resin is reduced, so that the anchor effect of desmear is reduced.
  • the conductive layer is free of roughening in the interlayer insulating material containing silica and a component aiming at low polarity such as active ester, which is used to solve the problem of transmission loss. Even if it is a low roughened surface, it has excellent adhesion after the HAST treatment with the conductor layer, and even if the surface of the interlayer insulating material and the conductor layer is a roughening free surface or a low roughened surface, as described above. It is required to have excellent adhesion after HAST treatment with a solder resist containing a large amount of silica particles.
  • an object of the present invention is to have a curable resin composition that has excellent adhesion after HAST treatment with a conductor layer and a solder resist, and that can obtain a cured product having a low dielectric loss tangent, and a resin layer obtained from the composition.
  • a dry film, a cured product of the resin layer of the composition or the dry film, and an electronic component having the cured product are examples of a curable resin composition that has excellent adhesion after HAST treatment with a conductor layer and a solder resist, and that can obtain a cured product having a low dielectric loss tangent, and a resin layer obtained from the composition.
  • a dry film, a cured product of the resin layer of the composition or the dry film, and an electronic component having the cured product are examples of the resin layer of the composition.
  • the present inventors diligently studied focusing on the surface treatment of silica used as an inorganic filler in order to achieve the above object. As a result, the inventors used silica particles coated with any one of aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide, and titanium hydrated oxide, And it discovered that the said subject could be solved by using a specific compound as a hardening
  • the curable resin composition of the present invention is coated with at least one of aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide, and titanium hydrated oxide.
  • the coated silica particles preferably further have a curable reactive group on the surface.
  • the dry film of the present invention is characterized by having a resin layer obtained by applying the curable resin composition to the film and drying it.
  • the cured product of the present invention is obtained by curing the curable resin composition or the resin layer of the dry film.
  • the electronic component of the present invention is characterized by having the cured product.
  • the curable resin composition which can obtain the hardened
  • a cured product of the resin layer of the film, the composition or the dry film, and an electronic component having the cured product can be provided.
  • the curable resin composition of the present invention is a silica coated with at least one of aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide, and titanium hydrated oxide. At least one of particles (hereinafter also referred to as “the coated silica particles”), an epoxy compound, a compound having an active ester group, a compound having a cyanate ester group, and a compound having a maleimide group as a curing agent It is characterized by including these.
  • the coated silica particles by including at least one of a compound having an active ester group, a compound having a cyanate ester group, and a compound having a maleimide group as a curing agent, and the coated silica particles, although it is a low dielectric loss tangent, the hardened
  • the problem of adhesion after the HAST treatment is particularly noticeable when the amount of filler is large, but according to the present invention, when the amount of silica is large, for example, 30% by mass or more, the HAST of the cured product It is possible to obtain a curable resin composition in which the adhesiveness is not easily lowered after the treatment.
  • the coated silica particles preferably have a curable reactive group on the surface.
  • the filler has a curable reactive group on the surface, it is possible to strengthen the bond between the filler and the curable resin.
  • the resin has a large specific surface area while the filler particle has a large specific surface area. Since the content is reduced, it is easy to cause a part that is not sufficiently familiar with the curable resin.
  • HAST high temperature and high humidity
  • the surface of the silica particles has more hydroxyl groups based on the hydrated oxide, and can effectively impart a curable reactive group therein, so that the melt viscosity can be further reduced. It is preferable to have.
  • coated silica particles are coated with at least one of aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide, and titanium hydrated oxide, Coarse particles are unlikely to occur in the curable resin, and further, by imparting a curable reactive group effectively, the fluidity is improved and the processability such as flattening and thinning is excellent.
  • (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
  • the curable resin composition of the present invention is a silica coated with at least one of aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide, and titanium hydrated oxide. Contains particles.
  • the silica particles to be coated are not particularly limited, and known and commonly used silica particles that can be used as an inorganic filler may be used.
  • Examples of the silica particles to be coated include fused silica, spherical silica, amorphous silica, and crystalline silica, and spherical silica is preferable.
  • silica particles with a hydrated oxide of aluminum for example, by adding an aqueous solution of a water-soluble aluminum compound such as sodium aluminate to an aqueous slurry of silica particles, and then neutralizing with an alkali or acid, Aluminum hydrated oxide can be deposited on the surface of the silica particles.
  • the amount of silica particles in the water slurry is not particularly limited, but usually 30 to 300 g / l is appropriate.
  • Sodium hydroxide, potassium hydroxide, ammonia are used as the alkali, and hydrochloric acid, nitric acid, etc. are used as the acid, and the amount added is such that the water-soluble aluminum compound can form a hydrated oxide of aluminum, preferably pH Is 7 ⁇ 0.5.
  • silica particles with a hydrated oxide of zirconium for example, by adding an aqueous solution of a water-soluble zirconium compound such as zirconium oxychloride to an aqueous slurry of silica particles, and then neutralizing with an alkali or acid, A zirconium hydrated oxide can be deposited on the surface of the silica particles.
  • the amount of silica particles in the water slurry is not particularly limited, but usually 30 to 300 g / l is appropriate.
  • the amount to be added is an amount such that the water-soluble zirconium compound can form a hydrated oxide of zirconium, and preferably the pH is 7 ⁇ 0.5. is there.
  • silica particles with a hydrated oxide of zinc for example, an aqueous solution of a water-soluble zinc compound such as zinc sulfate is added to an aqueous slurry of silica particles, and then neutralized with an alkali or an acid. Zinc hydrated oxide can be deposited on the surface of the particles.
  • the amount of silica particles in the water slurry is not particularly limited, but usually 30 to 300 g / l is appropriate.
  • the alkali, sodium hydroxide, potassium hydroxide, and ammonia are added in such an amount that the water-soluble zinc compound can form a hydrated oxide of zinc, and the pH is preferably 7 ⁇ 0.5.
