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WO2017010403A1 - Matière à mouler à base de résine époxy, produit moulé et produit durci - Google Patents

Matière à mouler à base de résine époxy, produit moulé et produit durci Download PDF

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Publication number
WO2017010403A1
WO2017010403A1 PCT/JP2016/070167 JP2016070167W WO2017010403A1 WO 2017010403 A1 WO2017010403 A1 WO 2017010403A1 JP 2016070167 W JP2016070167 W JP 2016070167W WO 2017010403 A1 WO2017010403 A1 WO 2017010403A1
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WO
WIPO (PCT)
Prior art keywords
epoxy resin
molding material
resin molding
material according
inorganic filler
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2016/070167
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English (en)
Japanese (ja)
Inventor
田中　賢治
片木　秀行
竹澤　由高
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Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
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Filing date
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Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to JP2017528648A priority Critical patent/JP6512295B2/ja
Publication of WO2017010403A1 publication Critical patent/WO2017010403A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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

Definitions

  • the present invention relates to an epoxy resin molding material, a molded product, and a cured product.
  • Thermosetting resins such as epoxy resins are widely used as insulating materials used in industrial and automotive motors, inverters, and other devices from the standpoints of high insulation performance, ease of molding, heat resistance, etc. ing.
  • the high output and miniaturization of these devices have rapidly progressed, and the level of characteristics required for insulating materials has become considerably high.
  • the amount of heat generated from a high-density conductor tends to increase with downsizing, and how to dissipate heat is an important issue. Accordingly, various attempts have been made to improve the thermal conductivity after molding of the thermosetting resin.
  • thermosetting resin As one of the techniques for improving the thermal conductivity after molding of the thermosetting resin, there is a method of mixing a highly heat conductive filler into the thermosetting resin (for example, see Patent Document 1).
  • the viscosity of the resin composition increases as the amount thereof increases, and the workability tends to deteriorate or the dispersibility of the inorganic filler tends to decrease. Therefore, if the amount of the inorganic filler that can be mixed with the thermosetting resin can be increased, further improvement in thermal conductivity after molding can be expected. Furthermore, improvement of other characteristics such as heat resistance is also desired.
  • This invention is made
  • R 1 to R 4 are each independently a hydrogen atom or a monovalent group, and at least two of R 1 to R 4 are each independently a hydroxyl group or an amino group.
  • ⁇ 3> The epoxy resin molding material according to ⁇ 2>, wherein in general formula (I), at least two of R 1 to R 4 are hydroxyl groups.
  • ⁇ 5> The epoxy resin molding material according to any one of ⁇ 2> to ⁇ 4>, wherein a ratio of the compound represented by the general formula (I) to the entire curing agent is 20% by mass or more.
  • ⁇ 6> The epoxy resin molding material according to any one of ⁇ 1> to ⁇ 5>, wherein the epoxy resin includes an epoxy resin having a mesogen skeleton.
  • ⁇ 7> The epoxy resin molding material according to ⁇ 6>, wherein a ratio of the epoxy resin having the mesogenic skeleton to the entire epoxy resin is 50% by mass or more.
  • ⁇ 8> The epoxy resin molding material according to ⁇ 6> or ⁇ 7>, wherein a ratio of the epoxy resin having the mesogenic skeleton to the entire epoxy resin is 90% by mass or more.
  • ⁇ 9> The epoxy resin molding material according to any one of ⁇ 1> to ⁇ 8>, further including a silane coupling agent.
  • the silane coupling agent having a phenyl group has a structure in which the phenyl group is directly bonded to a silicon atom.
  • the adhesion amount of silicon atoms derived from the silane coupling agent per specific surface area of the inorganic filler is 5.0 ⁇ 10 ⁇ 6 mol / m 2 to 10.0 ⁇ 10 ⁇ 6 mol / m 2 .
  • ⁇ 9>- ⁇ 11> The epoxy resin molding material according to any one of ⁇ 11>.
