WO2015075906A1 - Composition de résine isolante et article comprenant celle-ci - Google Patents

Composition de résine isolante et article comprenant celle-ci Download PDF

Info

Publication number
WO2015075906A1
WO2015075906A1 PCT/JP2014/005694 JP2014005694W WO2015075906A1 WO 2015075906 A1 WO2015075906 A1 WO 2015075906A1 JP 2014005694 W JP2014005694 W JP 2014005694W WO 2015075906 A1 WO2015075906 A1 WO 2015075906A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
phase
resin composition
inorganic filler
adhesive layer
Prior art date
Application number
PCT/JP2014/005694
Other languages
English (en)
Japanese (ja)
Inventor
友規 小谷
浩好 余田
Original Assignee
パナソニック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by パナソニック株式会社 filed Critical パナソニック株式会社
Publication of WO2015075906A1 publication Critical patent/WO2015075906A1/fr

Links

Images

Classifications

    • 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
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/301—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen or carbon in the main chain of the macromolecule, not provided for in group H01B3/302
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones
    • 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
    • H01B3/002—Inhomogeneous material in general
    • 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
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins

Definitions

  • the present invention relates to an insulating resin composition and an article having the same. More specifically, the present invention relates to an insulating resin composition used for a heat conductive component serving as a heat radiator for cooling electronic components and the like, and an article having the insulating resin composition.
  • a heat radiator is usually attached to an electronic component that generates heat.
  • a metal having high thermal conductivity has been used for such a radiator.
  • insulating resin compositions that have a high degree of freedom in shape selection and are easy to be reduced in weight and size are being used as heat radiators (see, for example, Patent Document 1).
  • the insulating resin composition contains a large amount of a heat conductive inorganic filler in the binder resin in order to improve the heat conductivity. Therefore, when the insulating resin composition is bonded to the base material, the resin component on the surface portion to be bonded to the base material is reduced, and the adhesive strength is reduced. As a result, the insulating resin composition is peeled off during thermal shock such as reflow or heat cycle.
  • the insulating resin composition according to the first aspect of the present invention has a first resin phase formed by the first resin and a second resin phase that is different from the first resin phase and formed by the second resin. It has a phase separation structure. Furthermore, the insulating resin composition has an inorganic filler dispersed inside the phase separation structure.
  • the phase-separated structure has an adhesive layer having a first resin or a second resin as a main component and a thickness of 0.1 ⁇ m or more and 5 ⁇ m or less on the surface.
  • the insulating resin composition of the present invention and another member can be bonded without attaching a separately prepared adhesive layer to the phase separation structure.
  • the insulating resin composition 10 according to the embodiment of the present invention will be described in detail.
  • the dimension ratio of drawing is exaggerated on account of description, and may differ from an actual ratio.
  • the insulating resin composition 10 includes a first resin phase 2 formed of a first resin, and a second resin phase 3 formed of a second resin that is different from the first resin phase 2. It has the phase-separation structure 1 which has these. Furthermore, the insulating resin composition 10 has an inorganic filler 4 dispersed inside the phase separation structure 1.
  • the insulating resin composition 10 has a first resin phase 2 and a second resin phase 3, and further has a structure in which these resin phases are mixed and phase-separated. Furthermore, the particles of the inorganic filler 4 dispersed in the phase separation structure 1 are in continuous contact with each other. For this reason, a heat conduction path is formed inside the phase separation structure 1 by contact between the particles of the inorganic filler 4. With this heat conduction path, the thermal conductivity of the insulating resin composition 10 can be improved.
  • the phase separation structure 1 has an adhesive layer 5 whose main component is the first resin forming the first resin phase 2 or the second resin forming the second resin phase 3 on the surface.
  • the adhesive layer 5 is mainly composed of the first resin or the second resin, and the content of the inorganic filler 4 is relatively small. Therefore, since the inorganic filler 4 at the interface between the insulating resin composition 10 and the base material to which the insulating resin composition 10 is bonded decreases and the first resin or the second resin constituting the adhesive layer 5 increases, the adhesive strength with the base material is increased. It becomes possible to improve.
  • the adhesive layer 5 is not separately attached to the phase-separated structure 1 after being separately manufactured, but the phase separation between the first resin phase 2 and the second resin phase 3 is performed. It is a layer formed on the surface of the phase separation structure 1 together with the structure. That is, the adhesive layer 5 is a layer formed integrally with the first resin phase 2 and the second resin phase 3 on the surface of the phase separation structure 1.
  • the adhesive layer 5 is formed together with the phase separation structure of the first resin phase 2 and the second resin phase 3, it is possible to simplify the manufacturing process.
  • the mechanism by which the adhesive layer 5 is formed on the surface of the phase separation structure 1 is considered as follows.
  • the insulating resin composition 10 of the present embodiment is obtained by the following procedure. First, an inorganic filler and a curing agent are added and kneaded to the first resin constituting the first resin phase 2 and the second resin constituting the second resin phase 3 to prepare an uncured resin composition. And the insulating resin composition 10 can be obtained by making it harden
