Classifications

• • 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
• • 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
  • C08G59/20—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 epoxy compounds used
• • 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
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • 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
  • C08L63/08—Epoxidised polymerised polyenes
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
• • 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 cured product, and a printed wiring board.
• Electronic devices such as smartphones and personal computers use printed wiring boards equipped with electronic elements having various functions.
• a circuit for electrically connecting electronic elements to each other is formed on an insulating base material.
• a circuit is made of copper and its thickness is, for example, about 18 ⁇ m. With the miniaturization of electronic devices, this circuit is designed to be thinner.
• solder resist ink for such circuits, in order to prevent the circuits from being short-circuited, it is common practice to apply an insulating material called solder resist ink to the surface of the printed wiring board to form an insulating layer. ing.
• a circuit having a thickness of more than 50 ⁇ m may be used for a printed wiring board to which a large current or a large voltage is applied, which is used for a communication server or an electric vehicle.
• the step that is, the height difference
• solder resist film in which the solder resist ink is previously formed into a film.
• solder resist film in Patent Document 1, after buffing a 1.6 mm thick FR-4 copper-clad laminate having a 35 ⁇ m thick copper foil on the entire surface and then buffing # 600 and then # 1000 once.
• the resist layer In the measurement in the color difference meter reflection mode after laminating the solder resist film with the vacuum laminator, it has a resist layer having a spectral reflectance of 65% or more measured every 10 nm between wavelengths of 430 to 700 nm.
• the resist layer contains a base polymer (A), an ethylenically unsaturated compound (B), a photopolymerization initiator (C), a white pigment (D), and a solvent (E).
• the photopolymerization initiator (C) contains an acylphosphine oxide-based photopolymerization initiator (C1) and an alkylphenone-based photopolymerization initiator (C2). ..
• An object of the present invention is to provide a curable resin composition, a cured product, and a printed wiring board capable of facilitating the polishing work of the cured product and flattening the surface thereof.
• the present inventors have found that the warp generated by the shrinkage of the curable resin composition during curing is used in the polishing work. Found to have an impact. Furthermore, as a result of diligent research, the present inventors have solved the problem of warpage when the cured product of the curable resin composition exhibits predetermined properties with respect to stress, elastic storage rate, and viscosity, and further, the polishing work of the cured product. It was found that the above can be facilitated.
• one of the present invention is a curable resin composition, which is a conical-plate type rotational viscometer measured by a conical-plate type rotational viscometer in accordance with JIS-Z8803: 2011, at 25 ° C., rotor rotation.
• the viscosity of the 30-second value measured under the condition of a speed of 5.0 rpm is 200 dPa ⁇ s or more and 3000 dPa ⁇ s or less
• the cured product of the curable resin composition has the following characteristics (1) to (2).
• Curable resin composition comprising: (1) The stress is 0.5N or more and less than 1.3N; (2) The storage elastic modulus at 30 ° C. is less than 8.8 GPa.
• the cured product of the curable resin composition has the following property (3): (3) The glass transition temperature is 120 ° C. or higher.
• the curable resin composition is (A) Epoxy resin having a liquid bisphenol skeleton, It is intended to contain (B) a curing agent and (C) an inorganic filler.
• the curable resin composition is (D) Polybutadiene epoxy resin is further contained.
• Another feature of the present invention is that it is a cured product obtained by curing a curable resin composition.
• Another feature of the present invention is a printed wiring board having the cured product.
• a curable resin composition capable of facilitating the polishing work of the cured product and flattening the surface thereof.
• the curable resin composition according to the present embodiment contains a curable resin, a curing agent, and an inorganic filler.
• the curable resin used in the present invention is a thermosetting resin or a photocurable resin, and may be a mixture thereof, but it is a thermosetting resin in that it is excellent in curability and heat resistance in a deep part. Is preferable.
• liquid means a liquid state or a semi-liquid state (paste state) which has fluidity at at least one of 20 degreeC and 45 degreeC.