  • silica particles As a method of coating silica particles with a hydrated oxide of titanium, for example, after adding an aqueous solution of water-soluble titanium such as titanyl sulfate to an aqueous slurry of silica particles, the silica particles are neutralized with an alkali or an acid. Titanium hydrated oxide can be deposited on the surface of the substrate.
  • the amount of silica particles in the water slurry is not particularly limited, but usually 30 to 300 g / l is appropriate.
  • the acid hydrochloric acid, nitric acid or the like is used, and the amount added is an amount such that the water-soluble titanium compound can form a hydrated oxide of titanium, and the pH is preferably 7 ⁇ 0.5.
  • Coating with the metal hydrated oxide that is, coating with at least one of aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide and titanium hydrated oxide
  • the hydrated oxide of the metal is preferably coated with 1 to 40 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the silica particles. By covering with 1 part by mass or more, it is possible to obtain a cured product that is excellent in dispersibility of silica particles in the curable resin and whose adhesion is not easily lowered after the HAST treatment.
  • the adhesion after HAST treatment is excellent, and a strong bond with the curable resin can be obtained.
  • the physical properties of the cured product can be improved by the group, for example, the CTE can be lowered.
  • the curable reactive group is not particularly limited as long as it is a group that undergoes a curing reaction with a component (for example, a curable resin or an alkali-soluble resin) blended in the curable resin composition, and even a photocurable reactive group. It may be a thermosetting reactive group.
  • curable reactive groups examples include epoxy groups, amino groups, hydroxyl groups, carboxyl groups, isocyanate groups, imino groups, oxetanyl groups, mercapto groups, methoxymethyl groups, methoxyethyl groups, ethoxymethyl groups, ethoxyethyl groups, oxazoline groups, methacrylic groups.
  • the method for introducing the curable reactive group to the surface of the coated silica particles is not particularly limited, and may be introduced using a known and commonly used method, and a surface treatment agent having a curable reactive group, for example, a curable reaction.
  • the surface of the coated silica particles may be treated with a coupling agent having a group as an organic group.
  • a coupling agent having a group as an organic group.
  • a silane coupling agent a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, or the like can be used. Of these, a silane coupling agent is preferable.
  • the curable reactive group on the surface of the coated silica particle is preferably a thermosetting reactive group.
  • the curable resin composition of the present invention contains a photocurable resin, it may be a photocurable reactive group.
  • the average particle size of the coated silica particles is preferably 1 ⁇ m or less.
  • the silica particles are coated as described above, so that the dispersibility is excellent and the aggregation is difficult. Further, it is preferably smaller than the exposure wavelength, and more preferably 0.4 ⁇ m or less. Moreover, it is preferable that it is 0.25 micrometer or more from a viewpoint of suppressing halation.
  • the average particle diameter of the silica particles is an average particle diameter (D50) including not only the primary particle diameter but also the secondary particle (aggregate) particle diameter.
  • the maximum particle diameter of the coated silica particles is preferably 2 ⁇ m or less, and more preferably 1 ⁇ m or less.
  • An example of a measuring apparatus using a laser diffraction method is Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. By being 2 ⁇ m or less, a uniform and fine roughened surface can be obtained.
  • the average particle diameter of the coated silica particles may be adjusted, for example, it is preferably predispersed with a bead mill or a jet mill. Further, the coated silica particles are preferably blended in a slurry state. By blending in the slurry state, high dispersion can be easily achieved, aggregation can be prevented, and handling can be facilitated.
  • the coated silica particles can be used singly or in combination of two or more.
  • the blended amount of the coated silica particles is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 45% by mass or more in the total solid content of the composition. .
  • the adhesion and dispersibility after HAST treatment are excellent, so that the physical properties of the cured product can be improved, for example, low CTE, warpage resistance, and heat resistance.
  • silica can be highly filled.
  • the curable resin composition of the present invention contains at least one of a compound having an active ester group, a compound having a cyanate ester group, and a compound having a maleimide group as a curing agent. By containing such a curing agent, a low dielectric cured product can be obtained. These curing agents can be used alone or in combination of two or more.
  • the compound having an active ester group is preferably 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.
  • cyclopentadiene type diphenol compounds such as HPC8000-65T (manufactured by DIC), HPC8100-65T (manufactured by DIC), HPC8150-65T (manufactured by DIC), EXB-8500-65T (manufactured by DIC) may be mentioned.
  • the compound having a cyanate ester group is preferably 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.
  • cyanate ester group Commercially available compounds having a cyanate ester group include a phenol novolak type polyfunctional cyanate ester resin (manufactured by Lonza Japan Co., Ltd., PT30S), and a prepolymer in which a part or all of bisphenol A dicyanate is triazine and becomes a trimer. (Lonza Japan, BA230S75), dicyclopentadiene structure-containing cyanate ester resin (Lonza Japan, DT-4000, DT-7000) and the like. Moreover, BA230 (made by Lonza Japan) is also mentioned.
  • 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.
  • BMI-1000 (4,4′-diphenylmethane bismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.)
  • BMI-2300 phenylmethane bismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.
  • BMI- 3000 m-phenylene bismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.
  • BMI-5100 (3,3′-dimethyl-5,5′-dimethyl-4,4′-diphenylmethane bismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.
  • BMI -7000 (4-methyl-1,3-phenylene bismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.
  • BMI-TMH ((1,6-bismaleimide-2,2,4-trimethyl) hexane, manufactured by Daiwa Kasei Ko
  • a compound having an active ester group is preferable because it is excellent in low dielectric loss.
  • Cyanate esters are also preferable because they are excellent in low dielectric loss.
  • a three-dimensional structure containing a triazine ring can be formed, so that water absorption characteristics are lowered and migration resistance is improved.
  • the blending amount of the curing agent is preferably 1 to 30% by mass when the solid content in the curable resin composition is 100% by mass.
  • the curable resin composition of the present invention contains an epoxy compound.
  • An epoxy compound can be used individually by 1 type or in combination of 2 or more types.
  • the epoxy compound is a compound having an epoxy group, and any conventionally known one can be used. Examples include polyfunctional epoxy compounds having a plurality of epoxy groups in the molecule. Note that a hydrogenated epoxy compound may be used.