  • the epoxy resin forms the adhesive layer 5. That is, since the surface of aluminum has a hydroxyl group and has high affinity with the epoxy resin, the epoxy resin self-assembles to form the adhesive layer 5 when forming the phase separation structure. Thus, by selecting these materials in consideration of the affinity between the resin and the substrate, it is possible to form the adhesive layer 5 made of a desired resin on the surface of the phase separation structure 1. However, even if the adhesive layer 5 of the present invention is formed by another mechanism, the technical scope of the present invention is not affected at all.
  • the thickness t of the adhesive layer 5 is preferably 0.1 ⁇ m or more and 5 ⁇ m or less.
  • the thickness t of the adhesive layer 5 is 0.1 ⁇ m or more, it is possible to increase the adhesive force with the base material.
  • the thickness t of the adhesive layer 5 is 5 ⁇ m or less, a decrease in thermal conductivity due to the presence of the adhesive layer 5 can be suppressed.
  • the thickness t of the adhesive layer 5 is more preferably not less than 0.3 ⁇ m and not more than 4 ⁇ m. By being in this range, it is possible to achieve both high adhesive strength and thermal conductivity.
  • the thickness t of the adhesive layer 5 can be measured by observing the cross section of the insulating resin composition 10 with a scanning electron microscope.
  • the adhesive layer 5 is mainly composed of the first resin or the second resin. Therefore, the content of the first resin or the second resin in the adhesive layer 5 needs to be 50 mol% or more, preferably 80 mol% or more, more preferably 95 mol% or more, and particularly preferably 99 mol% or more.
  • the adhesive layer 5 may contain not only the resin component but also the inorganic filler 4. Since the thermal conductivity of the adhesive layer 5 is improved by containing the inorganic filler 4, the thermal conductivity of the insulating resin composition 10 as a whole can be further improved. However, when the inorganic filler 4 is contained, the amount of the resin component of the adhesive layer 5 is decreased, and the adhesive strength with the base material is decreased. Therefore, it is preferable that the content of the inorganic filler 4 is small.
  • the insulating resin composition 10 has the first resin phase 2 and the second resin phase 3, and further has a structure in which these resin phases are mixed and phase-separated.
  • the inorganic filler 4 is dispersed inside the phase separation structure 1.
  • the inorganic filler 4 is preferably unevenly distributed in the first resin phase 2 inside the phase separation structure 1. In this case, since the heat conduction path is easily formed in the first resin phase 2 by the contact of the particles of the inorganic filler 4, the heat conductivity of the insulating resin composition 10 can be further improved. . Even when the inorganic filler 4 is unevenly distributed in the first resin phase 2, it is not necessary for the inorganic filler 4 to be disposed entirely inside the first resin phase 2, and a part thereof exists in the second resin phase 3. It does not matter.
  • the adhesive layer 5 preferably contains the second resin constituting the second resin phase 3 as a main component.
  • content of the 2nd resin in the contact bonding layer 5 is 50 mol% or more, 80 mol% or more is preferable, 95 mol% or more is more preferable, 99 mol% or more is especially preferable.
  • the first resin phase 2 is three-dimensionally continuous inside the phase separation structure 1. Furthermore, it is preferable that the inorganic filler 4 is unevenly distributed in the first resin phase 2 that is three-dimensionally continuous. Thereby, since a three-dimensional heat conduction path can be formed inside the phase separation structure 1, it is possible to improve the heat conductivity of the entire insulating resin composition even when the content of the inorganic filler 4 is small. It becomes.
  • the phase separation structure means any one of a sea-island structure, a continuous spherical structure, a composite dispersion structure, and a co-continuous structure.
  • the sea-island structure refers to a structure in which a dispersed phase 31 having a small volume is dispersed in the continuous phase 21, and is a structure in which fine particles or spherical dispersed phases 31 are scattered in the continuous phase 21.
  • the continuous spherical structure is a structure in which approximately spherical dispersed phases 31 are connected and dispersed in the continuous phase 21 as shown in FIG. 2B. As shown in FIG.
  • the composite dispersed structure is a structure in which the dispersed phase 31 is dispersed in the continuous phase 21 and the resin constituting the continuous phase is dispersed in the dispersed phase 31.
  • the co-continuous structure is a structure in which the continuous phase 21 and the dispersed phase 31 form a complicated three-dimensional network.
  • the continuous phase 21 is preferably the first resin phase 2.
  • the phase separation structure such as the sea-island structure, continuous spherical structure, composite dispersion structure, and co-continuous structure is achieved by controlling the curing conditions such as the curing speed and reaction temperature of the resin composition, the compatibility of the resin, and the mixing ratio. Obtainable.
  • the first resin phase 2 is formed of one of a thermosetting resin and a thermoplastic resin
  • the second resin phase 3 is formed of the other of the thermosetting resin and the thermoplastic resin. That is, when the 1st resin phase 2 is comprised with the thermosetting resin, it is preferable that the 2nd resin phase 3 is comprised with the thermoplastic resin. Moreover, when the 1st resin phase 2 is comprised with the thermoplastic resin, it is preferable that the 2nd resin phase 3 is comprised with the thermosetting resin. Thereby, it becomes easy to form the phase separation structure.
  • the adhesive layer 5 is mainly composed of a thermosetting resin or a thermoplastic resin.
  • thermosetting resins examples include epoxy resins, unsaturated polyester resins, vinyl ester resins, phenol resins, urethane resins, urea resins, melamine resins, maleimide resins, cyanate ester resins, alkyd resins, and addition curable polyimide resins. It is done.
