WO2021090630A1 - 絶縁性樹脂組成物、絶縁性樹脂硬化体、積層体及び回路基板 - Google Patents

絶縁性樹脂組成物、絶縁性樹脂硬化体、積層体及び回路基板 Download PDF

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WO2021090630A1
WO2021090630A1 PCT/JP2020/038031 JP2020038031W WO2021090630A1 WO 2021090630 A1 WO2021090630 A1 WO 2021090630A1 JP 2020038031 W JP2020038031 W JP 2020038031W WO 2021090630 A1 WO2021090630 A1 WO 2021090630A1
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Prior art keywords
insulating resin
mass
resin composition
inorganic filler
curing agent
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PCT/JP2020/038031
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English (en)
French (fr)
Japanese (ja)
Inventor
裕紀 木元
良太 熊谷
八島　克憲
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デンカ株式会社
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Priority to CN202080062853.1A priority Critical patent/CN114341263A/zh
Priority to JP2021554851A priority patent/JPWO2021090630A1/ja
Publication of WO2021090630A1 publication Critical patent/WO2021090630A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C08K5/25—Carboxylic acid hydrazides
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate

Definitions

  • the present invention relates to an insulating resin composition and a cured product thereof, which are suitably used for manufacturing a metal-based circuit board.
  • the present invention also relates to a laminate and a circuit board formed by using an insulating resin composition.
  • Circuit boards have been put into practical use as circuit boards for forming mixed integrated circuits by mounting electronic and electrical components such as semiconductor elements.
  • Circuit boards are classified into resin circuit boards, ceramic circuit boards, metal-based circuit boards, and the like based on the substrate material.
  • resin circuit boards are inexpensive, they have low thermal conductivity, so they are limited to applications that are used with relatively small power. Ceramic circuit boards are suitable for applications where they are used with relatively large power because of their high electrical insulation characteristics and high heat resistance, but they have the disadvantage of being expensive.
  • metal-based circuit boards have intermediate properties between the two, and are used for general-purpose applications that are used with relatively large amounts of electric power, such as refrigerator power supplies, household air conditioner power supplies, automobile power supplies, and high-speed railway power supplies. Suitable for applications such as power supplies.
  • Patent Document 1 a circuit board composition having a specific epoxy resin, a curing agent, and an inorganic filler as essential components is used to provide a circuit board having excellent stress relaxation resistance, heat resistance, moisture resistance, and heat dissipation. The method of obtaining is disclosed.
  • An object of the present invention is to provide an insulating resin composition capable of forming an insulating layer having both excellent adhesiveness and insulating properties and a low elastic modulus in a high temperature and high humidity environment, and a cured product thereof.
  • Another object of the present invention is to provide a circuit board provided with an insulating layer made of a cured product of the insulating resin composition and having excellent moisture insulation resistance, thermal conductivity and heat cycle resistance.
  • One aspect of the present invention relates to an insulating resin composition containing an organic material and an inorganic filler.
  • the organic material includes an epoxy resin, a curing agent, a phosphoric acid ester compound having one or more hydroxyl groups in one molecule, a heavy metal inactivating agent, and a hindered phenol-based oxidation.
  • the content of the inorganic filler is 50% by mass or more and 95% by mass or less.
  • the amine-based curing agent may contain a first amine-based curing agent having an amine equivalent of 300 or less and a second amine-based curing agent having an amine equivalent of 800 or more.
  • the content of the heavy metal inactivating agent may be 0.01 to 0.5% by mass based on the total amount of the organic material and the inorganic filler.
  • the content of the hindered phenolic antioxidant may be 0.05 to 5% by mass based on the total amount of the organic material.
  • the content of the phosphoric acid ester compound may be 0.05 to 0.4% by mass based on the total amount of the organic material and the inorganic filler.
  • Another aspect of the present invention relates to an insulating resin cured product, which is a cured product of the insulating resin composition.