  • ⁇ 13> The epoxy resin molding material according to any one of ⁇ 1> to ⁇ 12>, wherein the inorganic filler includes at least one selected from the group consisting of magnesium oxide and alumina.
  • ⁇ 14> The epoxy resin molding material according to any one of ⁇ 1> to ⁇ 13>, wherein the content of the inorganic filler is 60% by volume to 90% by volume in the solid content of the inorganic filler.
  • ⁇ 15> The epoxy resin molding material according to any one of ⁇ 1> to ⁇ 14>, in an A-stage state.
  • ⁇ 16> The epoxy resin molding material according to ⁇ 15>, wherein a mass reduction rate after heating at 180 ° C. for 1 hour is 0.1% by mass or less.
  • ⁇ 17> A molded product produced by molding the epoxy resin molding material according to any one of ⁇ 1> to ⁇ 16>.
  • ⁇ 18> A cured product produced by heat-treating the molded product according to ⁇ 17>.
  • an epoxy resin molding material excellent in thermal conductivity and heat resistance after molding and a molded product and a cured product using the same.
  • the term “process” includes a process that is independent of other processes and includes the process if the purpose of the process is achieved even if it cannot be clearly distinguished from the other processes. It is.
  • numerical values indicated by using “to” include numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the content of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. It means the content rate of.
  • the particle diameter of each component in the composition is a mixture of the plurality of types of particles present in the composition unless there is a specific indication when there are a plurality of types of particles corresponding to each component in the composition. Means the value of.
  • the term “layer” refers to the case where the layer is formed only in a part of the region in addition to the case where the layer is formed over the entire region. Is also included.
  • the epoxy resin molding material of the present embodiment contains an epoxy resin, a curing agent and an inorganic filler, and the curing agent is dibenzo [g, p having at least two substituents each independently a hydroxyl group or an amino group. ] Chrysene (hereinafter also referred to as a specific curing agent).
  • the amount of inorganic filler is increased without impairing the fluidity of the epoxy resin molding material as compared with the case of using a conventional curing agent. I knew it was possible. This indicates that the heat conductivity after the molding of the epoxy resin molding material can be improved. Furthermore, as a result of studies by the present inventors, it has been found that when a specific curing agent is used as the curing agent, the glass transition point (Tg) after molding is higher than when a conventional curing agent is used. This has shown that it is excellent in the heat resistance after shaping
  • the glass transition point of the molded product in a state where the epoxy resin molding material is removed from the mold after molding, and the glass transition point of the cured product obtained by heat-treating the molded product It was found that the difference was small. This indicates that heat resistance close to that after the heat treatment is achieved even after removal from the mold after molding, and that the heat treatment step after molding can be shortened or omitted.
  • epoxy resin molding material The kind of epoxy resin contained in the epoxy resin molding material is not particularly limited.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol AD type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol AD type epoxy resin, naphthalene type epoxy resin, and reactive diluent
  • An epoxy resin having only one epoxy group is included.
  • An epoxy resin may be used individually by 1 type, or may use 2 or more types together.
  • the epoxy resin molding material preferably contains an epoxy resin having a mesogenic skeleton as an epoxy resin.
  • the “mesogen skeleton” means a molecular structure that may exhibit liquid crystallinity.
  • specific examples include molecular structures including a biphenyl skeleton, a phenylbenzoate skeleton, an azobenzene skeleton, a stilbene skeleton, and derivatives thereof.
  • Epoxy resins having a mesogenic skeleton tend to form higher order structures and tend to have higher thermal conductivity when formed into molded articles.
  • the higher order structure is a state in which the constituent elements are arranged microscopically, and corresponds to, for example, a crystal phase and a liquid crystal phase. Whether or not such a higher-order structure exists can be easily determined by observation with a polarizing microscope.
  • the biphenyl type epoxy resin can be obtained by reacting a biphenol compound with epichlorohydrin by a known method.