  • One of these thermosetting resins may be used alone, or two or more may be used in combination.
  • an epoxy resin is preferable because it is excellent in heat resistance, electrical insulation, and mechanical properties.
  • thermosetting resin When an epoxy resin is used as the thermosetting resin, a known one can be used.
  • bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalenediol type epoxy resin, phenol novolac type epoxy resin can be used.
  • a cresol novolac type epoxy resin, a bisphenol A novolac type epoxy resin, a cyclic aliphatic epoxy resin, a heterocyclic epoxy resin (triglycidyl isocyanurate, diglycidyl hydantoin, etc.) can also be used.
  • modified epoxy resins obtained by modifying these epoxy resins with various materials can also be used.
  • halides such as bromides and chlorides of these epoxy resins can also be used.
  • One of these epoxy resins may be used alone, or two or more of them may be used in combination.
  • the curing agent for curing the epoxy resin is not particularly limited as long as it is a compound having an active group capable of reacting with an epoxy group.
  • Known epoxy curing agents can be used as appropriate, but compounds having an amino group, an acid anhydride group, or a hydroxyphenyl group are particularly suitable.
  • Examples of curing agents include dicyandiamide and derivatives thereof, organic acid hydrazine, amine imides, aliphatic amines, aromatic amines, tertiary amines, polyamine salts, microcapsule type curing agents, imidazole type curing agents, acid anhydrides, phenol novolacs. Etc. A hardening
  • curing agent may be used individually by 1 type of these, and may be used in combination of 2 or more type.
  • the tertiary accelerator is a tertiary amine curing accelerator, a urea derivative curing accelerator, an imidazole curing accelerator, or a diazabicycloundecene (DBU) curing.
  • Accelerators can be mentioned.
  • organophosphorus curing accelerators for example, phosphine curing accelerators
  • onium salt curing accelerators for example, phosphonium salt curing accelerators, sulfonium salt curing accelerators, ammonium salt curing accelerators, etc.
  • group hardening accelerator, an acid, and a metal salt type hardening accelerator etc. can be mentioned.
  • the thermoplastic resin generally has at least one bond selected from the group consisting of a carbon-carbon bond, an amide bond, an imide bond, an ester bond, and an ether bond in the main chain. Further, the thermoplastic resin may have at least one bond selected from the group consisting of a carbonate bond, a urethane bond, a urea bond, a thioether bond, a sulfone bond, an imidazole bond, and a carbonyl bond in the main chain.
  • thermoplastic resin examples include polyolefin resins, polyamide resins, elastomeric (styrene, olefin, polyvinyl chloride (PVC), urethane, ester, amide) resins, polyester resins, and the like. It is done. Further, engineering plastics, polyethylene, polypropylene, nylon resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylic resin, ethylene acrylate resin, ethylene vinyl acetate resin, and polystyrene resin can be used.
  • thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more type.
  • thermoplastic resin from the viewpoint of heat resistance.
  • polyethersulfone which is excellent in various points such as mechanical properties, insulating properties and solubility in a solvent is more preferable.
  • thermoplastic resins may have a functional group capable of reacting with an epoxy resin.
  • functional groups include amino groups, hydroxyl groups, chlorine atoms, and alkoxy groups.
  • thermosetting resin examples include the following combinations.
  • thermosetting resin examples include the thermosetting resin.
  • polyethersulfone or polyetherimide can be used as the thermoplastic resin.
  • unsaturated polyester resin when used as the thermosetting resin, polystyrene can be used as the thermoplastic resin.
  • the average particle diameter of the inorganic filler 4 is preferably 0.1 ⁇ m or more and 15 ⁇ m or less.
  • the average particle diameter of the inorganic filler 4 is 0.1 ⁇ m or more and 15 ⁇ m or less, it is easy to disperse inside the phase-separated structure 1, and an insulating resin composition having good workability and moldability can be obtained. it can. That is, when the average particle size is 0.1 ⁇ m or more, the viscosity of the resin can be prevented from becoming excessively high, and the fluidity of the resin is ensured, so that workability and moldability are improved.
  • the inorganic filler 4 becomes easy to be disperse
  • the average particle diameter means a median diameter.
  • the median diameter means a particle diameter (d 50 ) at which an integrated (cumulative) weight percentage is 50%.
  • the median diameter can be measured using, for example, a laser diffraction particle size distribution analyzer SALD2000 (manufactured by Shimadzu Corporation).
  • SALD2000 laser diffraction particle size distribution analyzer manufactured by Shimadzu Corporation.
  • the average particle diameter of the inorganic filler 4 contained in the insulating resin composition 10 can be measured by baking the insulating resin composition 10 and isolating the inorganic filler 4.
  • the ratio of the inorganic filler 4 in the insulating resin composition 10 is more preferably 15% by volume or more and 70% by volume or less, and particularly preferably 30% by volume or more and 60% by volume. By being in such a range, it becomes possible to achieve both high thermal conductivity and moldability.
  • the insulating resin composition 10 can provide a resin composition having electrical insulation by using a material exhibiting electrical insulation.
  • the constituent material of the inorganic filler 4 is preferably an inorganic compound having both thermal conductivity and electrical insulation.
  • the inorganic compound having thermal conductivity for example, an inorganic compound having a thermal conductivity of 1 W / m ⁇ K or more can be used.
  • the thermal conductivity of the inorganic compound having thermal conductivity is preferably 10 W / m ⁇ K or more, and more preferably 30 W / m ⁇ K or more.