  • Yet another aspect of the present invention is a laminate comprising a metal plate, the insulating resin cured body arranged on the metal plate, and a metal foil arranged on the insulating resin cured body. Regarding.
  • Yet another aspect of the present invention is a circuit board comprising a metal plate, the insulating resin cured body arranged on the metal plate, and a circuit portion arranged on the insulating resin cured body. Regarding.
  • an insulating resin composition capable of forming an insulating layer having both excellent adhesiveness and insulating properties and a low elastic modulus in a high temperature and high humidity environment, and a cured product thereof. Further, according to the present invention, there is provided a circuit board provided with an insulating layer made of a cured product of the insulating resin composition and excellent in moisture insulation resistance, thermal conductivity and heat cycle resistance.
  • the insulating resin composition of the present embodiment is a composition containing an organic material and an inorganic filler, and the content of the inorganic filler is 50% by mass or more and 95% by mass or less. Further, the insulating resin composition of the present embodiment contains an epoxy resin, a curing agent, a phosphoric acid ester compound having one or more hydroxyl groups in one molecule, a heavy metal inactivating agent, and a hinder as organic materials. Contains a dophenolic antioxidant.
  • the insulating resin composition it is possible to form a cured product (insulating layer) having both excellent adhesiveness and insulating properties and a low elastic modulus in a high temperature and high humidity environment. Therefore, the insulating resin composition can be suitably used for forming an insulating layer for a circuit board (particularly a metal-based circuit board). The reason why the above effect is obtained in this embodiment is not always clear, but it is considered as follows.
  • the phosphoric acid ester compound improves the dispersibility and adhesion between the resin component and the inorganic filler due to the presence of hydroxyl groups in the molecule, and improves the moisture-resistant adhesiveness.
  • the phosphate ester compound traps OH radicals generated under high temperature and high humidity environment and under the condition of applying DC voltage, thereby suppressing the deterioration of moisture insulation resistance due to oxidative deterioration of the insulating layer. Conceivable.
  • the hindered phenolic antioxidant further plays a role of trapping radicals, so that the oxidative deterioration of the insulating layer is more remarkably suppressed by the interaction with the phosphoric acid ester compound, and the insulation is moisture-resistant. It is considered that the sex is improved.
  • ionic impurities into the insulating layer can be considered as a cause of deterioration of adhesiveness and insulating property.
  • metal ions are trapped by the heavy metal inactivating agent, and the adverse effect of migration is suppressed. It is thought that it will be done.
  • metal ions for example, copper ions
  • the insulating resin composition of the present embodiment According to the above, it is possible to form an insulating layer capable of maintaining excellent moisture-resistant adhesiveness and moisture-insulating insulation even when adjacent to a metal plate.
  • the crosslinked structure of the epoxy resin and the amine-based curing agent is formed in the cured product, so that the effects of the above-mentioned phosphoric acid ester compound, hindered phenol-based antioxidant and heavy metal inactivating agent are obtained. It is considered that the elastic modulus of the cured product can be lowered while remarkably obtaining.
  • the epoxy resin may be one that is cured by an amine-based curing agent to exhibit an adhesive action.
  • the epoxy resin include bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol A / F type epoxy resin; novolak type epoxy resins such as phenol novolac type epoxy resin and cresol novolac type epoxy resin.
  • Polyfunctional epoxy resin such as trisphenol methane type epoxy resin; Glycidylamine type epoxy resin; Heterocyclic ring-containing epoxy resin such as triglycidyl isocyanurate, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin and other fats Ring-type epoxy resin and the like can be mentioned.
  • a bifunctional epoxy resin (bifunctional aromatic epoxy resin) and an alicyclic epoxy resin can be preferably used as the epoxy resin.
  • the insulating resin composition according to the present embodiment may contain at least one of a bifunctional epoxy resin and an alicyclic epoxy resin, and may contain both a bifunctional epoxy resin and an alicyclic epoxy resin. May be good.
