WO2019189171A1 - 放熱絶縁性樹脂組成物、及びそれを用いたプリント配線板 - Google Patents

放熱絶縁性樹脂組成物、及びそれを用いたプリント配線板 Download PDF

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Publication number
WO2019189171A1
WO2019189171A1 PCT/JP2019/012839 JP2019012839W WO2019189171A1 WO 2019189171 A1 WO2019189171 A1 WO 2019189171A1 JP 2019012839 W JP2019012839 W JP 2019012839W WO 2019189171 A1 WO2019189171 A1 WO 2019189171A1
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Prior art keywords
resin composition
heat
dissipating
insulating resin
meth
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PCT/JP2019/012839
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English (en)
French (fr)
Japanese (ja)
Inventor
義和 大胡
Original Assignee
太陽インキ製造株式会社
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Priority to CN201980016406.XA priority Critical patent/CN111788870B/zh
Priority to KR1020207030064A priority patent/KR102679624B1/ko
Publication of WO2019189171A1 publication Critical patent/WO2019189171A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/10—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives

Definitions

  • the present invention relates to an insulating resin composition excellent in heat dissipation and a printed wiring board using the same, and more particularly, has a heat dissipation useful for a resin insulating layer used for a package substrate, a surface-mounted light emitting diode, or the like.
  • the present invention relates to a heat insulating resin composition having excellent storage stability and a printed wiring board using the same.
  • a metal plate such as copper or aluminum is used, and an electric insulation layer such as a prepreg or a thermosetting resin composition is provided on one side or both sides of the metal plate.
  • a metal base substrate for forming a circuit pattern has been proposed (see, for example, Patent Document 1).
  • Patent Document 1 A metal base substrate for forming a circuit pattern has been proposed (see, for example, Patent Document 1).
  • the thermal conductivity of the electrical insulating layer is low, it is necessary to make the insulating layer thin. As a result, there is a problem that the dielectric strength of the electrical insulating layer is lowered.
  • solder resist compositions for example, see Patent Document 2
  • interlayer insulating materials used for such package substrates are based on low molecular weight epoxy compounds, and the filler has excellent electrical insulation and chemical resistance. Since precipitated barium sulfate was used, sufficient heat dissipation was not obtained.
  • the use of alumina, which is expected to have heat dissipation, electrical insulation, and chemical resistance, as a filler has also been studied. However, since the alumina settles severely and the precipitated alumina aggregates tightly, the storage stability is reduced. It was poor in practicality.
  • JP-A-6-224561 Japanese Patent Laid-Open No. 11-288091
  • the present invention has been made in view of the above-described problems, and its main purpose is that high- and close-packing of heat-dissipating fine particles is possible without causing sedimentation and aggregation, and storage stability and printability.
  • An object of the present invention is to provide a heat dissipating insulating resin composition excellent in heat conductivity (heat dissipating property) of a cured product.
  • Another object of the present invention is to provide a printed wiring board in which an insulating layer and / or a solder resist layer is formed from a cured product obtained by heat-curing and / or photocuring the heat-dissipating insulating resin composition.
  • the inventor conducted intensive studies focusing on silicon carbide particles that have not only high hardness but also high thermal conductivity and excellent high-temperature heat resistance.
  • silicon carbide particles that have not only high hardness but also high thermal conductivity and excellent high-temperature heat resistance.
  • ⁇ -type silicon carbide particles are relatively fine and can be highly packed or closely packed without being settled.
  • the heat radiation insulating resin composition it has been found that a cured product having excellent storage stability and printability and excellent thermal conductivity can be provided, and the present invention has been completed.
  • the heat-radiating insulating resin composition of the present invention is a heat-radiating insulating resin composition containing (A) heat-dissipating inorganic particles and (B) a curable resin composition, and the (A) heat-dissipating property.
  • the inorganic particles contain at least (A-1) ⁇ -silicon carbide particles, and the volume occupation ratio of the (A) heat-dissipating inorganic particles is based on the total capacity of the cured product of the heat-dissipating insulating resin composition. 60% by volume or more.