  • Polyfunctional epoxy compounds include epoxidized vegetable oils; bisphenol A type epoxy resins; hydroquinone type epoxy resins; bisphenol type epoxy resins; thioether type epoxy resins; brominated epoxy resins; novolac type epoxy resins; biphenol novolac type epoxy resins; Type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; bixylenol type or biphenol type epoxy resin or a mixture thereof; Bisphenol S type epoxy resin; Bisphenol A novolak type epoxy resin; Tetraphenylol ethane type epoxy resin; Heterocyclic epoxy resin; Phthalate resin; Tetraglycidylxylenoylethane resin; Naphthalene group-containing epoxy resin; Epoxy resin having dicyclopentadiene skeleton; Glycidyl methacrylate copolymer epoxy resin; Copolymer epoxy resin of
  • epoxy resins can be used alone or in combination of two or more.
  • novolak type epoxy resins bisphenol type epoxy resins, bixylenol type epoxy resins, biphenol type epoxy resins, biphenol novolac type epoxy resins, naphthalene type epoxy resins or mixtures thereof are particularly preferable.
  • the compounding amount of the epoxy compound is preferably 5 to 60% by mass when the solid content in the curable resin composition is 100% by mass.
  • the curing accelerator of the present invention can contain a curing accelerator.
  • the curing accelerator include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-Cyanoethyl) -2-ethyl-4-methylimidazole, imidazole derivatives such as imidazole and epoxy adducts; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy -N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, amine compounds such as 4-dimethylaminopyridine, hydrazine compounds such as adipic acid dihydrazide, sebacic acid
  • organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, and tin
  • organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate.
  • Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate.
  • organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
  • cobalt (II) acetylacetonate cobalt (III) acetylacetonate, zinc (II) acetylacetonate, zinc naphthenate, iron (III) acetylacetonate are Cobalt (II) acetylacetonate and zinc naphthenate are more preferable.
  • the curing accelerator a compound that also functions as an adhesion promoter is preferably used in combination with the curing accelerator.
  • a hardening accelerator can be used individually by 1 type or in combination of 2 or more types.
  • the blending amount of the curing accelerator is, for example, 0.01 to 30% by mass in the total solid content of the composition.
  • the curable 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 a solvent, the flexibility is improved when it is made into a dry film, 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.
  • thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.
  • the blending amount of the thermoplastic resin is, for example, 0.01 to 10% by mass in the total solid content of the composition.
  • the curable resin composition of the present invention may contain a colorant.
  • a known and commonly used flame retardant can be used.
  • Known and conventional flame retardants include phosphoric acid esters and condensed phosphoric acid esters, phosphorus element-containing (meth) acrylates, phosphorus-containing compounds having phenolic hydroxyl groups, cyclic phosphazene compounds, phosphazene oligomers, phosphorus-containing compounds such as phosphinic acid metal salts, Layered layers of antimony compounds such as antimony trioxide and antimony pentoxide, halides such as pentabromodiphenyl ether and octabromodiphenyl ether, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, hydrotalcite and hydrotalcite-like compounds A double hydroxide is mentioned.
  • a flame retardant can be used individually by 1 type or in combination of 2 or more types.
  • the blending amount of the flame retardant is, for example, 0.01 to 10% by mass in the total solid content of the composition.
  • the curable resin composition of the present invention may contain a colorant.
  • a colorant known colorants such as red, blue, green, yellow, black, and white can be used, and any of pigments, dyes, and pigments may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.
  • a coloring agent can be used individually by 1 type or in combination of 2 or more types.
  • the blending amount of the colorant is, for example, 0.01 to 10% by mass in the total solid content of the composition.
  • the curable resin composition of the present invention can contain an organic solvent for the purpose of preparing the composition and adjusting the viscosity when applied to a substrate or a carrier 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, carbitol
  • additives include thermal polymerization inhibitors, UV absorbers, silane coupling agents, plasticizers, antistatic agents, anti-aging agents, antioxidants, antibacterial / antifungal agents, antifoaming agents, leveling agents, Sticky agent, adhesion promoter, thixotropic agent, photoinitiator, sensitizer, organic filler, elastomer, mold release agent, surface treatment agent, dispersant, dispersion aid, surface modifier, stabilizer, Examples thereof include phosphors.
  • the curable resin composition of the present invention may contain a known and usual inorganic filler other than the coated silica particles as long as the effects of the present invention are not impaired.
  • inorganic filler include silica other than the coated silica particles, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, and aluminum hydroxide.
  • Inorganic fillers such as barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate and zinc white.
  • the curable resin composition of the present invention may contain a curing agent other than the above-mentioned curing agent as long as the effects of the present invention are not impaired.
  • a curing agent include compounds having a phenolic hydroxyl group, polycarboxylic acids and acid anhydrides thereof, and alicyclic olefin polymers.
  • the curable resin composition of the present invention may contain a thermosetting resin other than the epoxy compound as long as the effects of the present invention are not impaired.
  • thermosetting resins include isocyanate compounds, blocked isocyanate compounds, amino resins, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional oxetane compounds, episulfide resins, and the like.
  • polyfunctional oxetane compound examples include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3- Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3- In addition to polyfunctional oxetanes such as oxetanyl) 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-hydroxy
  • episulfide resin that is, a compound having a plurality of cyclic thioether groups in the molecule
  • examples of the episulfide resin include bisphenol A type episulfide resin.
  • episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
  • amino resins such as melamine derivatives and benzoguanamine derivatives include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.
  • polyisocyanate compound a polyisocyanate compound can be blended.
  • Polyisocyanate compounds include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, and Aromatic polyisocyanates such as 2,4-tolylene isocyanate dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; Alicyclic polyisocyanates such as bicycloheptane triisocyanate; and the isocyanate compounds listed above Adducts,
  • an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used.
  • an isocyanate compound which can react with an isocyanate blocking agent the above-mentioned polyisocyanate compound etc. are mentioned, for example.