  • ratios (A 2 / A 1 , mass ratio) are, for example, 1.5 to 8.0, 1.5 to 6.0, 1.5 to 4.0, 2.0 to 8.0, 2 It may be 0.0 to 6.0, 2.0 to 4.0, 2.5 to 8.0, 2.5 to 6.0 or 2.5 to 4.0.
  • the content of the epoxy resin in the insulating resin composition may be, for example, 50% by mass or more, preferably 55% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, based on the total amount of the organic material. It is mass% or more.
  • the content of the epoxy resin may be, for example, 90% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less, based on the total amount of the organic material.
  • the curing agent may be any curing agent capable of curing the epoxy resin.
  • the curing agent include amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and the like, among these, amine-based curing agents from the viewpoint of further improving moisture-resistant adhesiveness and moisture-insulating resistance. Is preferable.
  • an aliphatic amine-based curing agent is preferable from the viewpoint of further improving the heat cycle resistance of the circuit board.
  • the amine-based curing agent preferably contains a first amine-based curing agent having an amine equivalent of 300 or less and a second amine-based curing agent having an amine equivalent of 800 or more.
  • the amine-based curing agent preferably contains an amine-based curing agent having a polyether chain, and at least one of the first amine-based curing agent and the second amine-based curing agent has a polyether chain. Is more preferable, and it is further preferable that both the first amine-based curing agent and the second amine-based curing agent have a polyether chain. Since an amine-based curing agent having a polyether chain has excellent compatibility with an epoxy resin, it is easy to obtain a cured product having further excellent adhesiveness and heat resistance by using such an amine-based curing agent.
  • the polyether chain is preferably a polyoxyalkylene chain, and more preferably a polyoxyalkylene chain having an alkylene group selected from the group consisting of an ethylene group and a propylene group.
  • first amine-based curing agent and the second amine-based curing agent are both curing agents having two amino groups in one molecule.
  • the ratio of the content B 2 of the second amine-based curing agent to the content B 1 of the first amine-based curing agent in the insulating resin composition (B 2 / B 1 , mass ratio) is, for example, 0.2. It may be more than that, preferably 0.25 or more, and more preferably 0.3 or more. As a result, the heat cycle resistance of the circuit board tends to be further improved.
  • the ratio (B 2 / B 1 , mass ratio) may be, for example, 2.0 or less, preferably 1.5 or less, and more preferably 1.0 or less. As a result, the insulating property, adhesiveness and heat resistance of the cured product tend to be further improved.
  • ratios (B 2 / B 1 , mass ratio) are, for example, 0.2 to 2.0, 0.2 to 1.5, 0.2 to 1.0, 0.25 to 2.0, 0. It may be .25 to 1.5, 0.25 to 1.0, 0.3 to 2.0, 0.3 to 1.5 or 0.3 to 1.0.
  • the amount of the curing agent added is determined based on the ratio (C 2 / C 1 ) of the active hydrogen equivalent (or acid anhydride equivalent) (C 2 ) of the curing agent to the epoxy equivalent (C 1) of the epoxy resin. Good.
  • the ratio (C 2 / C 1 ) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more.
  • the ratio (C 2 / C 1 ) is preferably 2.5 or less, more preferably 2.0 or less, still more preferably 1.5 or less. That is, the ratio (C 2 / C 1 ) is, for example, 0.1 to 2.5, 0.1 to 2.0, 0.1 to 1.5, 0.2 to 2.5, 0.2 to 2. It may be 0.0, 0.2 to 1.5, 0.3 to 2.5, 0.3 to 2.0 or 0.3 to 1.5.
  • the phosphate ester compound has one or more hydroxyl groups in one molecule.
  • the phosphoric acid ester compound has an effect of improving the dispersibility and adhesion between the resin component and the inorganic filler and improving the moisture-resistant adhesiveness due to the presence of the hydroxyl group in the molecule. Be done.
  • the above-mentioned phosphoric acid ester compound has an effect of suppressing a decrease in moisture insulation resistance due to oxidative deterioration of the insulating layer by trapping OH radicals generated in a high temperature and high humidity environment and under the condition of applying a DC voltage. Is also considered to have.