• thermosetting resin may be any resin that is cured by heating and exhibits electrical insulation.
• specific examples of the thermocurable resin include novolac-type phenol resins such as phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, and triazine skeleton-containing phenol novolac resin; unmodified resolephenol resin, tung oil, flaxseed oil, and walnut oil.
• Phenol resins such as resol-type phenol resins such as oil-modified resol-phenol resins modified with, etc .; bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol E-type epoxy resin, bisphenol M-type epoxy resin, Bisphenol type epoxy resin such as bisphenol P type epoxy resin and bisphenol Z type epoxy resin; novolak type epoxy resin such as phenol novolac type epoxy resin and cresol novolac type epoxy resin; biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, arylalkylene type Epoxy resins such as epoxy resins, naphthalene-type epoxy resins, anthracene-type epoxy resins, phenoxy-type epoxy resins, dicyclopentadiene-type epoxy resins, norbornene-type epoxy resins, adamantan-type epoxy resins, and fluorene-type epoxy resins; urea (urea) resins, Resin having a
• photocurable resin examples include curable resins that can be cured by a radical addition polymerization reaction with active energy rays.
• Specific examples of the radical addition polymerization reactive component having one or more ethylenically unsaturated groups in the molecule include polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, and carbonate (meth). ) Acrylate, epoxy (meth) acrylate and the like can be mentioned.
• diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol
• acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, and N, N-dimethylaminopropylacrylamide.
• Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate; Or polyvalent acrylates such as these ethireoxyside adducts, propylene oxide adducts, or ⁇ -caprolactone adducts; phenoxyacrylates, bisphenol A diacrylates, and ethylene oxide adducts or propylene oxide adducts of these phenols, etc.
• Polyvalent acrylates Polyvalent acrylates; Polyvalent acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; not limited to the above, polyether polyols, polycarbonate diols, hydroxyl groups. Examples thereof include acrylates and melamine acrylates in which polyols such as terminal polybutadiene and polyester polyol are directly acrylated or urethane acrylated via diisocyanate, and at least one of each methacrylate corresponding to the acrylate.
• (meth) acrylate is a generic term for acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
• the above-mentioned photocurable resin is preferably liquid.
• the curable resin composition can contain an alkali-soluble resin.
• the alkali-soluble resin include a carboxyl group-containing resin and a phenol resin. It is preferable to use a carboxyl group-containing resin from the viewpoint of developability.
• the 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.
• the curable resin according to this embodiment is preferably an epoxy resin having (A) a liquid bisphenol skeleton.
• liquid bisphenol skeleton epoxy resin examples include bisphenol A type epoxy resin and its hydrogenated product, bisphenol F type epoxy resin and its hydrogenated product, bisphenol S type epoxy resin and its hydrogenated product, which satisfy the above-mentioned "liquid" conditions.
• liquid bisphenol skeleton epoxy resins include, for example, jER828 manufactured by Mitsubishi Chemical Co., Ltd., YD-127 and YD-128 manufactured by Nittetsu Chemical & Materials Co., Ltd., Araldite GY240 manufactured by Huntsman Japan Co., Ltd., and Araldite. GY250, Araldite GY260, Araldite GY261, Araldite GY266, Araldite GY2600 (all trade names), DIC Co., Ltd. Epicron 840, Epicron 850 (all trade names), etc. Bisphenol A type epoxy resin; Nittetsu Chemical & Materials Co., Ltd.
• Hydrogenated bisphenol F type epoxy resin such as YDF-170 and YDF-175 (both trade names) manufactured by the company; Epicron 830, Epicron 830-S, Epicron 835 manufactured by DIC Co., Ltd., manufactured by Mitsubishi Chemical Co., Ltd.
• Bisphenol F type epoxy resin such as JER807 (trade name); Water-added bisphenol A type epoxy resin of ST-3000 (trade name) manufactured by Nittetsu Chemical & Materials Co., Ltd .; EPOX-MK R710 manufactured by Printec Co., Ltd.