  • an isocyanate block agent for example, phenol block agent; lactam block agent; active methylene block agent; alcohol block agent; oxime block agent; mercaptan block agent; acid amide block agent; imide block agent; Examples include amine-based blocking agents; imidazole-based blocking agents; imine-based blocking agents.
  • the curable resin composition of the present invention may contain a photocurable resin.
  • a photocurable resin what is necessary is just a resin which is hardened
  • a photopolymerizable oligomer, a photopolymerizable vinyl monomer or the like, which is a known and commonly used photosensitive monomer can be used, and a radical polymerizable monomer or a cationic polymerizable monomer may be used.
  • the photocurable resin a polymer such as a carboxyl group-containing resin having an ethylenically unsaturated group as described later can be used.
  • a photocurable resin can be used individually by 1 type or in combination of 2 or more types.
  • a liquid (solid) or semi-solid photosensitive (meth) acrylate compound having at least one (meth) acryloyl group in the molecule at room temperature can be used as the photosensitive monomer.
  • the photosensitive (meth) acrylate compound that is liquid at room temperature is used for the purpose of increasing the photoreactivity of the composition, as well as adjusting the composition to a viscosity suitable for various coating methods and assisting in solubility in an aqueous alkali solution. Also fulfills.
  • 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-ethoxymethylacryl (Meth) acrylamides such as amide, N-butoxymethylacrylamide; allyl compounds such as triallyl isocyanurate,
  • the curable resin composition of the present invention may contain an alkali-soluble resin.
  • the alkali-soluble resin is more preferably a carboxyl group-containing resin.
  • the carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group or a carboxyl group-containing resin having no ethylenically unsaturated group.
  • Alkali-soluble resin can be used individually by 1 type or in combination of 2 or more types.
  • carboxyl group-containing resin examples include the compounds listed below (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 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 ( Carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its partial acid anhydride modified product, 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.
  • a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride
  • 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 resin obtained by reacting a polybasic acid anhydride with a product.
  • (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 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) Reaction with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and with respect to the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, anhydrous A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as adipic acid.
  • the acid value of the alkali-soluble resin is suitably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g.
  • the acid value of the alkali-soluble resin is 40 mgKOH / g or more, alkali development is facilitated, and on the other hand, it is preferable to draw a normal cured product pattern of 200 mgKOH / g or less.
  • the weight average molecular weight of the alkali-soluble resin varies depending on the resin skeleton, but is preferably in the range of 1,500 to 150,000, more preferably 1,500 to 100,000.
  • the weight average molecular weight is 1,500 or more, the tack-free performance is good, the moisture resistance of the coated film after exposure is good, the film loss during development can be suppressed, and the resolution can be suppressed from decreasing.
  • the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is also excellent.
  • the blending amount of the alkali-soluble resin is, for example, 5 to 50% by mass in the total solid content of the composition.
  • the curable resin composition of the present invention can contain a photoinitiator.
  • the photoreaction initiator may be any one that can cure the composition by light irradiation, and is any one of a photopolymerization initiator that generates radicals by light irradiation and a photobase generator that generates bases by light irradiation. Is preferred.
  • the photoinitiator may of course be a compound that generates both radicals and bases upon light irradiation.
  • Light irradiation means irradiation with ultraviolet rays having a wavelength in the range of 350 to 450 nm.
  • 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
  • Thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone 2
  • Anthraquinones such as methyl anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; ethyl-4 -Benzoic acid esters such as dimethylaminobenzoate, 2- (dimethyla
  • the photobase generator generates one or more basic substances that can function as a catalyst for a thermosetting reaction by changing the molecular structure upon irradiation with light such as ultraviolet rays or visible light, or by cleaving the molecules.
  • a compound examples include secondary amines and tertiary amines.
  • photobase generators examples include ⁇ -aminoacetophenone compounds, oxime ester compounds, acyloxyimino compounds, N-formylated aromatic amino compounds, N-acylated aromatic amino compounds, nitrobenzyl carbamate compounds, alkoxybenzyl carbamates. Compounds and the like. Of these, oxime ester compounds and ⁇ -aminoacetophenone compounds are preferred, oxime ester compounds are more preferred, and ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) is more preferred.
  • a photobase generator may be used individually by 1 type, and may be used in combination of 2 or more type.
  • examples of the photobase generator include quaternary ammonium salts.
  • WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate), WPBG-027 (trade name: (E) -1- [3- (2-hydroxyphenyl) -2- propenoyl] piperidine), WPBG-082 (trade name: guanidinium2- (3-benzoylphenyl) propionate), WPBG-140 (trade name: 1- (anthraquinon-2-yl) ethylidazole, etc. can also be used.
  • photopolymerization initiators also function as photobase generators.
  • the photopolymerization initiator that also functions as a photobase generator is preferably an oxime ester photopolymerization initiator or an ⁇ -aminoacetophenone photopolymerization initiator.
  • the blending amount of the photoinitiator is, for example, 0.01 to 30% by mass in the total solid content of the composition.
  • the curable resin composition of the present invention is not particularly limited, and may be any of a thermosetting resin composition, a photocurable thermosetting resin composition, and a photosensitive thermosetting resin composition, for example. Moreover, an alkali development type may be sufficient and a negative type or a positive type may be sufficient. Specific examples include a thermosetting resin composition, a photocurable thermosetting resin composition, a photocurable thermosetting resin composition containing a photopolymerization initiator, and a photocurable heat containing a photobase generator.
  • Curable resin composition negative photocurable thermosetting resin composition and positive photosensitive thermosetting resin composition, alkali developing photocurable thermosetting resin composition, solvent developing photocurable thermosetting Examples include, but are not limited to, a curable resin composition, a swollen peelable thermosetting resin composition, and a melt peelable thermosetting resin composition.
  • a known and commonly used component may be selected according to curability and application.
  • the curable resin composition of the present invention when it is a thermosetting resin composition (not including a photopolymerization initiator), it contains a thermosetting resin. Moreover, it is preferable to contain a hardening accelerator. It is preferable to contain a curing agent.