  • the number of hydroxyl groups contained in the phosphoric acid ester compound is more preferably 1 to 2 in one molecule, and further preferably 2 in one molecule.
  • the phosphoric acid ester compound preferably has a hydroxyl group directly bonded to a phosphorus atom. Further, it is more preferable that the phosphoric acid ester compound has two hydroxyl groups directly bonded to the phosphorus atom.
  • the phosphoric acid ester compound preferably contains a polyether chain from the viewpoint of excellent compatibility with the epoxy resin and the curing agent and further improving the adhesion between the inorganic filler and the resin component.
  • the polyether chain is preferably a polyoxyalkylene chain, and more preferably a polyoxyalkylene chain having an alkylene group selected from the group consisting of an ethylene group and a propylene group.
  • the phosphoric acid ester compound preferably contains an oxycarbonyl group from the viewpoint of excellent compatibility with the epoxy resin and the curing agent and further improving the adhesion between the inorganic filler and the resin component.
  • R represents a monovalent group having a polyether chain.
  • R may further have a polyester chain.
  • the content of the phosphoric acid ester compound in the insulating resin composition may be, for example, 0.05% by mass or more, preferably 0.1% by mass or more, based on the total amount of the organic material and the inorganic filler. .. As a result, the above-mentioned effect of the phosphoric acid ester compound is more prominently exhibited.
  • the content of the phosphoric acid ester compound in the insulating resin composition may be, for example, 0.4% by mass or less, preferably 0.3% by mass or less, based on the total amount of the organic material and the inorganic filler. Is.
  • the content of the phosphoric acid ester compound in the insulating resin composition is, for example, 0.05 to 0.4% by mass and 0.05 to 0.3% by mass based on the total amount of the organic material and the inorganic filler. , 0.1-0.4% by mass or 0.1-0.3% by mass.
  • the heavy metal inactivating agent may be, for example, one capable of chelating and capturing metal ions (for example, copper ions) in an insulating resin composition or a cured product thereof.
  • a nitrogen-containing inactivating agent such as a hydrazine-based heavy metal inactivating agent or a triazole-based heavy metal inactivating agent can be preferably used.
  • heavy metal inactivating agent examples include bis dodecanedioate [N2- (2-hydroxybenzoyl) hydrazide] (product name "CDA-6", manufactured by ADEKA), N- (2H-1,2,4-triazole). -5-yl) salicylamide (product name "CDA-1”, manufactured by ADEKA), N, N'-bis ⁇ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl ⁇ hydrazine (product) Names "CDA-10", manufactured by ADEKA), 3-amino-1,2,4-triazole and the like can be mentioned.
  • the heavy metal inactivating agent one having a low melting point is preferable from the viewpoint of further improving the dispersibility in the insulating resin composition.
  • the melting point of the heavy metal inactivating agent may be, for example, 250 ° C. or lower, preferably 240 ° C. or lower, more preferably 230 ° C. or lower, still more preferably 220 ° C. or lower.
  • the content of the heavy metal inactivating agent in the insulating resin composition is, for example, 0.01 to 0.5% by mass and 0.01 to 0.3% by mass based on the total amount of the organic material and the inorganic filler. %, 0.01 to 0.2% by mass, 0.03 to 0.5% by mass, 0.03 to 0.3% by mass, 0.03 to 0.2% by mass, 0.05 to 0.5% by mass %, 0.05 to 0.3% by mass or 0.05 to 0.2% by mass.
  • the hindered phenolic antioxidant may be a compound having a hindered phenol structure. Having a hindered phenol structure makes it difficult to decompose (for example, hydrolyze) even in a high temperature and high humidity environment, and the adverse effect on moisture resistance due to the decomposition is suppressed.
  • R 1 represents an alkyl group having 1 to 25 carbon atoms (preferably an alkyl group having 10 to 20 carbon atoms).