  • the (B) curable resin composition is preferably (B-1) a thermosetting resin composition.
  • thermosetting resin composition contains an epoxy compound and / or an oxetane compound, a curing agent and / or a curing catalyst.
  • the (B) curable resin composition is preferably (B-2) a photocurable resin composition.
  • the (B-2) photocurable resin composition contains a compound having one or more ethylenically unsaturated bonds in one molecule and a photopolymerization initiator. It is preferable.
  • the printed wiring board of the present invention is characterized in that an insulating layer and / or a solder resist layer is formed from a cured product obtained by heat-curing and / or photocuring the heat-dissipating insulating resin composition. Is.
  • thermo radiation insulation resin composition excellent in the thermal conductivity (heat dissipation) of hardened
  • Such a heat-dissipating insulating resin composition having excellent thermal conductivity (heat dissipating property) and excellent storage stability is applied to a package substrate or a resin insulating layer on which a semiconductor chip or a light-emitting diode with a large amount of heat is mounted. Since it can be used suitably and it is excellent in thermal conductivity, the package can be downsized.
  • the heat-dissipating insulating resin composition of the present invention is a heat-dissipating insulating resin composition comprising (A) heat-dissipating inorganic particles and (B) a curable resin composition, wherein (A) heat-dissipating inorganic particles And (A-1) containing ⁇ -silicon carbide particles, and the volume occupancy of the (A) heat-dissipating inorganic particles is 60 with respect to the total cured product volume of the heat-dissipating heat-insulating resin composition. It is characterized by being at least volume%.
  • the (A) heat-dissipating inorganic particles of the present invention contain at least (A-1) ⁇ -silicon carbide particles.
  • ⁇ -silicon carbide may be mixed as an impurity as long as it has no effect.
  • Silicon carbide includes (A-1) ⁇ -silicon carbide having a zinc blende structure (denoted as 3C) and an ⁇ shown by a combination of a wurtzite structure having the same characteristics as the zinc blende type. -There is silicon carbide. ⁇ -silicon carbide is industrially produced by the Atchison method, and usually has a coarse particle diameter, even if it is fine, the average particle diameter is about 5 ⁇ m, and is pulverized and sold. On the other hand, (A-1) ⁇ -silicon carbide synthesized in the low temperature range by the same Atchison method is produced with relatively fine particles.
  • ⁇ -silicon carbide sold as a pulverized powder is an irregular shape having a sharp crushing shape, so that it is difficult to achieve high filling or close packing in the composition. In the state, it could not be used as the heat dissipating inorganic particles for the heat dissipating insulating resin composition.
  • ⁇ -silicon carbide produced with relatively fine particles has a rounded shape, and can be filled in the composition at a high density or close-packed, which is used as heat-dissipating inorganic particles.
  • the heat-dissipating inorganic particles are unlikely to settle, and the thermal conductivity can be improved without deteriorating the printability.
  • A-1 Commercial products of ⁇ -silicon carbide particles include ⁇ -SiC 800 (supplied by Superior Graphite, average particle size 7.8 ⁇ m), ⁇ -SiC 1200 (supplied by Superior Graphite, average particle size 6.0 ⁇ m). ), ⁇ -SiC 1500 (manufactured by Superior Graphite, average particle size 1.3 ⁇ m), ⁇ -SiC 2500 (manufactured by Superior Graphite, average particle size 0.6 ⁇ m), and the like.
  • the ⁇ -silicon carbide particles are preferably substantially spherical, and are preferably used without being pulverized because they have a substantially spherical shape in an unground state.
  • (A-1) heat-dissipating inorganic particles that can be used in combination with ⁇ -silicon carbide particles include ceramic particles that emit far-infrared rays (also referred to as far-infrared ceramic particles).