  • the compounding amount of the thermosetting resin is preferably 1 to 50% by mass in the total solid content of the composition.
  • the blending amount of the curing accelerator is preferably 0.01 to 30% by mass in the total solid content of the composition.
  • the blending amount of the curing agent is preferably 0.01 to 30% by mass in the total solid content of the composition.
  • the curable resin composition of the present invention is a photocurable thermosetting resin composition
  • it contains a photocurable resin, a thermosetting resin, and a photoinitiator.
  • the photocurable resin may be an alkali-soluble resin, and may further contain an alkali-soluble resin.
  • the blending amount of the alkali-soluble resin is preferably 5 to 50% by mass in the total solid content of the composition.
  • the compounding amount of the thermosetting resin is preferably 1 to 50% by mass in the total solid content of the composition.
  • the blending amount of the photocurable resin (excluding the photocurable alkali-soluble resin) is preferably 1 to 50% by mass in the total solid content of the composition.
  • the blending amount of the photoinitiator is preferably 0.01 to 30% by mass in the total solid content of the composition.
  • the blending amount of the curing accelerator is preferably 0.01 to 30% by mass in the total solid content of the composition.
  • the curable 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 has a resin layer obtained by applying and drying the curable resin composition of the present invention on a carrier film.
  • the curable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, a rod coater, and a squeeze coater. Apply a uniform thickness on the carrier film using a reverse coater, transfer roll coater, gravure coater, spray coater or the like. Thereafter, the applied composition is usually dried at a temperature of 40 to 130 ° C. for 1 to 30 minutes to form a resin layer.
  • the coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 3 to 150 ⁇ m, preferably 5 to 60 ⁇ m.
  • a plastic film is used as the carrier film.
  • a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used.
  • the thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 ⁇ m. More preferably, it is in the range of 15 to 130 ⁇ m.
  • the surface of the resin layer is further protected to be peelable for the purpose of preventing dust from adhering to the surface of the resin layer. It is preferable to laminate a film (cover film).
  • a peelable protective film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used.
  • a protective film what is necessary is just a thing smaller than the adhesive force of a resin layer and a carrier film, when peeling a protective film.
  • a resin layer may be formed by applying and drying the curable resin composition of the present invention on the protective film, and a carrier film may be laminated on the surface. That is, as a film to which the curable resin composition of the present invention is applied when producing a dry film in the present invention, either a carrier film or a protective film may be used.
  • the curable resin composition of the present invention is a thermosetting resin composition (not containing a photopolymerization initiator), and a three-layer dry film in which a resin layer is sandwiched between a carrier film and a protective film
  • a printed wiring board can be manufactured by the following method. Either the carrier film or the protective film is peeled off from the dry film, heat laminated to the circuit board on which the circuit pattern is formed, and then thermally cured. The heat curing may be performed in an oven or by a hot plate press.
  • the copper foil or the substrate on which the circuit is formed can be laminated simultaneously.
  • a substrate having an insulating layer can be manufactured by forming a pattern or a via hole by laser irradiation or drilling at a position corresponding to a predetermined position on the substrate on which the circuit pattern is formed, and exposing the circuit wiring.
  • desmear processing is performed.
  • the remaining carrier film or protective film may be peeled off after lamination, after heat curing, after laser processing, or after desmear treatment.
  • a conductor layer is formed on the insulating layer by dry plating or wet plating.
  • dry plating a known method such as vapor deposition, sputtering, or ion plating can be used.
  • wet plating first, the surface of the cured resin composition layer (insulating layer) is coated with permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / Treat with an oxidizing agent such as sulfuric acid or nitric acid.
  • permanganate potassium permanganate, sodium permanganate, etc.
  • dichromate ozone
  • hydrogen peroxide / Treat such as sulfuric acid or nitric acid.
  • an aqueous sodium hydroxide solution alkaline permanganate aqueous solution
  • potassium permanganate and sodium permanganate is particularly preferably used.
  • a conductor layer is formed by a method in which electroless plating and electrolytic plating are combined.
  • a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating.
  • a subsequent pattern formation method for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.
  • the connection method of the interlayer circuit may be a connection using a copper pillar.
  • the surface of the conductor layer and the insulating layer is roughened.
  • an aromatic compound having an amino group and an aromatic ring, a polybasic acid having two or more carboxy groups, and a halide ion can be used.
  • An example of the product name is 01CZ manufactured by MEC.
  • Insulating layers and conductor layers may be alternately formed as described above, and a solder resist may be formed on the outermost circuit.
  • a solder resist may be formed according to the method described in paragraphs 70 to 76 of Patent 5941180.
  • the curable resin composition of the present invention is preferably used for forming a cured film on an electronic component, particularly for forming a cured film on a printed wiring board, and more preferably for forming a permanent film. Used for. More preferably, since the curable resin composition of the present invention is excellent in adhesion after HAST treatment with a conductor layer and a solder resist, it is used for forming an interlayer insulating layer. Further, it is suitable for forming a printed wiring board that requires high reliability, for example, a package substrate, particularly a permanent film (particularly an interlayer insulating layer) for FC-BGA.
  • the curable resin composition of this invention can be used suitably also for a printed wiring board provided with the wiring pattern with small roughness of a circuit surface, for example, the printed wiring board for high frequencies.
  • the surface roughness Ra is 0.05 ⁇ m or less, particularly 0.03 ⁇ m or less, it can be suitably used.
  • it can use suitably also when forming a cured film on a low polarity base material, for example, the base material containing an active ester.
  • an inorganic filler such as silica or barium sulfate is, for example, 30% by mass or more, and further 40% by mass. % Or more can be suitably used for forming a cured film that is in close contact with the cured product.
  • the curable resin composition of this invention can be used as a thing for forming a soldering resist and a coverlay.
  • the electronic component may be an application other than the printed wiring board, for example, a passive component such as an inductor.