• bisphenol E type epoxy resins such as.
• the blending amount of the liquid epoxy resin having a bisphenol skeleton is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, based on the total amount of the epoxy resin in terms of solid content. preferable.
• Curing agents include, for example, imidazole latent curing agents such as amines, imidazoles, polyfunctional phenols, acid anhydrides, isocyanates, and imidazole adducts, and polymers containing these functional groups, and if necessary. A plurality of these may be used. Examples of amines include dicyandiamide and diaminodiphenylmethane. Examples of imidazoles include alkyl-substituted imidazoles and benzimidazoles.
• polyfunctional phenols include hydroquinone, resorcinol, bisphenol A and halogen compounds thereof, and novolak and resor resins which are condensates of aldehydes.
• acid anhydride include phthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, benzophenone tetracarboxylic acid and the like.
• isocyanates include tolylene diisocyanate and isophorone diisocyanate, and those isocyanates masked with phenols or the like may be used.
• amines and imidazoles can be preferably used.
• Adduct compounds of aliphatic polyamines such as alkylenediamines having 2 to 6 carbon atoms, polyalkylene polyamines having 2 to 6 carbon atoms, aromatic ring-containing aliphatic polyamines having 8 to 15 carbon atoms, or isophorone diamines, 1,3-bis.
• the main component is an adduct compound of an alicyclic polyamine such as (aminomethyl) cyclohexane, or a mixture of the adduct compound of the aliphatic polyamine and the adduct compound of the alicyclic polyamine.
• a curing agent containing an adduct compound of xylylenediamine or isophoronediamine as a main component is preferable.
• adduct compound of the aliphatic polyamine those obtained by addition reaction of aryl glycidyl ether (particularly phenyl glycidyl ether or trill glycidyl ether) or alkyl glycidyl ether to the aliphatic polyamine are preferable.
• aryl glycidyl ether particularly phenyl glycidyl ether or trill glycidyl ether
• alkyl glycidyl ether alkyl glycidyl ether
• alkyl glycidyl ether alkyl glycidyl ether
• Aliphatic polyamines include alkylenediamines having 2 to 6 carbon atoms such as ethylenediamine and propylenediamine, polyalkylene polyamines having 2 to 6 carbon atoms such as diethylenetriamine and triethylenetriamine, and aromatic ring-containing fats having 8 to 15 carbon atoms such as xylylenediamine. Examples include group polyamines. Examples of commercially available modified aliphatic polyamines include FXE-1000 or FXR-1020, Fujicure FXR-1030, Fujicure FXR-1080, FXR-1090M2 (trade names, all manufactured by T & K TOKA Co., Ltd.), Ancamin 2089K, and the like. Examples thereof include Sanmide P-117, Sanmide X-4150, Ancamin 2422, Surfet R, Sanmide TX-3000, and Sanmide A-100 (trade names, all manufactured by Evonik Japan Co., Ltd.).
• Examples of the alicyclic polyamine include isophorone diamine, 1,3-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, norbornene diamine, 1,2-diaminocyclohexane, and laromine.
• Commercially available products of the modified alicyclic polyamine include, for example, Ancamine 1618, Ancamine 2074, Ancamine 2596, Ancamine 2199, Sanmide IM-544, Sanmide I-544, Ancamine 2075, Ancamine 2280, Ancamine 1934, Ancamine 2228 (all trade names).
• imidazoles include reactants of epoxy resin and imidazole.
• imidazoles of 2E4MZ, C11Z, C17Z, 2PZ all trade names, which are reactants of epoxy resin and imidazole
• 2MZ-A, 2E4MZ-A, and 2MZA-PW Any trade name, these are AZINE compounds of imidazole
• 2MZ-OK, 2PZ-OK both trade names, these are isocyanurates of imidazole
• 2PHZ, 2P4MHZ both trade names, these are imidazoles) (Hydroxymethyl compound) (all of the above are manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like.