  • the content of the hindered phenolic antioxidant in the insulating resin composition may be, for example, 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.05% by mass or more, based on the total amount of the organic material. It is 0.1% by mass or more, more preferably 0.15% by mass or more.
  • the content of the hindered phenolic antioxidant in the insulating resin composition may be, for example, 10% by mass or less, preferably 7% by mass or less, and more preferably 5% by mass or less, based on the total amount of the organic material. , More preferably 4% by mass or less. This tends to further improve the thermal conductivity of the insulating resin composition. That is, the content of the hindered phenol-based antioxidant in the insulating resin composition is, for example, 0.01 to 10% by mass, 0.01 to 7% by mass, or 0.01 to 5 based on the total amount of the organic material.
  • Mass% 0.01-4% by mass, 0.05-10% by mass, 0.05-7% by mass, 0.05-5% by mass, 0.05-4% by mass, 0.1-10% by mass , 0.1-7% by mass, 0.1-5% by mass, 0.1-4% by mass, 0.15-10% by mass, 0.15-7% by mass, 0.15-5% by mass or 0 It may be .15 to 4% by mass.
  • the inorganic filler is not particularly limited, and a known inorganic filler used for applications requiring insulation and thermal conductivity can be used without particular limitation.
  • the inorganic filler contains an inorganic material selected from the group consisting of aluminum oxide, silica, silicon nitride and boron nitride as a main component from the viewpoint of suppressing a decrease in moisture insulation resistance due to hydrolysis of the inorganic material. Is preferable.
  • the content of the inorganic material in the inorganic filler is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, based on the total amount of the inorganic filler.
  • the inorganic filler when the inorganic filler contains a large amount of aluminum nitride, the aluminum nitride may be hydrolyzed in a high temperature and high humidity environment, and the insulating property may be lowered. Therefore, the content of aluminum nitride in the inorganic filler is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, based on the total amount of the inorganic filler. As described above, by using an inorganic material selected from the group consisting of aluminum oxide, silica, silicon nitride and boron nitride as a main component, the decrease in insulating property due to such hydrolysis is remarkably suppressed. ..
  • the shape of the inorganic filler is not particularly limited, and may be particle-like, scaly, polygonal, or the like, and is preferably particle-like.
  • the maximum particle size of the inorganic filler may be, for example, 250 ⁇ m or less, preferably 200 ⁇ m or less, and more preferably 150 ⁇ m or less. As a result, the insulating property of the cured product tends to be further improved.
  • the minimum particle size of the inorganic filler is not particularly limited, but from the viewpoint of further improving the thermal conductivity, it may be, for example, 0.05 ⁇ m or more, preferably 0.1 ⁇ m or more. In the present specification, the maximum particle size and the minimum particle size of the inorganic filler indicate the d90 diameter and the d10 diameter in the volume-based particle size distribution, and these are measured by a laser diffraction type particle size distribution measuring device.
  • the inorganic filler may contain two or more kinds of inorganic fillers having different average particle diameters.
  • the inorganic filler may contain a first inorganic filler having an average particle diameter of 25 ⁇ m or more and a second inorganic filler having an average particle diameter of 4 ⁇ m or less.
  • the filling density is increased and the thermal conductivity of the cured product is further improved by filling the gap between the first inorganic filler with the second inorganic filler.
  • the average particle size of the inorganic filler indicates the d50 diameter in the volume-based particle size distribution.
  • the volume-based particle size distribution is measured with a laser diffraction type particle size distribution measuring device.
  • the average particle size of the first inorganic filler is preferably 30 ⁇ m or more, more preferably 40 ⁇ m or more.
  • the average particle size of the first inorganic filler may be, for example, 200 ⁇ m or less, preferably 150 ⁇ m or less. With such an average particle size, the above-mentioned effect is more prominently exhibited. That is, the average particle size of the first inorganic filler may be, for example, 30 to 200 ⁇ m, 30 to 150 ⁇ m, 40 to 200 ⁇ m, or 40 to 150 ⁇ m.