  • silica particles coated with zirconia hydrated oxide After heating 50 g of water slurry of spherical silica particles (SFP-20M, Denka Corp., average particle size: 0.4 ⁇ m) to 70 ° C., an aqueous solution of a water-soluble zirconium compound such as 100 g / l zirconium oxychloride is added to the silica particles. 2 to 3% in terms of zirconia (ZrO 2 ) was added. Thereafter, a 20% sodium hydroxide aqueous bath solution was added to adjust the pH to 7, followed by aging for 30 minutes. Thereafter, the slurry was washed with filtered water with a filter press and vacuum-dried to obtain a solid of silica particles coated with zirconia hydrated oxide.
  • SFP-20M spherical silica particles
  • ZrO 2 zirconia
  • silica particles coated with zinc hydrated oxide A water slurry of 50 g of spherical silica particles (SFP-20M, Denka Corp., average particle size: 0.4 ⁇ m) was heated to 70 ° C., and an aqueous solution of zinc sulfate was added in an amount of 2 to 3% in terms of ZnO with respect to the silica particles. . Thereafter, a 20% sodium hydroxide aqueous bath solution was added to adjust the pH to 7, followed by aging for 30 minutes. Thereafter, the slurry was washed with filtered water with a filter press and vacuum-dried to obtain a solid of silica particles coated with hydrated zinc oxide.
  • silica particles coated with hydrated aluminum oxide and surface-treated with methacrylic silane 50 g of silica particles coated with the hydrated oxide of aluminum obtained above, 48 g of PMA as a solvent, and 1 g of a silane coupling agent having a methacryl group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) were dispersed uniformly. Filtration, washing with water, and vacuum drying gave a solid product of silica particles surface-treated with methacrylic silane.
  • silica particles coated with hydrated aluminum oxide and surface-treated with epoxy silane 50 g of silica particles coated with the aluminum hydrated oxide obtained above, 48 g of PMA as a solvent, and 1 g of a silane coupling agent having an epoxy group (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) were dispersed uniformly. Filtration, washing with water, and vacuum drying gave a solid product of silica particles surface-treated with epoxysilane.
  • silica particles coated with hydrated aluminum oxide and surface-treated with phenylaminosilane 50 g of silica particles coated with the hydrated oxide of aluminum obtained above, 48 g of PMA as a solvent, and 1 g of a silane coupling agent having a phenylamino group (KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.) are uniformly dispersed. Then, a solid body of silica particles surface-treated with phenylaminosilane was obtained by filtration, washing with water, and vacuum drying.
  • silica particles surface-treated with phenylaminosilane 50 g of spherical silica particles (SFP-20M manufactured by Denka Co., Ltd., average particle size: 0.4 ⁇ m), 48 g of PMA as a solvent, and 1 g of a silane coupling agent having a phenylamino group (KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.) Dispersion was performed, and a solid of silica particles surface-treated with phenylaminosilane was obtained by filtration, washing with water, and vacuum drying.
  • silica particles surface-treated with methacrylic silane 50 g of spherical silica particles (SFP-20M manufactured by Denka Co., Ltd., average particle size: 0.4 ⁇ m), 48 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and a silane coupling agent having a methacryl group (KBM manufactured by Shin-Etsu Chemical Co., Ltd.) -503) 1 g was uniformly dispersed, and a solid of silica particles surface-treated with methacrylic silane was obtained by filtration, washing with water, and vacuum drying.
  • SFP-20M manufactured by Denka Co., Ltd., average particle size: 0.4 ⁇ m
  • PMA propylene glycol monomethyl ether acetate
  • silane coupling agent having a methacryl group KBM manufactured by Shin-Etsu Chemical Co., Ltd.
  • talc solid material coated with aluminum hydrated oxide 50 g of talc coated with the hydrated oxide of aluminum obtained above, 48 g of PMA as a solvent, and 1 g of a silane coupling agent having a phenylamino group (KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.) were dispersed uniformly. Filtration, washing with water, and vacuum drying gave a talc solid that was surface treated with phenylaminosilane.
  • reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide.
  • the nonvolatile content was 62.1%, and the hydroxyl value was 182.2 mgKOH / g (307. 9 g / eq.) Of a novolak-type cresol resin propylene oxide reaction solution. This was an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
  • reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution.
  • 332.5 parts of the obtained novolak acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was supplied at a rate of 10 ml / min.
  • Examples 1 to 13 Comparative Examples 1 to 5
  • Various components shown in Tables 1 to 3 below are blended in proportions (parts by mass) shown in Tables 1 to 3, and after adjusting the viscosity with an organic solvent, premixed with a stirrer, kneaded with a bead mill, and cured.
  • a resin composition was prepared.
  • solder resist composition A curable resin composition for forming a solder resist (hereinafter, also referred to as “solder resist composition”) used for evaluation of the adhesion with the solder resist (SR)> was prepared. These curable resin compositions were passed through a filtration filter having an opening of 15 ⁇ m, and after removing coarse particles, the following dry film was produced.
  • the curable resin composition obtained as described above was diluted by adding 300 g of methyl ethyl ketone, and stirred for 15 minutes with a stirrer to obtain a coating solution.
  • the coating solution was applied onto a 38 ⁇ m thick polyethylene terephthalate film (PET film, Emblet PTH-25 manufactured by Unitika Co., Ltd.) having an arithmetic surface roughness Ra of 150 nm.
  • PET film polyethylene terephthalate film, Emblet PTH-25 manufactured by Unitika Co., Ltd.
  • Examples 1 to 13 and Comparative Examples 1 to 5 were The solder resist composition was dried at 80 ° C. for 10 minutes at a temperature of 100 ° C. to form a resin layer having a thickness of 20 ⁇ m.
  • a 18 ⁇ m-thick polypropylene film (protective film, OPP-FOA manufactured by Futamura Co., Ltd.) was bonded onto the resin layer to produce a dry film having a resin layer thickness of 20 ⁇ m.
  • a dry film having a resin layer thickness of 30 ⁇ m was produced.