  • the inorganic compound having electrical insulation an inorganic compound having a volume resistivity of 10 ⁇ ⁇ cm or more at room temperature (25 ° C.) can be used.
  • the volume resistivity of the electrically insulating inorganic compound is preferably 10 5 ⁇ ⁇ cm or more, more preferably 10 8 ⁇ ⁇ cm or more, and particularly preferably 10 13 ⁇ ⁇ cm or more.
  • inorganic compounds having both heat dissipation and electrical insulation include borides, carbides, nitrides, oxides, silicides, hydroxides, carbonates, and the like.
  • Specific examples include magnesium oxide (MgO), aluminum oxide (Al 2 O 3 ), boron nitride (BN), aluminum nitride (AlN), and aluminum hydroxide (Al (OH) 3 ).
  • the inorganic filler 4 preferably contains at least one selected from the group consisting of MgO, Al 2 O 3 , BN, and AlN.
  • the surface of the inorganic filler 4 may be treated by a coupling treatment or the like, or a dispersant may be added to the insulating resin composition 10.
  • a dispersant may be added to the insulating resin composition 10.
  • organic surface treatment agents such as fatty acids, fatty acid esters, higher alcohols, and hardened oils can be used.
  • an inorganic surface treatment agent such as a silicone oil, a silane coupling agent, an alkoxysilane compound, or a silylated material can also be used for the surface treatment.
  • water resistance may be improved, and dispersibility in the resin may be further improved.
  • a processing method There exist (1) dry method, (2) wet method, (3) integral blend method etc.
  • the dry method is a method in which a surface treatment agent is dropped onto a surface treatment agent while stirring the inorganic filler by mechanical stirring such as a Henschel mixer, a Nauter mixer, or a vibration mill.
  • a solution obtained by diluting silane with an alcohol solvent a solution obtained by diluting silane with an alcohol solvent, further adding water, diluting silane with an alcohol solvent, and further adding water and an acid.
  • a preparation method of a surface treating agent is described in the catalog of the manufacturer of a silane coupling agent, etc., a preparation method is suitably determined according to the hydrolysis rate of silane and the kind of inorganic filler.
  • the wet method is a method in which an inorganic filler is directly immersed in a surface treatment agent.
  • the surface treatment agent that can be used is the same as in the dry method.
  • the method for preparing the surface treatment agent is the same as the dry method.
  • the integral blend method is a method of diluting a surface treatment agent with a stock solution or alcohol and directly adding it to a mixer when mixing the resin and filler, followed by stirring.
  • the preparation method of the surface treatment agent is the same as the dry method and the wet method, but the amount of the surface treatment agent in the case of the integral blend method is generally larger than that in the dry method and the wet method.
  • the surface treatment agent is dried as necessary.
  • a surface treatment agent using alcohol or the like it is necessary to volatilize the alcohol. If alcohol eventually remains in the formulation, the alcohol is generated as a gas that adversely affects the polymer content. Therefore, it is preferable that the drying temperature be equal to or higher than the boiling point of the solvent used.
  • the apparatus is used to heat to a high temperature (for example, 100 ° C. or higher, 150 ° C.) in order to quickly remove the silane that has not reacted with the inorganic filler. It is preferable. However, considering the heat resistance of the silane, it is preferable to keep the temperature below the decomposition point of the silane.
  • the treatment temperature is preferably about 80 ° C. or more, 150 ° C.
  • the treatment time is preferably 0.5 hours or more and 4 hours.
  • the amount of silane necessary for treating the surface of the inorganic filler can be calculated by the following equation.
  • Silane amount (g)] [Amount of inorganic filler (g)] ⁇ [Specific surface area of inorganic filler (m 2 / g)] / [Minimum coverage area of silane (m 2 / g)]
  • the minimum covering area of silane can be obtained by the following calculation formula.
  • the required amount of silane is preferably 0.5 times or more and less than 1.0 times the amount of silane calculated by this calculation formula. Even if the amount of silane is 1.0 times or more, the dispersibility of the inorganic filler 4 can be improved. However, when the amount of silane is 1.0 times or more, an unreacted component remains, which may cause deterioration of physical properties such as deterioration of mechanical properties and water resistance. Therefore, the upper limit is preferably less than 1.0 times. Moreover, the reason why the lower limit value is set to 0.5 times the amount calculated by the above formula is that even this amount is sufficiently effective for improving the filler filling property into the resin.
  • the insulating resin composition 10 includes a colorant, a flame retardant, a flame retardant aid, a fiber reinforcing material, a viscosity reducing agent for adjusting viscosity in production, and a toner as long as thermal conductivity and adhesiveness are not impaired.
  • a dispersion adjusting agent, a release agent and the like for improving the dispersibility of (colorant) may be contained. These may be known ones, and examples thereof include the following.
  • an inorganic pigment such as titanium oxide, an organic pigment or the like, or a toner containing them as a main component
  • a toner containing them as a main component can be used. These may be used individually by 1 type and may be used in combination of 2 or more types.
  • flame retardants examples include organic flame retardants, inorganic flame retardants, and reactive flame retardants. These may be used individually by 1 type and may be used in combination of 2 or more types.
  • a flame retardant aid examples include antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimonate, antimony compounds such as antimony tartrate, zinc borate, and barium metaborate.
  • hydrated alumina, zirconium oxide, ammonium polyphosphate, tin oxide, iron oxide, and the like are also included. These may be used individually by 1 type and may be used in combination of 2 or more types.