  • Examples of such a biphenyl type epoxy resin include 4,4′-bis (2,3-epoxypropoxy) biphenyl and the like, and YL-6121H (manufactured by Mitsubishi Chemical Corporation) is commercially available.
  • Epoxy resins having a mesogenic skeleton may be used alone or in combination of two or more.
  • the epoxy equivalent of the epoxy resin having a mesogenic skeleton is preferably 130 g / eq to 500 g / eq, more preferably 135 g / eq to 400 g / eq, and further preferably 140 g / eq to 300 g / eq.
  • the epoxy resin having a mesogenic skeleton may be in a prepolymer state in which a part thereof is partially reacted with a curing agent or the like.
  • Epoxy resins having a mesogenic skeleton are generally easily crystallized and often have low solubility in a solvent.
  • crystallization tends to be suppressed. For this reason, the moldability of a molding material may improve by setting it as the state of a prepolymer.
  • the ratio of the epoxy resin having a mesogen skeleton to the entire epoxy resin is preferably 50% by mass or more, and 90% by mass More preferably, it is more preferably 95% by mass or more.
  • the curing agent contained in the epoxy resin molding material contains dibenzo [g, p] chrysene (hereinafter also referred to as a specific curing agent) having at least two substituents each independently being a hydroxyl group or an amino group.
  • the at least two substituents are preferably located on different condensed aromatic rings of dibenzo [g, p] chrysene, respectively.
  • the number of at least two substituents is preferably 2 to 4, and more preferably 4.
  • the specific curing agent is preferably dibenzo [g, p] chrysene having at least two hydroxyl groups, and more preferably dibenzo [g, p] chrysene having four hydroxyl groups.
  • curing agent may be used individually by 1 type, or may use 2 or more types together.
  • the specific curing agent is preferably a compound represented by the following general formula (I).
  • JP-A-2014-152164 can be referred to.
  • R 1 to R 4 are each independently a hydrogen atom or a monovalent group, and at least two of R 1 to R 4 are each independently a hydroxyl group or an amino group.
  • the monovalent group is not particularly limited.
  • the monovalent group include a hydroxyl group, an amino group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Of these, a hydroxyl group, an amino group and an aliphatic hydrocarbon group are preferred, and a hydroxyl group and an amino group are more preferred.
  • the carbon number of the aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group may be independently 1 to 10, for example, preferably 1 to 5, and preferably 1 to 3. It is more preferable.
  • R 1 ⁇ R 4 is preferably at least two hydroxyl groups of R 1 ⁇ R 4, and more preferably all of R 1 ⁇ R 4 is a hydroxyl group .
  • the epoxy resin molding material of the present embodiment may contain a curing agent other than the specific curing agent as the curing agent.
  • a curing agent other curing agents, those usually used can be used without particular limitation, and phenol compounds, phenol resins obtained by novolacizing phenol compounds, and the like can be used.
  • the ratio of the specific curing agent in the entire curing agent is preferably 20% by mass or more, and more preferably 50% by mass or more. 80% by mass or more is more preferable.
  • the content of the curing agent in the epoxy resin molding material is not particularly limited.
  • the ratio of the number of equivalents of active hydrogen contained in the curing agent to the number of equivalents of epoxy groups contained in the epoxy resin is preferably 0.5 to 2. More preferably, it is 8 to 1.2.
  • the epoxy resin molding material may contain a curing accelerator. By using a curing agent and a curing accelerator in combination, curing of the epoxy resin molding material is promoted.
  • the type and blending amount of the curing accelerator are not particularly limited, and an appropriate one can be selected from the viewpoint of reaction rate, reaction temperature, storage property, and the like.
  • curing accelerator examples include imidazole compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts and the like.
  • a hardening accelerator may be used individually by 1 type, or may use 2 or more types together.
  • organic phosphorus compound is preferable.