  • the average particle size of the second inorganic filler is preferably 3.5 ⁇ m or less, more preferably 3 ⁇ m or less.
  • the average particle size of the second inorganic filler may be, for example, 0.05 ⁇ m or more, preferably 0.1 ⁇ m or more.
  • the average particle size of the second inorganic filler may be, for example, 0.05 to 3.5 ⁇ m, 0.05 to 3 ⁇ m, 0.1 to 3.5 ⁇ m, or 0.1 to 3 ⁇ m.
  • the inorganic filler may further contain a third inorganic filler having an average particle size of more than 4 ⁇ m and less than 25 ⁇ m. According to such a third inorganic filler, the above-mentioned effect is more prominently exhibited.
  • the content of the inorganic filler in the insulating resin composition is 50% by mass or more, preferably 55% by mass or more, and more preferably 60% by mass or more, based on the total amount of the insulating resin composition. As a result, the moisture resistance and thermal conductivity of the cured product tend to be further improved.
  • the content of the inorganic filler in the insulating resin composition is 95% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less based on the total amount of the insulating resin composition. .. This makes it easier to obtain a cured product having improved adhesiveness and insulating properties in a high temperature and high humidity environment, and tends to further improve the heat cycle resistance of the circuit board.
  • the content of the inorganic filler in the insulating resin composition is, for example, 50 to 95% by mass, 50 to 90% by mass, 50 to 85% by mass, 55 to 95% by mass based on the total amount of the insulating resin composition. %, 55-90% by mass, 55-85% by mass, 60-95% by mass, 60-90% by mass or 60-85% by mass.
  • the cured insulating resin according to the present embodiment is a cured product of the above-mentioned insulating resin composition.
  • the heat insulating resin cured product can form an insulating layer having both excellent adhesiveness and insulating properties and a low elastic modulus in a high temperature and high humidity environment.
  • the storage elastic modulus of the cured insulating resin at 85 ° C. is preferably 500 MPa or less, more preferably 400 MPa or less, further preferably 300 MPa or less, and even more preferably 200 MPa or less. According to such an insulating resin cured product, a circuit board having further excellent heat cycle resistance can be realized.
  • the method for producing the cured insulating resin is not particularly limited.
  • the cured insulating resin can be produced by heat-treating and curing the insulating resin composition.
  • the heat treatment may be performed in one step or in two steps. By performing the heat treatment in two steps, an insulating resin cured product can be formed via the semi-cured product of the insulating resin composition.
  • the heat treatment temperature may be, for example, 150 to 250 ° C., preferably 160 to 240 ° C.
  • the heat treatment time may be, for example, 2 to 15 hours, preferably 2. . 5-10 hours.
  • the temperature of the first stage heat treatment may be, for example, 60 to 130 ° C., preferably 65 to 100 ° C.
  • the heat treatment time is, for example, 0.3 to 8 hours. It is preferably 0.5 to 5 hours.
  • the temperature of the second stage heat treatment may be, for example, 150 to 250 ° C., preferably 160 to 240 ° C., and the heat treatment time may be, for example, 2 to 15 hours, preferably 2.5. ⁇ 10 hours.
  • an insulating resin cured product having a predetermined shape By performing heat treatment while maintaining the insulating resin composition or its semi-cured body in a predetermined shape, an insulating resin cured product having a predetermined shape can be obtained.
  • a layered insulating resin cured product can be formed on the metal plate by applying the insulating resin composition on the metal plate, laminating the metal foil as needed, and curing the metal foil.
  • the laminate according to the present embodiment includes a metal plate, an insulating resin cured body arranged on the metal plate, and a metal foil arranged on the insulating resin cured body.
  • the metal plate and the metal foil may be separated by an insulating resin cured body, and the insulating resin cured body may function as an insulating layer.
  • the metal material constituting the metal plate is not particularly limited, and examples thereof include aluminum, aluminum alloy, copper, copper alloy, iron, and stainless steel.
  • the metal plate may be composed of one kind of metal material, or may be composed of two or more kinds of metal materials. Further, the metal plate may have a single-layer structure or a multi-layer structure.