  • Al 2 O 3 aluminum oxide (Al 2 O 3 ), silica (SiO 2 ), zirconia (ZrO 2 ), titanium oxide (TiO 2 ), magnesium oxide (MgO), mullite (3Al 2 O 3 .2SiO 2 ), zircon (and Among these, ZrO 2 ⁇ SiO 2 ), cordierite (2MgO ⁇ 2Al 2 O 3 ⁇ 5SiO 2 ), silicon nitride (Si 3 N 4 ), manganese oxide (MnO 2 ), iron oxide (Fe 2 O 3 ), Examples include cobalt oxide (CoO).
  • the far infrared ray indicates an electromagnetic wave having a wavelength of 4 to 1000 ⁇ m, which is a general concept.
  • the ceramic particles that emit far infrared rays are ceramics having a high far infrared ray emissivity of preferably 80% or more with respect to an ideal black body, as described in, for example, Japanese Patent Application Laid-Open No. 2003-136618. Particles.
  • aluminum oxide is preferable because it is chemically stable and has excellent insulating properties.
  • the use of spherical aluminum oxide can alleviate the increase in viscosity when highly filled.
  • Commercially available aluminum oxide particles include DAW-05 (manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 5 ⁇ m), DAW-07 (manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 8 ⁇ m), DAW-10 (Electric Chemical Industry Co., Ltd., average particle size 10 ⁇ m), AS-40 (Showa Denko Co., Ltd., average particle size 12 ⁇ m), AS-50 (Showa Denko Co., Ltd., average particle size 9 ⁇ m), ASFP-20 (Made by Showa Denko KK, average particle size 0.3 ⁇ m).
  • (A-1) The content ratio of (A) ⁇ -silicon carbide particles in (A) heat-dissipating inorganic particles becomes clear when the content is 10% by volume or more, and preferably 20% by volume or more.
  • (A-1) the heat-dissipating inorganic particles containing ⁇ -silicon carbide particles do not transmit ultraviolet light
  • the heat-dissipating inorganic particles (A) of the present invention containing at least ⁇ -silicon carbide particles preferably have an average particle size of 0.01 to 30 ⁇ m, more preferably 0.01 to 20 ⁇ m. is there.
  • the average particle size is 0.01 ⁇ m or more, the viscosity of the composition does not become too high, the dispersion is easy, and the application to the coating object becomes easy.
  • the average particle size is 30 ⁇ m or less, the cueing from the coating film is less likely to occur and the sedimentation rate is sufficiently slow, so that the storage stability is improved.
  • the heat-dissipating inorganic particles of the present invention can be further filled by blending those having an average particle size of two or more kinds having a particle size distribution that results in closest packing. It is preferable from both sides of stability and thermal conductivity.
  • the average particle size of the heat-dissipating inorganic particles is not only the particle size of the primary particles, but also the average particle size including the particle size of the secondary particles (aggregates) (D50). It is the value of D50 measured by the laser diffraction method.
  • An example of a measuring apparatus using a laser diffraction method is Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd.
  • the (A) heat-dissipating inorganic particles of the present invention are preferably surface-treated with a coupling agent such as a silane coupling agent in terms of improving the low water absorption, thermal shock resistance and crack resistance of the cured product.
  • a coupling agent such as a silane coupling agent
  • coupling agents such as silane, titanate, aluminate and zircoaluminate can be used. Of these, silane coupling agents are preferred. Examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) -3-amino.
  • These coupling agents are prepared by separately blending the surface-untreated (A) heat-dissipating inorganic particles and the coupling agent, and (A) the heat-dissipating inorganic particles may be surface-treated in the composition. It is preferable to immobilize the coupling agent on the surface of the heat-dissipating inorganic particles in advance by adsorption or reaction (A). In this case, the amount of the coupling agent used for the surface treatment and the surface treatment method are not particularly limited.
  • the blending amount of the (A) heat-dissipating inorganic particles of the present invention containing ⁇ -silicon carbide particles is 60% by volume or more with respect to the total capacity of the cured product of the heat-dissipating insulating resin composition.
  • the (B) curable resin composition used in the present invention is (B-1) a thermosetting resin composition or (B-2) a photocurable resin composition, and may be a mixture thereof. .