  • Examples 1 to 13 and Comparative Examples 1 to 5 using a vacuum laminator were vacuum resisted at 3 hPa, 100 ° C., solder resist in the first chamber.
  • the composition is laminated on the object to be attached at 90 ° C. under a vacuum time of 30 seconds, and pressed under conditions of a press pressure of 0.5 MPa, 80 ° C., and a press time of 30 seconds.
  • ⁇ Dielectric loss tangent> The dry film having a resin layer thickness of 30 ⁇ m produced in the examples and comparative examples is laminated on the glossy surface of electrolytic copper foil GTS-MP-18 ⁇ m (Furukawa Circuit Foil) under the above conditions, and then flattened on the resin. After peeling off the PET film, the resin layer was completely cured (190 ° C., 60 minutes). Thereafter, the cured film was peeled from the copper foil to obtain a cured film having a thickness of 30 ⁇ m. The cured film was cut into a length of 80 mm and a width of 2 mm, and a measurement temperature of 22 ° C.
  • the 18 ⁇ m copper support was peeled off, and the ultrathin copper foil was fully etched with an etching solution (Meck Bright QE-7300, manufactured by MEC) to obtain a substrate having a cured film.
  • a 20 ⁇ m dry film having a resin layer made of the solder resist composition prepared above was laminated on the cured film under the above conditions.
  • the entire surface of the dry film was exposed (exposure amount: 400 to 600 mJ / cm 2 ), and then the polyethylene terephthalate film was peeled from the dry film, and the resin layer was removed. Exposed. Thereafter, development was performed for 60 seconds under the conditions of 30 ° C. and a spray pressure of 2 kg / cm 2 using a 1 wt% Na 2 CO 3 aqueous solution. Subsequently, after the resin layer was irradiated with an exposure amount of 1 J / cm 2 in a UV conveyor furnace equipped with a high-pressure mercury lamp, the resin layer was completely cured by heating at 160 ° C.
  • a high-pressure mercury lamp short arc lamp
  • Electrolytic copper foil GTS-MP-18 ⁇ m (Furukawa Circuit Foil Co., Ltd.) glossy surface is pre-processed by spraying MEC 01CZ to roughen the surface, and the surface roughness Ra is 0.04 ⁇ m.
  • a dry film having a resin layer thickness of 20 ⁇ m prepared in each Example and Comparative Example was laminated on this treated surface, and heat cured at 190 ° C. for 60 minutes to obtain a sample in which an insulating layer was formed.
  • the insulating layer of this sample and the FR-4 (glass epoxy) substrate were bonded with an adhesive (AR-S 30 manufactured by Nichiban).
  • This bonded body was treated for 100 hours in a high-temperature and high-humidity tank in an atmosphere of 130 ° C. and 85% humidity. Thereafter, the copper foil was peeled off using a tensile tester AG-X, and the strength at that time was evaluated. After the initial value of this sample and the HAST test at 130 ° C. and 85% RH for 100 hours, the peel strength of both samples was measured based on JIS C6481 by Autograph AG-X manufactured by Shimadzu Corporation. The higher the peel strength, the better the adhesion, and the lower the strength reduction rate before and after the HAST test, the better. (Before HAST-After HAST) / Before HAST x 100 (%) HAST 130 ° C. 85% 100 hrs A reduction rate of 40% or less is desirable.
  • the curable resin compositions of Examples 1 to 13 of the present invention have excellent adhesion after HAST treatment with the conductor layer and the solder resist, and a cured product having a low dielectric loss tangent is obtained.

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

Abstract

L'invention concerne : une composition de résine durcissable qui est excellente en matières d'adhérence de couche conductrice/réserve de soudure après un traitement HAST et qui peut donner des objets durcis présentant un faible facteur de dissipation diélectrique ; un film sec comprenant une couche de résine obtenue à partir de la composition ; un objet durci obtenu par durcissement d'une couche de résine correspondant soit à la composition, soit au film sec ; et un composant électronique comprenant l'objet durci. La composition de résine durcissable est caractérisée en ce qu'elle comprend : des particules de silice revêtues d'au moins un élément parmi un oxyde d'aluminium hydraté, un oxyde de zirconium hydraté, un oxyde de zinc hydraté et un oxyde de titane hydraté ; un composé époxy ; et un durcisseur qui correspond à l'un quelconque parmi des composés contenant un groupe ester actif, des composés contenant un groupe ester de cyanate et des composés contenant un groupe maléimide.