  • the thermal conductivity of the insulating resin composition 10 of the present embodiment is preferably 3 W / m ⁇ K or more. Even if the thermal conductivity is less than 3 W / m ⁇ K, the effect of the present invention can be exhibited. However, with such a thermal conductivity, when the insulating resin composition 10 is used as a heat radiator for an electronic component, the electronic component can be efficiently cooled even if the size is reduced.
  • a method for producing the insulating resin composition of the present embodiment will be described.
  • a first resin, a second resin, an inorganic filler, and a curing agent are added and kneaded to produce an uncured resin composition.
  • the kneading of each component may be performed in one step, or each component may be added sequentially or in multiple steps. When adding each component sequentially, it can add in arbitrary orders.
  • a part or all of the second resin is kneaded with the first resin to adjust the viscosity.
  • the order of addition is not particularly limited, but the curing agent is preferably added last from the viewpoint of the storage stability of the resin composition.
  • additives such as a colorant, a flame retardant, a flame retardant aid, a fiber reinforcement, a viscosity reducer, a dispersion regulator, and a release agent are added to the resin composition as necessary. May be. Also, the order of addition of these additives is not particularly limited and can be added at an arbitrary stage. However, as described above, the curing agent is preferably added last.
  • the kneading machine used for the production of the resin composition conventionally known ones can be used. Specific examples include a roll mill, a planetary mixer, a kneader, an extruder, a Banbury mixer, a mixing vessel provided with a stirring blade, and a horizontal mixing vessel.
  • the kneading temperature at the time of producing the resin composition is not particularly limited as long as it can be kneaded, but is preferably in the range of, for example, 10 ° C. or more and 150 ° C. or less. When it exceeds 150 degreeC, a partial hardening reaction will start and the storage stability of the resin composition obtained may fall. If it is lower than 10 ° C., the viscosity of the resin composition is high, and it may be difficult to knead substantially. Preferably it is 20 to 120 degreeC, More preferably, it is the range of 30 to 100 degreeC.
  • the resin composition is cured while the uncured resin composition is in contact with the substrate.
  • a method such as heating, light irradiation, or electron beam irradiation can be used depending on the type of the curing agent.
  • resin with high affinity with a base material comprises an adhesive layer among the 1st and 2nd resin which forms a phase-separation structure. Therefore, the adhesive layer can be formed by performing a curing treatment in a state where the uncured resin composition is in contact with the substrate.
  • the uncured resin composition can be formed into an arbitrary shape.
  • the molding method can be any method, and for example, various means such as compression molding (direct pressure molding), transfer molding, injection molding, extrusion molding, and screen printing can be used.
  • the material of the base material is not particularly limited, but may be basically anything such as ceramic, metal, glass, plastic, decorative plywood or a composite thereof.
  • the shape of the substrate is not particularly limited, and may be a simple shape or a complex shape such as a plate-like object, a spherical object, a columnar object, a cylindrical object, a rod-like object, a prismatic object, or a hollow prismatic object.
  • the insulating resin composition 10 is a phase-separated structure 1 having a first resin phase 2 formed of a first resin and a second resin phase 3 that is different from the first resin phase 2 and formed of a second resin.
  • the insulating resin composition 10 has an inorganic filler 4 dispersed inside the phase separation structure 1.
  • the phase-separation structure 1 has the contact bonding layer 5 which has 1st resin or 2nd resin as a main component on the surface, and thickness is 0.1 micrometer or more and 5 micrometers or less.
  • the adhesive layer is formed by self-composition, a process of attaching a separately formed adhesive layer to the phase separation structure as in the related art becomes unnecessary.
  • the insulating resin composition 10 By using the insulating resin composition 10, it is possible to simplify the manufacturing process while ensuring high adhesiveness with electronic components and the like described later.
  • the thickness of the adhesive layer 5 formed by self-composition is 0.1 ⁇ m or more and 5 ⁇ m or less, and is relatively thin. Therefore, it can suppress that the contact bonding layer 5 becomes obstructive of heat conduction.
  • the inorganic filler 4 is dispersed inside the phase separation structure 1, the insulating resin composition 10 can ensure high thermal conductivity. Furthermore, since the insulating resin composition 10 is made of a material having electrical insulation as described above, even the entire resin composition can have high electrical insulation.
  • FIG. 4 is a conceptual diagram of an article 6 composed of the insulating resin composition 10 and the electronic component 60. Since the insulating resin composition 10 has high thermal conductivity while ensuring electrical insulation as described above, it can be used as a thermal conductive component that cools the electronic component 60 and the like. Specifically, it can be used for the article 6 such as a sealing material which is one of the materials constituting the semiconductor package.
  • articles 6 such as metal / resin hybrid products such as light emitting diode lighting (LED lighting), electronic boards, IC chips, motor sealing materials, power devices, etc. that require heat dissipation. That is, in the article 6, the electronic component 60 and the insulating resin composition 10 are in contact with each other.
  • LED lighting light emitting diode lighting
  • Example # 1 To 100 parts by mass of bisphenol A type epoxy resin, 22.3 parts by mass of polyethersulfone (PES) pulverized so as to have an average particle diameter of 5 ⁇ m is added. Furthermore, this mixture is stirred in an oil bath warmed to 120 ° C., and the polyethersulfone is completely dissolved in the epoxy resin to obtain an epoxy resin solution.