  • thermosetting resin composition is a composition that is cured by heating and exhibits electrical insulation, for example, an epoxy resin composition, an oxetane resin composition, a melamine resin composition, a silicone resin composition.
  • a thermosetting resin composition containing an epoxy compound and / or an oxetane compound and a curing agent and / or a curing catalyst can be preferably used.
  • epoxy compound known compounds can be used as long as they have one or more, preferably two or more epoxy groups in one molecule.
  • bisphenol A type epoxy resin bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3 -Diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris (2,3-epoxypropyl)
  • examples thereof include compounds having two or more epoxy groups in one molecule such as isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate.
  • monoepoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl (meth) acrylate may be added as long as the cured coating film characteristics are not deteriorated. Moreover, these can be used individually or in combination of 2 or more types according to the request
  • the oxetane compound is represented by the following general formula (I): (In the formula, R1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
  • a compound containing an oxetane ring, and specific compounds include 3-ethyl-3-hydroxymethyl oxetane (trade name OXT-101 manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (phenoxymethyl) Oxetane (trade name OXT-211 manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (trade name OXT-212 manufactured by Toagosei Co., Ltd.), 1,4-bis ⁇ [(3-Ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene (trade name OXT-121 manufactured by Toagosei Co., Ltd.), bis (3
  • the above oxetane compound can be used in combination with the above epoxy compound or used alone. However, since the reactivity is lower than that of the epoxy compound, it is necessary to take care such as increasing the curing temperature.
  • examples of the curing agent include polyfunctional phenol compounds, polycarboxylic acids and acid anhydrides thereof, aliphatic or aromatic primary or secondary amines, polyamide resins, and polymercapto compounds.
  • polyfunctional phenol compounds, polycarboxylic acids and acid anhydrides thereof are preferably used from the viewpoints of workability and insulation.
  • polyfunctional phenol compound known compounds can be used as long as they have two or more phenolic hydroxyl groups in one molecule. Specific examples include phenol novolac resins, cresol novolac resins, bisphenol A, allylated bisphenol A, bisphenol F, bisphenol A novolac resins, vinylphenol copolymer resins, and the like. Is preferable because it has a high effect on increasing heat resistance. Such a polyfunctional phenol compound also undergoes an addition reaction with the epoxy compound and / or oxetane compound in the presence of a suitable curing catalyst.
  • the polycarboxylic acid and its acid anhydride are a compound having two or more carboxyl groups in one molecule and its acid anhydride, for example, a copolymer of (meth) acrylic acid, a copolymer of maleic anhydride, Examples include condensates of dibasic acids.
  • Examples of commercially available products include John Crill (product group name) manufactured by Johnson Polymer Co., Ltd., SMA Resin (product group name) manufactured by Arco Chemical Co., and polyazeline acid anhydride manufactured by Shin Nippon Science Co., Ltd.
  • an epoxy compound and / or an oxetane compound a compound serving as a curing catalyst for the reaction of a polyfunctional phenol compound and / or a polycarboxylic acid and its acid anhydride, or a polymerization catalyst when a curing agent is not used.
  • a curing catalyst for example, tertiary amines, tertiary amine salts, quaternary onium salts, tertiary phosphines, crown ether complexes, and phosphonium ylides, which can be arbitrarily selected from these, Can be used alone or in combination of two or more.
  • imidazoles such as trade names 2E4MZ, C11Z, C17Z, 2PZ, AZINE compounds of imidazoles such as trade names 2MZ-A, 2E4MZ-A, trade names 2MZ-OK, 2PZ-OK.
  • Isocyanurate of imidazole such as imidazole, and imidazole hydroxymethyl compounds such as trade names 2PHZ and 2P4MHZ (all trade names are manufactured by Shikoku Chemicals Co., Ltd.), dicyandiamide and derivatives thereof, melamine and derivatives thereof, diaminomaleonitrile and Derivatives, amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, bis (hexamethylene) triamine, triethanolamine diaminodiphenylmethane, organic acid dihydrazide, 1,8-diazabicyclo [5,4,0] undecene- (Trade name DBU, manufactured by San Apro Co., Ltd.), 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (trade name ATU, Ajinomoto Co., Inc.) Manufactured), or organic phosphine compounds
  • the blending amount of these curing catalysts is sufficient in a normal quantitative ratio. For example, 0.1 to 10 parts by mass is appropriate per 100 parts by mass of the total of the epoxy compound and / or oxetane compound.