• imidazole-type latent curing agents examples include Cure Duct P-0505 (trade name, manufactured by Shikoku Chemicals Corporation). Further, as the curing agent to be used in combination with imidazoles, a modified aliphatic polyamine, a polyamine type curing agent, and an imidazole type latent curing agent are preferable.
• curing agents may be used alone, or two or more types may be used in combination. When two or more kinds are used in combination, one of them may be imidazoles.
• the amount of the curing agent (B) to be blended is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin in terms of solid content, and is preferably 3 to 10 parts by mass. It is more preferable to contain a part.
• a known inorganic filler used in a general resin composition can be used. Specifically, for example, non-metals such as silica, barium sulfate, calcium carbonate, silicon nitride, aluminum nitride, boron nitride, alumina, magnesium oxide, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, talc, and organic bentonite. Examples include fillers and metal fillers such as copper, gold, silver, palladium and silicone. One type of these inorganic fillers may be used alone, or two or more types may be used in combination.
• calcium carbonate, silica, barium sulfate, and aluminum oxide which are excellent in low moisture absorption and low volume expansion, are preferably used, and among them, silica and calcium carbonate are more preferably used.
• the silica may be amorphous or crystalline, or a mixture thereof. Amorphous (molten) silica is particularly preferable.
• the calcium carbonate may be either natural heavy calcium carbonate or synthetic precipitated calcium carbonate.
• the shape of the inorganic filler is not particularly limited, and examples thereof include a spherical shape, a needle shape, a plate shape, a scale shape, a hollow shape, an indefinite shape, a hexagonal shape, a cubic shape, and a flaky shape. From the viewpoint, a spherical shape is preferable.
• the amount of the inorganic filler (C) in the curable resin composition of the present invention is preferably 20 to 150 parts by mass and 30 to 120 parts by mass with respect to 100 parts by mass of the epoxy resin in terms of solid content. It is more preferable to do so.
• the curable resin composition according to the present embodiment is more preferable because it contains (D) a polybutadiene epoxy resin, so that the warpage of the cured product can be further suppressed.
• Polybutadiene epoxy resin has a double bond at the residue of the polymer, and a part of it is epoxidized.
• an epoxidized copolymer polyene having a butadiene structure can be mentioned.
• epoxidized polybutadiene is preferable.
• Specific examples of such resins include PB3600 and PB4700 manufactured by Daicel Corporation, JP-100 and JP-200 manufactured by Nippon Soda Corporation, BF-1000 manufactured by ADEKA Corporation, and YX7400 series manufactured by Mitsubishi Chemical Corporation. Can be mentioned.
• the amount of the polybutadiene epoxy resin (D) in the curable resin composition of the present invention is preferably 5 to 40% by mass with respect to the total amount of the epoxy resin in terms of solid content, and 5 to 30% by mass is contained. It is more preferable to do so.
• the curable resin composition of the present embodiment is preferable in that it does not contain a solvent (that is, a solvent-free system), so that the foam removal property is further improved, and as a result, the heat resistance is further improved.
• the curable resin composition of the present embodiment does not exclude any resin component other than a liquid (for example, a solid or semi-solid resin component). That is, if the curable resin composition is in a liquid state having fluidity at at least one of 20 ° C. and 45 ° C., a resin component that is not a liquid alone at at least one of 20 ° C. and 45 ° C. It may be included.
• the curable resin composition of the present invention further contains, if necessary, a photopolymerization initiator, a photoacid generator, a photobase generator, a photoinitiator aid, a cyanate compound, an elastomer, a mercapto compound, a urethanization catalyst, and a thixo.
• Agents adhesion accelerators, block copolymers, chain transfer agents, polymerization inhibitors, copper damage inhibitors, antioxidants, rust preventives, organic bentonite, thickeners such as montmorillonite, silicone-based, fluorine-based, high At least one of a polymer-based defoaming agent and a leveling agent, a silane coupling agent such as an imidazole type, a thiazole type, and a triazole type, a flame retardant such as a phosphorus compound such as a phosphinate, a phosphoric acid ester derivative, and a phosphazene compound. Ingredients such as can be blended. As these, those known in the field of electronic materials can be used.