  • PES polyethersulfone
  • alumina filler 125 parts by mass is kneaded into the above-mentioned epoxy resin solution heated to 80 ° C. using a rotation / revolution mixer. Further, 26 parts by mass of 4,4'-methylenedianiline is kneaded into the kneaded epoxy resin solution. Then, the obtained kneaded material is put into a vacuum dryer set at 120 ° C., and degassed under reduced pressure for 5 minutes to obtain a resin composition.
  • a copper foil having a thickness of 18 ⁇ m is put into a mold set at 150 ° C., and a resin composition is further introduced, followed by heating and pressing under a pressure of 3 MPa for 120 minutes. Thereby, the test piece of sample # 1 whose thickness is 1 mm can be created.
  • the epoxy resin for example, “jER (registered trademark) 828” manufactured by Mitsubishi Chemical Corporation can be used.
  • the polyethersulfone for example, “Sumika Excel (registered trademark) 5003P” manufactured by Sumitomo Chemical Co., Ltd. can be used.
  • 4,4'-methylenedianiline for example, a reagent manufactured by Wako Pure Chemical Industries, Ltd. can be used.
  • As the alumina filler for example, “AO-502” manufactured by Admatechs Co., Ltd. having an average particle diameter of 0.7 ⁇ m can be used.
  • sample # 2 The point which knead
  • Example # 3 In 100 parts by mass of the bisphenol A type epoxy resin, 5 parts by mass of dicyandiamide and 90 parts by mass of alumina filler are kneaded. Further, 12 parts by mass of methyl ethyl ketone is added as a solvent and kneaded with a planetary mixer. The obtained slurry is applied to an organic film and dried by heating at 120 ° C. or higher and 140 ° C. for 5 ⁇ m or longer for 10 minutes to remove the solvent and to semi-cure the resin component (B-stage) to obtain a B-stage resin sheet Is made.
  • the resin sheet and a copper foil having a thickness of 18 ⁇ m are superposed and heated and pressed for 90 minutes under conditions of a temperature of 170 ° C. and a pressure of 3 MPa. Thereby, a test piece of sample # 3 having a thickness of 1 mm can be prepared.
  • the epoxy resin for example, “EPICLON (registered trademark) 840S” manufactured by DIC Corporation can be used.
  • the alumina filler for example, “AO-502” manufactured by Admatechs Co., Ltd. having an average particle diameter of 0.7 ⁇ m can be used.
  • the organic film for example, “Lumirror (registered trademark) S10” manufactured by Toray Industries, Inc. can be used.
  • Example # 4 100 parts by mass of bisphenol A type epoxy resin is kneaded with 5 parts by mass of dicyandiamide, 1000 parts by mass of first alumina filler having an average particle diameter of 20 ⁇ m, and 430 parts by mass of second alumina filler having an average particle diameter of 5 ⁇ m. . Further, 230 parts by mass of methyl ethyl ketone is added as a solvent and kneaded with a planetary mixer.
  • a B-stage resin sheet is prepared in the same manner as in Sample # 3. Further, similarly to the sample # 3, a test piece of the sample # 4 can be prepared by heat-pressing the resin sheet and the copper foil.
  • a test piece of the sample # 4 can be prepared by heat-pressing the resin sheet and the copper foil.
  • the first alumina filler for example, “CB-A20S” manufactured by Showa Denko KK can be used.
  • the second alumina filler for example, “CB-A05S” manufactured by Showa Denko KK can be used.
  • Table 1 shows the blending amounts of thermosetting resin, thermoplastic resin, curing agent and inorganic filler of Samples # 1 to # 4.
  • volume ratio of inorganic filler First, the volume of the test piece of each example is calculated by an underwater substitution method. Next, each test piece is fired at 625 ° C. using a muffle furnace, and the ash weight is measured. Since ash is an inorganic filler, the volume ratio of the filler in the test piece can be measured from the density of the inorganic filler, the ash weight, and the volume of the test piece. In addition, the density of the alumina which is an inorganic filler is 3.9 g / cm 3 .
  • the thermal diffusivity is measured by the xenon flash method (z-axis direction), and the thermal conductivity is calculated from the following equation.
  • specific heat calculates the specific heat of each substance comprised from a composite law, and a density can be measured by the underwater substitution method.
  • Thermal conductivity (W / m ⁇ K) thermal diffusivity (m2 / s) ⁇ specific heat (J / kg ⁇ K) ⁇ density (kg / m 3 ) (Copper foil adhesion)
  • the adhesive force between the copper foil and the resin composition is evaluated according to JIS C6481 (Test method for copper-clad laminate for printed wiring board).
  • a copper foil adhesive strength by a peel test of 1.5 kN / m or more is evaluated as sufficient (Good), and a copper foil adhesive strength of less than 1.5 kN / m is evaluated as insufficient (NG).
  • FIG. 3 shows the observation result of the cross section of the test piece.
  • symbol 22 is a resin phase in which polyether sulfone exists.
  • symbol 22 is the ball
  • the inorganic filler 4 is observed in white in the SEM image, the inorganic filler 4 and the epoxy resin sphere can be distinguished.
  • Sample # 1 and Sample # 2 have both high thermal conductivity and adhesive strength compared to Sample # 3 and Sample # 4, respectively.
  • sample # 1 and sample # 3 contain the same volume of inorganic filler, and both contain a large amount of resin. Therefore, both adhesive strengths are good.
  • the resin composition of Sample # 1 has a good thermal conductivity because a thermal conduction path is formed by an inorganic filler.
  • sample # 3 does not contain a thermoplastic resin. Therefore, the heat conduction path is not sufficiently formed, and the heat conductivity is lower than that of the sample # 1.
  • sample # 4 has the same thermal conductivity as sample # 2. However, since sample # 4 contains more filler than sample # 2, the amount of resin is insufficient, and the adhesive force is lower than that of sample # 2.
  • test piece of sample # 1 has a bicontinuous phase separation structure, and it can be confirmed that the inorganic filler is unevenly distributed on one side of the resin layer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)
  • Insulating Bodies (AREA)
  • Inorganic Insulating Materials (AREA)