  • the thickness of the metal plate is not particularly limited, and may be, for example, 0.5 to 3.0 mm from the viewpoint of being suitable for producing a circuit board.
  • the metal material constituting the metal foil is not particularly limited, and examples thereof include copper, aluminum, and nickel.
  • the metal leaf may be composed of one kind of metal material, or may be composed of two or more kinds of metal materials. Further, the metal foil may have a single-layer structure or a multi-layer structure.
  • the thickness of the cured insulating resin is not particularly limited, and may be, for example, 50 ⁇ m to 300 ⁇ m from the viewpoint of being suitable for producing a circuit board.
  • the manufacturing method of the laminated body is not particularly limited.
  • the laminate is a step of applying an insulating resin composition on a metal plate and curing or semi-curing, and a cured or semi-cured insulating resin composition (that is, an insulating resin cured body or semi-cured body).
  • a cured or semi-cured insulating resin composition that is, an insulating resin cured body or semi-cured body.
  • the method may further include a step of curing the semi-cured body of the insulating resin composition.
  • the metal foils may be joined by, for example, a roll laminating method, a laminated pressing method, or the like.
  • the laminate is a step of applying an insulating resin composition on a metal foil and curing or semi-curing, and a cured or semi-cured insulating resin composition (that is, an insulating resin cured body or a semi-cured body). )
  • a cured or semi-cured insulating resin composition that is, an insulating resin cured body or a semi-cured body.
  • FIG. 1 is a cross-sectional view showing a preferred embodiment of the laminated body.
  • the laminate 10 shown in FIG. 1 includes a metal plate 1, a metal foil 3, and an insulating layer 2 composed of an insulating resin cured body interposed between the metal plate 1 and the metal foil 3.
  • a circuit board can be easily formed by processing the metal foil 3 of the laminated body 10 into a predetermined pattern.
  • the circuit part may be made of a metal material.
  • the metal material constituting the circuit portion include the same metal materials as those constituting the above-mentioned metal foil.
  • the circuit unit may be a metal leaf processed into a predetermined pattern.
  • the thickness of the circuit portion is not particularly limited, and may be, for example, 5 ⁇ m to 1 mm from the viewpoint of heat resistance and workability.
  • the thickness of the cured insulating resin is not particularly limited, and may be, for example, 50 ⁇ m to 300 ⁇ m from the viewpoint of thermal conductivity and insulating properties.
  • the manufacturing method of the circuit board is not particularly limited.
  • the circuit board can be manufactured by a method including a step of processing the metal foil of the above-mentioned laminate into a predetermined pattern.
  • the method of processing (etching) the metal foil is not particularly limited, and a conventionally known method may be applied.
  • FIG. 2 is a cross-sectional view showing a preferred embodiment of the circuit board.
  • the circuit board 20 shown in FIG. 2 includes a metal plate 1, a circuit unit 4, and an insulating layer 2 composed of an insulating resin cured body interposed between the metal plate 1 and the circuit unit 4.
  • the circuit board 20 may be, for example, a metal foil 3 of the laminated body 10 processed into a circuit portion 4.
  • An insulating resin composition is applied onto an aluminum plate having a thickness of 1.5 mm (manufactured by Amano Aluminum Co., Ltd., "A1050 1.5 mm thickness") and dried at 120 ° C. for 15 minutes in a B stage (semi-cured) state. And said. The amount of the insulating resin composition applied was adjusted so that the thickness of the insulating layer after curing was 100 ⁇ m.
  • a copper foil with a thickness of 70 ⁇ m (manufactured by Furukawa Electric Co., Ltd., “electrolytic copper foil 70 ⁇ m thickness”) was placed on a semi-cured body of the insulating resin composition, and was subjected to a heat press method in a laminated state 180 The semi-cured product was cured by heat treatment at ° C. for 6 hours to obtain a laminated product.