  • the photo-curable resin composition may be any electrically insulating composition that is cured by irradiation with active energy rays, and a compound having one or more ethylenically unsaturated bonds in one molecule.
  • a composition containing a photopolymerization initiator is preferred because of its excellent heat resistance and electrical insulation.
  • the compound having one or more ethylenically unsaturated bonds in one molecule known and commonly used photopolymerizable oligomers, photopolymerizable vinyl monomers and the like are used.
  • Examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers.
  • Examples of (meth) acrylate oligomers include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, epoxy (meth) acrylates such as bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meta ) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like.
  • (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
  • photopolymerizable vinyl monomer known and commonly used monomers, for example, styrene derivatives such as styrene, chlorostyrene, ⁇ -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-ethoxymethyl (Meth) acrylamides such as chloramide and N-butoxymethylacrylamide; allyl compounds such as triallyl isocyanurate, dial,
  • photopolymerization initiator examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl methyl ketone, and alkyl ethers thereof.
  • tertiary amines such as triethanolamine and methyldiethanolamine; 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate and the like can be used in combination with a photoinitiator aid such as a benzoic acid derivative.
  • a wetting / dispersing agent can be added as necessary to facilitate high filling.
  • a wetting / dispersing agent include compounds having a polar group such as a carboxyl group, a hydroxyl group, and an acid ester, polymer compounds such as acid-containing compounds such as phosphate esters, copolymers containing an acid group, and hydroxyl groups. Containing polycarboxylic acid esters, polysiloxanes, salts of long-chain polyaminoamides and acid esters, and the like can be used.
  • Disperbyk registered trademark
  • Bykumen registered trademark
  • BYK-P105, -P104, -P104S, -240 all manufactured by Big Chemie Japan
  • EFKA-polymer 150 EFKA-44, -63, -64, -65, -66, -71, -764, -766, N (all manufactured by Efka).
  • the heat radiation insulating resin composition of the present invention may contain an organic solvent for adjusting the composition and adjusting the viscosity.
  • the organic solvent 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 Glycol ethers such as monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, Propylene glycol monomethyl ether acetate, di
  • the heat-dissipating insulating resin composition of the present invention may further include a known and commonly used colorant such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc.
  • a known and commonly used colorant such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc.
  • Hydroquinone hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine and other known and conventional thermal polymerization inhibitors, fine silica, organic bentonite, montmorillonite and other known and conventional thickeners, silica, barium sulfate, talc, clay, Known and conventional additives such as extender pigments such as hydrotalcite, conventional antifoaming agents and / or leveling agents such as silicones, fluorines, and polymers can be blended.
  • the heat radiation insulating resin composition of the present invention is adjusted to a viscosity suitable for the coating method with the organic solvent, and is coated on the substrate by a method such as a screen printing method.
  • thermosetting resin composition a thermosetting resin composition
  • a cured coating film is obtained by heating to a temperature of about 140 ° C. to 180 ° C. and thermosetting after coating. Can do.
  • the insulating curable resin composition is (B-2) a photocurable resin composition
  • it is irradiated with ultraviolet rays using a high pressure mercury lamp, a metal halide lamp, a xenon lamp or the like to obtain a cured coating film.
  • a high pressure mercury lamp a metal halide lamp, a xenon lamp or the like
  • the insulating curable resin composition is an alkali development type photocurable resin composition which is a mixture of (B-1) a thermosetting resin composition and (B-2) a photocurable resin composition.
  • an alkali development type photocurable resin composition which is a mixture of (B-1) a thermosetting resin composition and (B-2) a photocurable resin composition.