• Examples of the photoacid generator include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4 -Chlorphenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] Examples thereof include sulfide bishexafluoroantimonate, (2,4-cyclopentadiene
• Examples of the photobase generator include an oxime ester compound, an ⁇ -aminoacetophenone compound, an acyloxyimino group, an N-formylated aromatic amino group, an N-acylated aromatic amino group, a nitrobenzyl carbamate group, and an alcoholoxybenzyl carbamate.
• Examples thereof include compounds having a substituent such as a group.
• the curable resin composition according to the present embodiment includes a thermosetting resin composition, a photocurable resin composition, and a photocurable thermosetting resin composition.
• the thermosetting resin composition is preferable in terms of excellent curability and heat resistance.
• the cured product according to the present embodiment is a cured product of the above-mentioned curable resin composition.
• the cured product of the curable resin composition in the present embodiment means that when the curable resin composition is used as the thermosetting resin composition, a differential scanning calorimeter (DSC) before and after curing of the curable resin composition is used. 5 ° C / min.
• the reaction rate calculated from the ratio of each calorific value measured by measuring in the range of 20 to 250 ° C. at the temperature rising rate of is 80% or more.
• Examples of the measuring device include a differential scanning calorimeter DSC8500 manufactured by PerkinElmer.
• the curable resin composition of the present invention is used as a photocurable resin composition
• the curable resin composition is exposed with an integrated light amount of 1000 mJ / cm 2 using an ultraviolet exposure machine equipped with a high-pressure mercury lamp. It means something.
• the curable resin composition of the present invention is used as a photocurable thermosetting resin composition
• the curable resin composition is dried at 80 ° C. for 30 minutes in a hot air circulation type drying furnace, and then a high-pressure mercury lamp is used. It refers to a product that has been exposed with an integrated light amount of 1000 mJ / cm 2 using an ultraviolet exposure machine equipped with a lamp, and further cured at 180 ° C. for 60 minutes in a hot air circulation type drying furnace.
• the cured product of the curable resin composition of the present embodiment has the following characteristics (1) and (2).
• the stress is 0.5 N or more and less than 1.3 N.
• the storage elastic modulus at 30 ° C. is less than 8.8 GPa.
• the measurement of the storage elastic modulus in this embodiment is as follows. That is, the curable resin composition was applied to the glossy surface of the 18 ⁇ m copper foil (GTS-MP foil (manufactured by Furukawa Electric Co., Ltd.)) so that the coating thickness after curing was 100 ⁇ 50 ⁇ m. Is applied by screen printing. Then, the curable resin composition is heat-cured at 150 ° C. for 60 minutes to prepare a cured product. The produced cured product is peeled off from the copper foil and cut into pieces of 5 ⁇ 0.3 mm ⁇ 50 ⁇ 5 mm.
• GTS-MP foil manufactured by Furukawa Electric Co., Ltd.
• the storage elastic modulus in this embodiment is preferably 6.0 GPa or less at 30 ° C.
• the stress measurement in this embodiment is as follows. That is, in the above-mentioned measurement of the storage elastic modulus, the value obtained by subtracting the minimum value from the maximum value of the axial force is defined as the stress value (that is, the stress applied during reflow).
• the stress in this embodiment is preferably 0.5 N or more and 1.2 N or less.
• the measurement of the viscosity of the curable resin composition in the present embodiment is as follows. That is, the cone-plate type rotational viscometer (cone-plate type) (cone plate type) in accordance with JIS-Z8803: 2011, specifically JIS-Z8803: 2011 10 "Conical-Viscosity measurement method using a flat plate type rotational viscometer” (cone plate type) A 30-second value measured under the conditions of 25 ° C. and a rotor rotation speed of 5.0 rpm using TVE-33H, rotor 3 ° ⁇ R9.7) manufactured by Toki Sangyo Co., Ltd. was used as the viscosity.