  • organic phosphorus compounds include organic phosphine compounds, organic phosphine compounds such as maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, Quinone compounds such as 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, ⁇ bonds such as diazophenylmethane, phenol resin, etc.
  • a compound having an intramolecular polarization formed by adding a compound having an organic group and a complex of an organic phosphine compound and an organic boron compound such as tetraphenylborate, tetra-p-tolylborate, and tetra-n-butylborate. More preferred is at least one of
  • organic phosphine compound examples include triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, and tris (dialkylphenyl).
  • Phosphine tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine And alkyldiarylphosphine.
  • the content of the curing accelerator in the epoxy resin molding material is not particularly limited. From the viewpoint of fluidity and moldability, the content of the curing accelerator is preferably 0.1% by mass to 1.5% by mass of the total mass of the epoxy resin and the curing agent, preferably 0.2% by mass to More preferably, it is 1 mass%.
  • the epoxy resin molding material includes an inorganic filler.
  • the inorganic filler is preferably insulating.
  • the “insulating property” of the inorganic filler means the property that the inorganic filler itself does not flow current even when a voltage of several hundred volts to several thousand volts is applied, and is the most occupied by electrons. This is because the valence band having a high energy level is separated from the next band (conduction band) above it by a large energy gap.
  • the inorganic filler examples include boron nitride, alumina, silica, aluminum nitride, magnesium oxide, silicon oxide, aluminum hydroxide, and barium sulfate.
  • at least one selected from the group consisting of magnesium oxide and alumina is preferable from the viewpoints of fluidity, thermal conductivity, and electrical insulation.
  • boron nitride, silica, aluminum nitride or the like may be further contained within a range not impeding fluidity.
  • the proportion of at least one inorganic filler selected from the group consisting of magnesium oxide and alumina in the inorganic filler is preferably 50% by mass or more, more preferably 80% by mass or more, and 90% More preferably, it is at least mass%.
  • the inorganic filler may have a single peak or a plurality of peaks when a particle size distribution curve is drawn with the particle diameter on the horizontal axis and the frequency on the vertical axis.
  • the average particle size (D50) corresponding to 50% cumulative from the small particle size side of the weight cumulative particle size distribution of the inorganic filler is From the viewpoint of conductivity, the thickness is preferably 0.1 ⁇ m to 100 ⁇ m, more preferably 0.1 ⁇ m to 70 ⁇ m.
  • the inorganic filler having a plurality of peaks in the particle size distribution curve can be constituted, for example, by combining two or more inorganic fillers having different average particle diameters.
  • the average particle size of the inorganic filler is measured using a laser diffraction method, and when the weight cumulative particle size distribution curve is drawn from the small particle size side, the particle size is such that the weight cumulative is 50%.
  • the particle size distribution measurement using the laser diffraction method can be performed using a laser diffraction scattering particle size distribution measuring apparatus (for example, LS230 manufactured by Beckman Coulter).
  • the specific surface area of the inorganic filler is not particularly limited, for example, 0.01 m 2 / g can be selected from ⁇ 2m 2 / g, it is preferably selected from 0.1m 2 /g ⁇ 1.5m 2 / g .
  • the specific surface area of the inorganic filler is a value measured by the BET method.
  • the BET method is a gas adsorption method in which inert gas molecules such as nitrogen (N 2 ), argon (Ar), and krypton (Kr) are adsorbed on solid particles, and the specific surface area of the solid particles is measured from the amount of adsorbed gas molecules. Is the law.
  • the specific surface area can be measured using a specific surface area pore distribution measuring apparatus (for example, SA3100, manufactured by Beckman Coulter, Inc.).
  • the content of the inorganic filler in the epoxy resin molding material is not particularly limited. From the viewpoint of thermal conductivity and moldability, when the total volume of the solid content of the epoxy resin molding material is 100% by volume, it is preferably 60% by volume to 90% by volume, and 70% by volume to 85% by volume. It is more preferable that When the content of the inorganic filler is 60% by volume or more, higher thermal conductivity tends to be achieved. On the other hand, when the content of the inorganic filler is 90% by volume or less, the moldability of the epoxy resin molding material tends to be excellent.