PCT/JP2019/002809 2018-03-30 2019-01-28 Composition de résine durcissable, film sec, objet durci et composant électronique WO2019187588A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113281965A (zh) * 2020-02-20 2021-08-20 东友精细化工有限公司 固化性树脂组合物、图案以及图像显示装置

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021014545A (ja) * 2019-07-12 2021-02-12 味の素株式会社 樹脂組成物
JP7474592B2 (ja) * 2019-12-27 2024-04-25 太陽ホールディングス株式会社 硬化性樹脂組成物、ドライフィルム、樹脂付き銅箔、硬化物、および電子部品
JP7402681B2 (ja) * 2019-12-27 2023-12-21 太陽ホールディングス株式会社 硬化性樹脂組成物、ドライフィルム、樹脂付き銅箔、硬化物、及び電子部品
JP7489775B2 (ja) 2019-12-27 2024-05-24 太陽ホールディングス株式会社 硬化性樹脂組成物、ドライフィルム、樹脂付き銅箔、硬化物、および電子部品
JPWO2022190600A1 (fr) * 2021-03-08 2022-09-15
CN113423183A (zh) * 2021-07-01 2021-09-21 定颖电子（昆山）有限公司 5g通讯高频信号板制造工艺

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11310688A (ja) * 1998-04-27 1999-11-09 Shin Etsu Chem Co Ltd 半導体封止用エポキシ樹脂組成物及び半導体装置
JP2002161151A (ja) * 2000-11-27 2002-06-04 Matsushita Electric Works Ltd プリプレグ及び積層板
WO2005108459A1 (fr) * 2004-05-11 2005-11-17 Nitto Denko Corporation Composition de résine époxy liquide
JP2005336472A (ja) * 2004-04-28 2005-12-08 Konoshima Chemical Co Ltd 水酸化マグネシウム系難燃剤とその製造方法、及び難燃性樹脂組成物
WO2010035571A1 (fr) * 2008-09-24 2010-04-01 コニカミノルタオプト株式会社 Composition pour couche antireflet, film antireflet, plaque polarisante et dispositif d’affichage d’image
US20110082239A1 (en) * 2009-10-02 2011-04-07 Nan Ya Plastics Corporation Thermosetting epoxy composition with low expansibility
WO2011118584A1 (fr) * 2010-03-26 2011-09-29 パナソニック電工株式会社 Composition de résine époxy pour pré-imprégné, pré-imprégné, et carte de circuit imprimé multicouche
JP2012241179A (ja) * 2011-05-24 2012-12-10 Panasonic Corp プリプレグ用エポキシ樹脂組成物、プリプレグ、および多層プリント配線板
JP2013095855A (ja) * 2011-11-01 2013-05-20 Sumitomo Bakelite Co Ltd プリプレグ、積層板および電子部品
WO2013111345A1 (fr) * 2012-01-23 2013-08-01 味の素株式会社 Composition de résine
WO2016010033A1 (fr) * 2014-07-18 2016-01-21 三菱瓦斯化学株式会社 Composition de résine, préimprégné, stratifié revêtu d'une feuille métallique, et carte à câblage imprimé
WO2016047682A1 (fr) * 2014-09-25 2016-03-31 積水化学工業株式会社 Film de résine, et film stratifié
WO2016088358A1 (fr) * 2014-12-02 2016-06-09 日本ゼオン株式会社 Composition de résine durcissable, objet moulé en résine durcissable, objet durci, produit stratifié, composite et carte à circuit imprimé multicouche
JP2017179014A (ja) * 2016-03-28 2017-10-05 味の素株式会社 樹脂組成物

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101323703B (zh) * 2008-07-29 2011-01-19 武汉科技学院 一种聚氨双马来酰亚胺树脂组合物、制备方法及其在覆铜板中的应用
TWI551587B (zh) * 2009-03-27 2016-10-01 Hitachi Chemical Co Ltd A thermosetting resin composition, and an insulating film, a laminate, and a printed wiring board
JP5565005B2 (ja) * 2010-03-10 2014-08-06 いすゞ自動車株式会社 Ｄｐｆ故障検出方法及びｄｐｆ故障検出装置
JP5582348B2 (ja) 2010-10-08 2014-09-03 日立化成株式会社 感光性樹脂組成物及び感光性フィルム
CN102337068B (zh) * 2011-06-29 2013-05-08 江苏大学 一种水性聚氨酯丙烯酸酯二氧化硅光固化涂料的制备方法
JP5770604B2 (ja) * 2011-11-04 2015-08-26 旭化成イーマテリアルズ株式会社 テトラカルボン酸二無水物
JP6492544B2 (ja) * 2014-10-31 2019-04-03 日立化成株式会社 光半導体封止用樹脂組成物及び光半導体装置
JP2016108499A (ja) * 2014-12-09 2016-06-20 株式会社ダイセル 硬化性エポキシ樹脂組成物及びその硬化物、光半導体素子搭載用基板、並びに光半導体装置

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11310688A (ja) * 1998-04-27 1999-11-09 Shin Etsu Chem Co Ltd 半導体封止用エポキシ樹脂組成物及び半導体装置
JP2002161151A (ja) * 2000-11-27 2002-06-04 Matsushita Electric Works Ltd プリプレグ及び積層板
JP2005336472A (ja) * 2004-04-28 2005-12-08 Konoshima Chemical Co Ltd 水酸化マグネシウム系難燃剤とその製造方法、及び難燃性樹脂組成物
WO2005108459A1 (fr) * 2004-05-11 2005-11-17 Nitto Denko Corporation Composition de résine époxy liquide
JP2005350647A (ja) * 2004-05-11 2005-12-22 Nitto Denko Corp 液状エポキシ樹脂組成物
WO2010035571A1 (fr) * 2008-09-24 2010-04-01 コニカミノルタオプト株式会社 Composition pour couche antireflet, film antireflet, plaque polarisante et dispositif d’affichage d’image
US20110082239A1 (en) * 2009-10-02 2011-04-07 Nan Ya Plastics Corporation Thermosetting epoxy composition with low expansibility
WO2011118584A1 (fr) * 2010-03-26 2011-09-29 パナソニック電工株式会社 Composition de résine époxy pour pré-imprégné, pré-imprégné, et carte de circuit imprimé multicouche
JP2012241179A (ja) * 2011-05-24 2012-12-10 Panasonic Corp プリプレグ用エポキシ樹脂組成物、プリプレグ、および多層プリント配線板
JP2013095855A (ja) * 2011-11-01 2013-05-20 Sumitomo Bakelite Co Ltd プリプレグ、積層板および電子部品
WO2013111345A1 (fr) * 2012-01-23 2013-08-01 味の素株式会社 Composition de résine
WO2016010033A1 (fr) * 2014-07-18 2016-01-21 三菱瓦斯化学株式会社 Composition de résine, préimprégné, stratifié revêtu d'une feuille métallique, et carte à câblage imprimé
WO2016047682A1 (fr) * 2014-09-25 2016-03-31 積水化学工業株式会社 Film de résine, et film stratifié
WO2016088358A1 (fr) * 2014-12-02 2016-06-09 日本ゼオン株式会社 Composition de résine durcissable, objet moulé en résine durcissable, objet durci, produit stratifié, composite et carte à circuit imprimé multicouche
JP2017179014A (ja) * 2016-03-28 2017-10-05 味の素株式会社 樹脂組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113281965A (zh) * 2020-02-20 2021-08-20 东友精细化工有限公司 固化性树脂组合物、图案以及图像显示装置

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