• the viscosity in this embodiment is preferably 400 dPa ⁇ s or more and 1200 dPa ⁇ s or less in a 30-second value measured under the conditions of 25 ° C. and a rotor rotation speed of 5.0 rpm.
• the polishing work of the cured product of the curable resin composition becomes easy, and the reason why the surface thereof can be flattened is presumed as follows. .. That is, the cured product of the curable resin composition has an appropriate hardness for polishing work because the storage elastic modulus is in the range of (1). Further, when the stress is in the range of (2), the warp of the cured product (or the warp of the printed wiring board coated with the cured product) can be suppressed. That is, the cured product of such a curable resin composition has an appropriate hardness and the warp is suppressed, so that the cured product is in an appropriate state for performing the polishing operation. As a result, the polishing operation of the cured product can be easily performed.
• a smooth solder resist layer can be formed on the printed circuit board.
• the viscosity in the 30-second value measured under the conditions of the viscosity of 25 ° C. and the rotor rotation speed of 5.0 rpm, when the viscosity is in the range of 200 dPa ⁇ s or more and 3000 dPa ⁇ s or less, in the defoaming step performed before curing, Good defoaming property become. Therefore, it is presumed that it can be suitably used as a filler used for printed wiring boards. The explanation of the above reason does not deny other reasons.
• the stress and storage elastic modulus of the cured product of the curable resin composition are 0.5N or more and less than 1.3N, respectively, by appropriately adjusting the type and blending amount of each component contained in the curable resin composition. And can be less than 8.8 GPa. For example, even if the resin component contains a component that easily generates stress, it can be set in a desired range by adjusting at least one component of the inorganic filler and the curing agent. ..
• the viscosity of the cured product of the curable resin composition can be adjusted to 200 dPa ⁇ s or more and 3000 dPa ⁇ s or less by appropriately adjusting the type and blending amount of each component of the curable resin composition. For example, even if the size of the inorganic filler is small and the viscosity tends to be high, the viscosity can be adjusted to this range by appropriately adjusting at least one of the components of the resin and the curing agent, the manufacturing method, and the like. be able to.
• Examples of the cured product of the curable resin composition include a cured film obtained by applying the curable resin composition to the object to be coated and curing it.
• the body to be coated is not particularly limited, and any body to be coated may be used as long as it is provided with a cured film.
• the method for applying the curable resin composition is not particularly limited, and the dip coating method, flow coating method, roll coating method, bar coater method, screen printing method, curtain coating method, inkjet coating method, dispensing method, etc. Various methods can be applied. Of these, the screen printing method is preferable.
• the curable resin composition according to the present embodiment can be used to fill a recess formed between copper circuits having a predetermined thickness arranged on a printed wiring board. For example, after applying the curable resin composition according to the present embodiment to a copper circuit (for example, a step portion with a printed wiring board, a side surface of the copper circuit) and filling the recess formed between the copper circuits. It is cured by at least one of heating and light irradiation.
• This curable resin composition can be suitably used in the case of a printed wiring board having a copper circuit thickness of more than 50 ⁇ m. In particular, it is preferable to use it in the range where the thickness of the copper circuit is in the range of 50 ⁇ m to 600 ⁇ m.
• the viscosity suitable for coating the curable resin composition on the printed wiring board is, for example, 200 dPa ⁇ s or more and 3000 dPa ⁇ s or less (measured with a conical-plate type rotational viscometer in accordance with JIS-Z8803: 2011 5). (Viscosity at 0.0 rpm).
• the curable resin composition in the printed wiring board can be cured by heating at 60 to 220 ° C. for 20 to 240 minutes, and is circulated with hot air.
• the thermosetting resin composition contains, for example, a photobase generator
• the generated base is liquid by irradiating light before the heating step
• the thermosetting resin such as an epoxy resin having a bisphenol skeleton is thermosetting.