Abstract

La présente invention concerne une composition de résine isolante comprenant une structure à phases séparées composée d'une première phase de résine, qui est formée d'une première résine, et d'une seconde phase de résine qui est différente de la première phase de résine et qui est formée d'une seconde résine. La composition de résine isolante comprend également une charge inorganique qui est dispersée à l'intérieur de la structure à phases séparées. La structure à phases séparées comprend, formée sur sa surface, une couche adhésive contenant la première résine ou la seconde résine comme constituant principal et ayant une épaisseur de 0,1 à 5 µm inclus.
PCT/JP2014/005694 2013-11-20 2014-11-13 Composition de résine isolante et article comprenant celle-ci WO2015075906A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013239603A JP2017014302A (ja) 2013-11-20 2013-11-20 絶縁樹脂組成物及びこれを備えた物品
JP2013-239603 2013-11-20

Publications (1)

Publication Number Publication Date
WO2015075906A1 true WO2015075906A1 (fr) 2015-05-28

Family

ID=53179193

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/005694 WO2015075906A1 (fr) 2013-11-20 2014-11-13 Composition de résine isolante et article comprenant celle-ci

Country Status (2)

Country Link
JP (1) JP2017014302A (fr)
WO (1) WO2015075906A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021105191A (ja) * 2017-01-19 2021-07-26 東亞合成株式会社 有機−無機複合物およびその製造方法
WO2022009887A1 (fr) * 2020-07-08 2022-01-13 昭和電工マテリアルズ株式会社 Composition de résine, film et produit durci
EP4195462A4 (fr) * 2020-08-07 2024-02-28 Resonac Corporation Matériau isolant pour stator, stator et procédé de fabrication de stator

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7337840B2 (ja) * 2018-11-30 2023-09-04 デンカ株式会社 積層体
WO2020111180A1 (fr) * 2018-11-30 2020-06-04 デンカ株式会社 Corps stratifié
JP2022138157A (ja) * 2021-03-09 2022-09-22 パナソニックＩｐマネジメント株式会社 熱伝導性樹脂組成物及び熱伝導性樹脂材料

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0959511A (ja) * 1995-08-18 1997-03-04 Tokai Rubber Ind Ltd 熱伝導性樹脂組成物
JP2002371190A (ja) * 2001-06-13 2002-12-26 Toppan Printing Co Ltd 多層プリント配線板用絶縁性樹脂組成物、これを用いた多層プリント配線板、及びこれを用いた製造方法
JP2007327010A (ja) * 2006-06-09 2007-12-20 Kaneka Corp 高熱伝導性熱可塑性樹脂組成物
JP2010132894A (ja) * 2008-10-30 2010-06-17 Nitto Denko Corp 有機−無機複合物およびその製造方法
JP2010132838A (ja) * 2008-12-08 2010-06-17 Mitsubishi Electric Corp 高熱伝導性熱硬化性樹脂組成物
JP2013136712A (ja) * 2011-01-31 2013-07-11 Toray Ind Inc ポリマーアロイの製造方法およびポリマーアロイ