  • the solid content of the epoxy resin molding material means a remaining component obtained by removing a volatile component such as an organic solvent from the epoxy resin molding material.
  • the content rate (volume%) of the inorganic filler in an epoxy resin molding material be the value calculated
  • Inorganic filler content (volume%) ⁇ (Cw / Cd) / ((Aw / Ad) + (Bw / Bd) + (Cw / Cd) + (Dw / Dd)) ⁇ ⁇ 100
  • each variable is as follows.
  • Aw mass composition ratio of epoxy resin (mass%) Bw: mass composition ratio (% by mass) of curing agent Cw: mass composition ratio of inorganic filler (mass%) Dw: Mass composition ratio (mass%) of other components (arbitrary components) Ad: Specific gravity of epoxy resin Bd: Specific gravity of curing agent Cd: Specific gravity of inorganic filler Dd: Specific gravity of other components (optional component)
  • the epoxy resin molding material may contain a silane coupling agent.
  • a silane coupling agent By including a silane coupling agent, an interaction occurs between the surface of the inorganic filler and the epoxy resin surrounding it, improving fluidity, achieving high thermal conductivity, and further intruding moisture. Insulating reliability tends to improve insulation reliability.
  • the type of the silane coupling agent is not particularly limited, and one type may be used alone or two or more types may be used in combination. Among these, a silane coupling agent containing a phenyl group is preferable.
  • a silane coupling agent containing a phenyl group is likely to interact with an epoxy resin having a mesogenic skeleton. For this reason, when the epoxy resin molding material contains an epoxy resin having a mesogen skeleton as an epoxy resin, a better thermal conductivity tends to be achieved by using a silane coupling agent containing a phenyl group.
  • silane coupling agent containing a phenyl group is not particularly limited. Specific examples include 3-phenylaminopropyltrimethoxysilane, 3-phenylaminopropyltriethoxysilane, N-methylanilinopropyltrimethoxysilane, N-methylanilinopropyltriethoxysilane, 3-phenyliminopropyltrimethoxysilane.
  • silane examples thereof include silane, 3-phenyliminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane, and triphenylethoxysilane.
  • the silane coupling agent containing a phenyl group may be used individually by 1 type, or may use 2 or more types together.
  • the proportion of the silane coupling agent having a phenyl group in the silane coupling agent is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
  • the phenyl group-containing silane coupling agent has the phenyl group directly bonded to the silicon atom. More preferably, a silane coupling agent is included.
  • the proportion of the silane coupling agent in which the phenyl group in the silane coupling agent having a phenyl group is directly bonded to the silicon atom is preferably 30% by mass or more, more preferably 50% by mass or more, More preferably, it is 80 mass% or more.
  • the silane coupling agent may be present in a state of adhering to the surface of the inorganic filler or in a state of not adhering to the surface of the inorganic filler. , Both may be mixed. From the viewpoint of moldability, it is preferable that at least a part of the silane coupling agent is attached to the surface of the inorganic filler, and at least a part of the silane coupling agent is interposed via the silicon atom in the molecule. More preferably, it adheres to the surface.
  • Whether or not at least a part of the silane coupling agent adheres to the surface of the inorganic filler is determined by the “method for measuring the amount of silicon atoms deposited from the silane coupling agent per specific surface area of the inorganic filler” described later. You can investigate.
  • the adhesion amount of silicon atoms derived from the silane coupling agent per specific surface area of the inorganic filler is 5.0 ⁇ 10 ⁇ 6 mol. / M 2 to 10.0 ⁇ 10 ⁇ 6 mol / m 2 is preferable, and 5.5 ⁇ 10 ⁇ 6 mol / m 2 to 9.5 ⁇ 10 ⁇ 6 mol / m 2 is more preferable, and 6.0 ⁇ 10. It is more preferably from ⁇ 6 mol / m 2 to 9.0 ⁇ 10 ⁇ 6 mol / m 2 .