• the curing of the curable resin composition on the printed wiring board is about 500 to 2000 mJ / cm 2 when the curable resin composition is a photocurable resin composition, for example, using an ultraviolet exposure machine equipped with a high-pressure mercury lamp.
• exposure light irradiation
• the exposed portion light-irradiated portion
• the solvent is used, for example, in a hot air circulation type drying furnace at about 80 to 100 ° C.
• the resin layer obtained after heating to a temperature and volatilizing and drying is exposed (light irradiation) with an integrated light amount of about 500 to 2000 mJ / cm 2 using, for example, an ultraviolet exposure machine equipped with a high-pressure mercury lamp.
• the exposed part (the part irradiated with light) is cured.
• the unexposed portion is exposed to a dilute alkaline aqueous solution (a dilute alkaline aqueous solution) by selectively exposing the unexposed portion with an active energy ray through a photomask in which a pattern is formed by a contact method or a non-contact method, or by directly exposing the pattern with a laser direct exposure machine.
• a resist pattern is formed by developing with 0.3 to 3 mass% sodium carbonate aqueous solution). Further, for example, it can be cured by heating to a temperature of about 100 to 180 ° C. and thermosetting (post-curing).
• the obtained cured product is then polished. Specifically, it is carried out by a buffing machine or the like using a high-cut buff until the copper surface of the copper circuit is exposed.
• * 1 to * 25 in Tables 1 and 2 indicate the following contents.
• the viscosity, storage elastic modulus, glass transition temperature, and stress of the curable resin composition were measured by the following methods.
• the curable resin composition is applied to the glossy surface of a copper foil (GTS-MP foil (manufactured by Furukawa Electric Co., Ltd.)) with a storage elastic modulus of 18 ⁇ m, and the coating thickness after curing is 100 ⁇ 50 ⁇ m. It was applied by screen printing so as to become. Then, the curable resin composition was heat-cured at 150 ° C. for 60 minutes to prepare a cured product. The produced cured product was peeled off from the copper foil and cut into pieces of 5 ⁇ 0.3 mm ⁇ 50 ⁇ 5 mm.
• GTS-MP foil manufactured by Furukawa Electric Co., Ltd.
• the measurement temperature is 25 to 300 ° C.
• the heating rate is 5 ° C./min
• the loading gap is 10 mm
• the frequency is 1 Hz
• the axial force (axial force) is 0.05 N.
• the storage elastic modulus of the piece was measured. At this time, the storage elastic modulus at 30 ° C. in the measurement was used as the measured value.
• the value obtained by subtracting the minimum value from the maximum value of the axial force was defined as the stress value (that is, the stress applied during reflow).
• a differential scanning calorimeter manufactured by PerkinElmer, DSC8500
• the temperature rise rate was measured in the range of 20 to 250 ° C., and the reaction rate was calculated from the ratio of each calorific value measured, and it was confirmed that the reaction rate was 80% or more.
• the curable resin composition was applied to the entire surface of the dried substrate by a screen printing method in a direction parallel to the pattern so that the cured coating thickness was 120 ⁇ m. Then, after leaving it at 20 ° C. for 10 minutes, the curable resin composition was heat-cured under the conditions of 150 ° C. for 60 minutes. While irradiating the substrate side of the double-sided printed circuit board with transmitted illumination, the coated side of the curable resin composition was observed at 20 times using an optical microscope (Digital Microscope VHX-6000 manufactured by KEYENCE CORPORATION), and the circuit and circuit Counted the number of bubbles between. The bubble removal property was evaluated as follows based on the number of bubbles.
• ⁇ 5 or less bubbles of 100 ⁇ m or more.
• ⁇ More than 5 bubbles of 100 ⁇ m or more and 10 or less bubbles.
• X More than 10 bubbles of 100 ⁇ m or more.
• XX The curable resin composition could not be applied to the substrate.