  • Example 1 to 4 and Comparative Examples 1 to 4 The blending components of Examples 1 to 4 and Comparative Examples 1 to 4 shown in Table 1 below were kneaded with a three-roll mill to obtain a heat radiation insulating resin composition.
  • Spherical aluminum oxide * 6 manufactured by Denki Kagaku Kogyo Co., Ltd., spherical aluminum oxide having an average particle size of about 0.3 ⁇ m * 7: phenol novolac epoxy resin manufactured by DIC Corporation * 8: bisphenol A manufactured by Mitsubishi Chemical Corporation Type epoxy resin * 9: 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine * 10: photopolymerizable oligomer (b-2) synthesized above * 11: Trimethylolpropane triacrylate * 12: Photopolymerization initiator manufactured by BASF * 13: Wetting agent manufactured by Big Chemie Japan Co., Ltd. * 14: Silicone defoamer manufactured by Shin-Etsu Chemical Co., Ltd. * 15: Organic bentonite manufactured by Wilber Ellis
  • the obtained curable resin composition was evaluated by the following evaluation methods. The evaluation results are shown in Table 2.
  • thermosetting resin compositions containing the thermosetting resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were stored in a sealed black container made of polyethylene and stored at 5 ° C.
  • the sedimentation state after 1 day, 2 days, 7 days, 30 days, and 90 days was evaluated.
  • the thermal radiation insulating resin composition containing the thermosetting resin composition and the photocurable resin composition of Examples 3 and 4 and Comparative Examples 3 and 4 was put in a sealed black container made of polyethylene at 20 ° C. Stored in the dark.
  • the sedimentation state after 1 day, 2 days, 7 days, 30 days, and 90 days was evaluated.
  • ⁇ Slightly settled, but there is no aggregation, and there is no problem in use by stirring.
  • X Sedimentation and aggregation. Even if it is stirred, it becomes lumpy and cannot be used.
  • thermosetting resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were screen-printed on a circuit-formed FR-4 substrate with a dry coating film of about 30 ⁇ m. The pattern was printed as such, and cured at 150 ° C. for 60 minutes.
  • the heat-dissipating insulating resin composition containing the thermosetting resin composition and the photocurable resin composition of Examples 3 and 4 and Comparative Examples 3 and 4 was screen-printed on the circuit-formed FR-4 substrate.
  • a pattern was printed so that the dried coating film had a thickness of about 30 ⁇ m, and after irradiating a cumulative light amount of 2 J / cm 2 at a wavelength of 350 nm with a metal halide lamp, it was thermally cured at 150 ° C. for 60 minutes.
  • the obtained substrate was immersed in propylene glycol monomethyl ether acetate for 30 minutes, dried, and then subjected to a peel test using a cellophane adhesive tape to evaluate peeling and discoloration of the coating film.
  • ⁇ No peeling or discoloration.
  • X There exists peeling and discoloration.
  • thermosetting resin composition containing the thermosetting resin composition (Heat-resistant) Examples 1, 2 and Comparative Examples 1, 2 of the heat-dissipating insulating resin composition containing the thermosetting resin composition, Examples 3, 4 and Comparative Examples 3, 4 of the thermosetting resin composition and light
  • the heat-dissipating insulating resin composition containing the curable resin composition it was cured in the same manner as the solvent resistance. Applying rosin flux to the obtained substrate, allowing it to flow in a solder bath at 260 ° C. for 10 seconds, washing and drying with propylene glycol monomethyl ether acetate, then performing a peel test with a cellophane adhesive tape, and peeling of the coating film evaluated.
  • ⁇ There is no peeling.
  • X There is peeling.
  • thermosetting resin composition containing the thermosetting resin composition examples 1, 2 and Comparative Examples 1, 2 of the heat-dissipating insulating resin composition containing the thermosetting resin composition, Examples 3, 4 and Comparative Examples 3, 4 of the thermosetting resin composition and light
  • the heat-dissipating insulating resin composition containing the curable resin composition it was cured in the same manner as the solvent resistance.
  • the obtained substrate was sharpened with a pencil core from B to 9H so that the tip was flat, and pressed at an angle of about 45 ° to record the hardness of the pencil at which the coating film was not peeled off.