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0959511A (ja) * 1995-08-18 1997-03-04 Tokai Rubber Ind Ltd 熱伝導性樹脂組成物
JP2002371190A (ja) * 2001-06-13 2002-12-26 Toppan Printing Co Ltd 多層プリント配線板用絶縁性樹脂組成物、これを用いた多層プリント配線板、及びこれを用いた製造方法
JP2007327010A (ja) * 2006-06-09 2007-12-20 Kaneka Corp 高熱伝導性熱可塑性樹脂組成物
JP2010132894A (ja) * 2008-10-30 2010-06-17 Nitto Denko Corp 有機−無機複合物およびその製造方法
JP2010132838A (ja) * 2008-12-08 2010-06-17 Mitsubishi Electric Corp 高熱伝導性熱硬化性樹脂組成物
JP2013136712A (ja) * 2011-01-31 2013-07-11 Toray Ind Inc ポリマーアロイの製造方法およびポリマーアロイ

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021105191A (ja) * 2017-01-19 2021-07-26 東亞合成株式会社 有機−無機複合物およびその製造方法
JP7136261B2 (ja) 2017-01-19 2022-09-13 東亞合成株式会社 有機－無機複合物およびその製造方法
WO2022009887A1 (fr) * 2020-07-08 2022-01-13 昭和電工マテリアルズ株式会社 Composition de résine, film et produit durci
EP4195462A4 (fr) * 2020-08-07 2024-02-28 Resonac Corporation Matériau isolant pour stator, stator et procédé de fabrication de stator

Also Published As

Publication number Publication date
JP2017014302A (ja) 2017-01-19

Similar Documents

Publication Publication Date Title
WO2015075906A1 (fr) Composition de résine isolante et article comprenant celle-ci
JP6025967B2 (ja) 絶縁熱伝導性樹脂組成物
TWI814907B (zh) 樹脂組成物、薄膜、層合板及半導體裝置
JP6501211B2 (ja) 半導体パッケージ用熱硬化性樹脂組成物とこれを用いたプリプレグ
TWI555733B (zh) 預浸體及積層板
TW201609943A (zh) 電子材料用環氧樹脂組成物、其硬化物及電子構件
JP2013001807A (ja) 電子回路基板材料用樹脂組成物、プリプレグ及び積層板
JP5547032B2 (ja) 熱伝導性樹脂組成物、樹脂シート、プリプレグ、金属積層板およびプリント配線板
WO2021079900A1 (fr) Composition de résine, film de résine, film métallique attaché à la résine, préimprégné, feuille stratifiée à plaquage métallique, et carte de câblage imprimée
TW201815957A (zh) 樹脂組成物、預浸體、覆金屬箔疊層板、樹脂片及印刷電路板
WO2017022721A1 (fr) Composition de résine époxy, composition de résine époxy en forme de film et dispositif électronique
CN108463321A (zh) 预浸渍体、印刷布线板、半导体封装体及印刷布线板的制造方法
JP6504472B2 (ja) 絶縁熱伝導性樹脂組成物
CN103897406A (zh) 用于印刷电路板的绝缘薄膜及其制造方法和使用所述绝缘薄膜的印刷电路板
JP6422230B2 (ja) プリント回路基板用絶縁樹脂組成物およびこれを用いた製品
TWI829809B (zh) 樹脂組成物、預浸體、附樹脂之薄膜、附樹脂之金屬箔、覆金屬積層板及印刷配線板
JP2008195835A (ja) エポキシ樹脂ワニスの製造法、プリプレグの製造法、積層板および配線板の製造法
JP5767540B2 (ja) エピスルフィド樹脂材料であるｂステージフィルム、多層基板及び積層フィルム
KR20160096606A (ko) 접착층 부착 이형 폴리이미드 필름, 접착층 부착 이형 폴리이미드 필름이 부착된 적층판, 적층판, 접착층 부착 이형 폴리이미드 필름이 부착된 단층 또는 다층 배선판, 및 다층 배선판의 제조 방법
JP7209267B2 (ja) 樹脂組成物、樹脂フィルム、樹脂付き金属箔、プリプレグ、金属張積層板及びプリント配線板
TW201611669A (zh) 覆金屬箔基板、電路基板及電子零件搭載基板
JP5712488B2 (ja) 絶縁性樹脂フィルム及びそれを用いた積層板、配線板
JP6617710B2 (ja) 金属箔張基板、回路基板および発熱体搭載基板
TWI688603B (zh) 樹脂組成物及使用該樹脂組成物的絕緣膜和產品
JP5727325B2 (ja) 熱硬化性樹脂材料及び多層基板

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14863480

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: JP

122 Ep: pct application non-entry in european phase

Ref document number: 14863480

Country of ref document: EP

Kind code of ref document: A1