• a substrate similar to the substrate whose foam removal property was evaluated was prepared, and one surface of the substrate was CZ coarse with an etching rate of 1.0 ⁇ m using CZ-8101B (manufactured by MEC COMPANY Ltd.) as a chemical solution. After the chemical treatment, it was washed with water and dried. The curable resin composition was applied to the entire surface of the dried substrate by a screen printing method in a direction parallel to the pattern so that the cured coating thickness was 120 ⁇ m. Then, the substrate to which the curable resin composition was applied was heated at 150 ° C. for 60 minutes to thermally cure the applied curable resin composition.
• the composition of the substrate was applied and the surface on the cured side was polished to remove the cured product on the copper circuit.
• the cured product was polished by a buff polishing machine (manufactured by Ishii Notation Co., Ltd.) using a high-cut buff # 320 (manufactured by Sumitomo 3M Ltd.) until the copper surface of the copper circuit was exposed to prepare an evaluation substrate.
• ⁇ The difference in thickness is less than 30 ⁇ m.
• X The difference in thickness is 30 ⁇ m or more.
• a substrate similar to the substrate whose defoaming property was evaluated was prepared, and one surface of the substrate was polished with Baflor as a pretreatment, then washed with water and dried.
• the curable resin composition was applied to the entire surface of the dried substrate by a screen printing method in a direction parallel to the pattern so that the cured coating thickness was 120 ⁇ m.
• the curable resin composition was heat-cured at 150 ° C. for 30 minutes, and then the obtained printed circuit board (that is, the evaluation substrate) left to stand until room temperature was subjected to the following treatment.
• the evaluation substrate coated with the rosin-based flux is immersed in a solder bath set at 260 ° C. in advance, the flux is washed with a modified alcohol, and then the swelling and peeling of the resin layer of the cured product are visually observed.
• the heat resistance was evaluated as follows. " ⁇ ”: No peeling is observed even after one immersion for 30 seconds. " ⁇ ”: There is slight peeling after one immersion for 30 seconds, but there is no effect on the whole. "X”: Immersion is performed once for 30 seconds, causing swelling and peeling. "-”: Not evaluated because the foam removal property is "XX".
• a curable resin composition was applied onto a 300 mm ⁇ 150 mm copper foil having a warp of 35 ⁇ m so that the coating thickness after curing was 100 ⁇ 50 ⁇ m.
• the curable resin composition was heat-cured under the conditions of 150 ° C. and 60 minutes.
• the copper foil on which the cured product was formed was cut out with a piece of 70 mm ⁇ 70 mm and placed on a predetermined flat plate. Then, each distance from the surface of the flat plate to each apex of the piece was measured with a ruler as a "warp amount" and evaluated as follows.
• the film thickness after curing, the curing conditions, and the cut-out area were given widths, but these widths were set within the range where the evaluation of warpage did not change.
• Table 1 shows the results of evaluation of the physical property values and properties of the cured product of the curable resin composition according to the examples.
• Table 2 shows the results of evaluation of the physical property values and properties of the cured product of the curable resin composition according to the comparative example.
• the characteristics of the cured product of the curable resin composition are that the stress is 0.5 N or more and less than 1.3 N, and the storage elastic modulus at 30 ° C. is less than 8.8 GPa. It was confirmed that the viscosity is preferably 200 dPa ⁇ s or more and 3000 dPa ⁇ s or less.
• the curable resin composition according to Example 1-8 is a solvent-free system. Therefore, it is considered that bubbles (that is, voids) are less likely to be generated in the first place and the performance as a filling material is excellent.
• the heat resistance of the cured product of the curable resin composition according to Example 1-9 was " ⁇ ” or " ⁇ ", and the glass transition temperature was 120 ° C. or higher. Therefore, it can be said that the printed wiring board using the cured product having such a glass transition temperature has excellent heat resistance.
• the viscosity of the curable resin composition is preferably 300 dPa ⁇ s or more and 1200 dPa ⁇ s or less.

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