  • Example 2 The amount of "DAS45” added is 30.4 parts by mass, the amount of “DAS10” added is 30.4 parts by mass, the amount of “AA2” added is 25.8 parts by mass, and the heavy metal inactivating agent ("CDA-6"). ) was changed to 0.4 parts by mass. Except for the above, an insulating resin composition and a circuit board were obtained in the same manner as in Example 1.
  • Example 3 The amount of "YX-8000” added was changed to 1.0 part by mass, and the amount of heavy metal inactivating agent (“CDA-6") added was changed to 0.02 part by mass. Except for the above, an insulating resin composition and a circuit board were obtained in the same manner as in Example 1.
  • Example 4 As the heavy metal inactivating agent, 0.1 part by mass of "CDA-10" (manufactured by ADEKA, melting point 227 ° C.) was used instead of "CDA-6". Except for the above, an insulating resin composition and a circuit board were obtained in the same manner as in Example 1.
  • Example 5 As the heavy metal inactivating agent, 0.1 part by mass of "CDA-1” (manufactured by ADEKA, melting point 320 ° C.) was used instead of "CDA-6". Except for the above, an insulating resin composition and a circuit board were obtained in the same manner as in Example 1.
  • Example 6 An insulating resin composition and a circuit board were obtained in the same manner as in Example 1 except that the amount of the hindered phenolic antioxidant 1 (“Adecastab AO-50”) was changed to 0.4 parts by mass. It was.
  • Adecastab AO-50 the hindered phenolic antioxidant 1
  • Example 7 An insulating resin composition and a circuit board were obtained in the same manner as in Example 1 except that the amount of the hindered phenolic antioxidant 1 (“Adecastab AO-50”) was changed to 0.02 parts by mass. It was.
  • Example 8 As the hindered phenolic antioxidant, 0.1 part by mass of "ADEKA STAB AO-60" (manufactured by ADEKA) was used instead of "ADEKA STAB AO-50". Except for the above, an insulating resin composition and a circuit board were obtained in the same manner as in Example 1.
  • Example 11 The addition amount of "YD-6020” is 1.2 parts by mass, the addition amount of “YX8000” is 3.6 parts by mass, the addition amount of “D400” is 1.2 parts by mass, and the addition amount of "D2000” is 0.
  • the measurement was performed using a "laser diffraction type particle size distribution measuring device SALD-200" manufactured by Shimadzu Corporation. Specifically, 50 cc of pure water and 5 g of an inorganic filler were added to a glass beaker, stirred with a spatula, and then dispersed with an ultrasonic cleaner for 10 minutes. The dispersion of the inorganic filler was added drop by drop to the sampler part of the device with a dropper, and the mixture was waited for stabilization until the absorbance became measurable. The measurement was performed when the absorbance became stable. In the laser diffraction type particle size distribution measuring device, the particle size distribution was calculated from the data of the light intensity distribution of the diffracted / scattered light by the particles detected by the sensor. The maximum particle size was d90 and the average particle size was d50.
  • the insulating resin composition obtained in Examples and Comparative Examples and the circuit board obtained in Example 1 were evaluated by the following methods. The results are shown in Tables 1 and 2.
  • an insulating layer having both a low elastic modulus and a high thermal conductivity can be formed, and a circuit board having excellent moisture insulation resistance, moisture adhesion resistance and heat cycle resistance can be obtained. It was confirmed that.
  • the present invention it is possible to form an insulating layer having both excellent adhesiveness and insulating properties and a low elastic modulus in a high temperature and high humidity environment.
  • a circuit board provided with the above-mentioned insulating layer and excellent in moisture insulation resistance, thermal conductivity and heat cycle resistance can be obtained. Therefore, the present invention can be suitably used in fields where heat cycle resistance, moisture insulation resistance, heat dissipation, etc. are required (for example, circuit boards for in-vehicle fillers).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2020/038031 2019-11-08 2020-10-07 絶縁性樹脂組成物、絶縁性樹脂硬化体、積層体及び回路基板 WO2021090630A1 (ja)

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