  • thermosetting resin composition of Examples 1 and 2 and Comparative Examples 1 and 2 was screen-printed on the FR-4 substrate on which the circuit was formed, and the dry coating film was about 30 ⁇ m. The pattern was printed as described above and cured at 150 ° C. for 60 minutes.
  • the heat-dissipating insulating resin composition containing the thermosetting resin composition and the photocurable resin composition of Examples 3 and 4 and Comparative Examples 3 and 4 was screen-printed on the circuit-formed FR-4 substrate.
  • the obtained substrate was made with 100 1 mm grids (10 ⁇ 10) on the film of each sample, and transparent adhesive tape (Nichiban Co., width: 18 mm) was completely formed on the grids. The tape was attached and immediately pulled away while keeping one end of the tape at a right angle to the glass substrate, and it was examined whether peeling occurred on the grid.
  • the evaluation criteria are as follows. ⁇ : No peeling occurred on the grid. X: Peeling occurred on the grid.
  • thermosetting resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were screen-printed on an FR-4 substrate on which IPC standard B pattern comb-shaped electrodes were formed. Pattern printing was performed so that the dried coating film had a thickness of about 30 ⁇ m, and curing was performed at 150 ° C. for 60 minutes. Moreover, the comb-shaped electrode of the IPC standard B pattern was formed from the heat radiation insulating resin composition containing the thermosetting resin composition and the photocurable resin composition of Examples 3 and 4 and Comparative Examples 3 and 4.
  • Pattern printing was performed on the FR-4 substrate by screen printing so that the dried coating film had a thickness of about 30 ⁇ m, and the film was cured by irradiation with an accumulated light amount of 2 J / cm 2 at a wavelength of 350 nm with a metal halide lamp.
  • the insulation resistance value between the electrodes of the obtained substrate was measured at an applied voltage of 500V.
  • thermosetting resin composition of Examples 1 and 2 and Comparative Examples 1 and 2 The heat-dissipating insulating resin composition containing the thermosetting resin composition of Examples 1 and 2 and Comparative Examples 1 and 2 was printed on a rolled copper foil so that the dry coating film was about 50 ⁇ m by screen printing. Cured at 150 ° C. for 60 minutes. Further, the heat-dissipating insulating resin composition containing the thermosetting resin composition and the photocurable resin composition of Examples 3 and 4 and Comparative Examples 3 and 4 was screen-printed on a rolled copper foil to form a dry coating film.
  • thermosetting or photocurable resin composition As is clear from the results shown in Table 2, according to the heat-insulating insulating resin composition of the present invention, storage stability and heat conduction can be achieved regardless of whether the thermosetting or photocurable resin composition is contained. It was possible to obtain a heat radiation insulating resin composition having excellent properties and sufficient characteristics as a heat-resistant insulating material for printed wiring boards.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
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  • Inorganic Insulating Materials (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)
  • Structure Of Printed Boards (AREA)
PCT/JP2019/012839 2018-03-30 2019-03-26 放熱絶縁性樹脂組成物、及びそれを用いたプリント配線板 WO2019189171A1 (ja)

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JP3659825B2 (ja) 1997-12-19 2005-06-15 太陽インキ製造株式会社 アルカリ現像可能な光硬化性・熱硬化性組成物及びそれから得られる硬化皮膜
JP3989349B2 (ja) * 2002-09-30 2007-10-10 京セラケミカル株式会社 電子部品封止装置
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JP5104507B2 (ja) * 2007-04-26 2012-12-19 日立化成工業株式会社 セミｉｐｎ型複合体の熱硬化性樹脂を含有する樹脂ワニスの製造方法、並びにこれを用いたプリント配線板用樹脂ワニス、プリプレグ及び金属張積層板
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JP2012111807A (ja) * 2010-11-22 2012-06-14 Uniplus Electronics Co Ltd 熱硬化性樹脂組成物及びその熱硬化性樹脂組成物を使用したプリプレグシート又は積層板
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