  • the amount of silicon atoms derived from the silane coupling agent per specific surface area of the inorganic filler means the amount A (mol) of silicon atoms derived from the silane coupling agent contained in 1 g of the inorganic filler. It means a value (A / B) divided by the surface area B (m 2 ) per 1 g of the inorganic filler.
  • the measuring method of the adhesion amount of the silicon atom derived from the silane coupling agent per specific surface area of the inorganic filler is as follows.
  • the BET method is mainly applied as a method for measuring the specific surface area of the inorganic filler.
  • the BET method is a gas adsorption method in which inert gas molecules such as nitrogen (N 2 ), argon (Ar), and krypton (Kr) are adsorbed on solid particles, and the specific surface area of the solid particles is measured from the amount of adsorbed gas molecules. Is the law.
  • the specific surface area can be measured using a specific surface area pore distribution measuring apparatus (for example, SA3100, manufactured by Beckman Coulter, Inc.).
  • silicon atoms derived from the silane coupling agent present on the surface of the inorganic filler are quantified.
  • a quantification method 29 Si CP / MAS solid state NMR (nuclear magnetic resonance), fluorescent X-ray analysis or the like is used. Since the nuclear magnetic resonance apparatus (for example, JNM-ECA700, manufactured by JEOL Ltd.) has high resolution, even when the epoxy resin molding material contains silica as an inorganic filler, the silicon atoms derived from silica as the inorganic filler and It is possible to distinguish from silicon atoms derived from silane coupling agents.
  • the silicon atoms derived from the silane coupling agent are also quantified using a fluorescent X-ray analyzer (for example, Supermini 200, manufactured by Rigaku Corporation). can do.
  • a fluorescent X-ray analyzer for example, Supermini 200, manufactured by Rigaku Corporation.
  • the silane coupling agent per specific surface area of the inorganic filler The amount of silicon atoms attached is calculated.
  • the inorganic filler contained in the epoxy resin molding material can be taken out of the epoxy resin molding material by, for example, the following method.
  • An epoxy resin molding material is put in a magnetic crucible and heated in a muffle furnace or the like (for example, 600 ° C.) to burn the resin component.
  • the resin component of the epoxy resin molding material is dissolved in an appropriate solvent, and the inorganic filler is recovered by filtration and dried.
  • the method for adding the silane coupling agent to the epoxy resin molding material is not particularly limited. Specifically, an integral method in which a silane coupling agent is also added when mixing other materials such as epoxy resin and inorganic filler, after mixing a certain amount of silane coupling agent with a small amount of resin, Master batch method to mix with other materials such as inorganic filler, before mixing with other materials such as epoxy resin, mix inorganic filler and silane coupling agent in advance on the surface of inorganic filler Examples include a pretreatment method for treating a ring agent.
  • a dry method in which an undiluted solution or solution of a silane coupling agent is dispersed together with an inorganic filler by high-speed stirring, and the inorganic filler is slurried with a dilute solution of a silane coupling agent, or an inorganic filler
  • a wet method in which a silane coupling agent treatment is performed on the surface of the inorganic filler by immersing the silane coupling agent in the surface.
  • the epoxy resin molding material may contain other components in addition to the components described above.
  • Other components include oxidized or non-oxidized polyolefins, carnauba wax, montanic acid esters, montanic acid, stearic acid and other mold release agents, silicone oil, silicone rubber powder and other stress relieving agents, and glass fiber reinforcement. Materials.
  • the method for preparing the epoxy resin molding material is not particularly limited.
  • As a general technique there is a method in which components of a predetermined blending amount are sufficiently mixed with a mixer or the like, and then the mixture is melt-kneaded, cooled, and pulverized.
  • the melt kneading can be performed, for example, with a kneader, a mixing roll, an extruder or the like that has been heated to 70 ° C. to 140 ° C. in advance.
  • the epoxy resin molding material may be tableted with a size and mass that meet the molding conditions.
  • the epoxy resin molding material is preferably in an A-stage state.
  • the epoxy resin molding material is in the A-stage state, when the epoxy resin molding material is cured by heat treatment, the epoxy resin molding material is between the epoxy resin and the curing agent compared to the case where the epoxy resin molding material is in the B-stage state
  • the amount of reaction heat generated during the curing reaction increases, and the curing reaction easily proceeds.
  • the definitions of the terms A-stage and B-stage are based on JIS K 6800: 1985.
  • Whether or not the epoxy resin molding material is in the A-stage state is determined according to the following criteria.
  • a certain amount of the epoxy resin molding material is put into an organic solvent (tetrahydrofuran, acetone, etc.) in which the epoxy resin contained in the epoxy resin molding material is soluble, and the inorganic filler remaining after a certain period of time is filtered off. To do. If the difference between the mass after drying of the residue obtained by filtration and the mass of ash after high-temperature treatment is within ⁇ 0.5% by mass, it is judged that the epoxy resin molding material was in the A-stage state. Is done. The mass of ash is measured and calculated in accordance with JIS K 7250-1: 2006.
  • reaction heat per fixed mass of the epoxy resin molding material that has been previously determined to be in the A-stage state is measured by DSC (for example, Pyris 1 manufactured by Perkin Elmer Co., Ltd.) and used as a reference value. Thereafter, if the difference between the measured value of the heat of reaction per fixed mass of the prepared epoxy resin molding material and the reference value is within ⁇ 5%, it is determined that the A-stage state has been reached.
  • DSC for example, Pyris 1 manufactured by Perkin Elmer Co., Ltd.
  • the mass reduction rate after heating the A-stage epoxy resin molding material at 180 ° C. for 1 hour is preferably 0.1% by mass or less.
  • the mass reduction rate after heating the A-stage epoxy resin molding material at 180 ° C. for 1 hour is 0.1% by mass or less, which means that the A-stage epoxy resin molding material is so-called “solvent-free”. This means that it is a “mold” epoxy resin molding material.
  • the epoxy resin molding material is a solventless type, it is possible to obtain a molded product of the epoxy resin molding material without passing through a drying step, and the process for obtaining the molded product or the cured product can be simplified.
  • the molded product of the present embodiment is produced by molding the epoxy resin molding material of the present embodiment.
  • the cured product of the present embodiment is produced by heat-treating (post-curing) the molded product of the present embodiment.
  • the method for molding the epoxy resin molding material is not particularly limited, and can be selected from known methods such as a press molding method according to the application.
  • the transfer molding method is the most common method for molding the epoxy resin molding material, but a compression molding method or the like may be used.
  • the epoxy resin molding material can be used as it is after being molded and removed from the mold.
  • the molded product of the present embodiment tends to have a sufficiently high glass transition point and excellent heat resistance even when heat treatment is not performed, as compared with a conventional molded product.
  • the method for heat-treating the molded product is not particularly limited. For example, it can be performed using an oven set at a desired temperature.
  • the heat treatment conditions can be selected according to the type and amount of components such as epoxy resin and curing agent contained in the epoxy resin molding material.
  • the heat treatment temperature is preferably 130 ° C. to 200 ° C., more preferably 150 ° C. to 180 ° C.
  • the heat treatment time is preferably 1 hour to 10 hours, more preferably 2 hours to 6 hours.
  • the molded product and cured product of the present embodiment can be used in fields such as printed wiring boards and semiconductor element sealing materials, as well as industrial and automotive motors and inverters.
  • the molded product and the cured product of the present embodiment are used as a sealing material for a semiconductor element
  • examples of the electronic component device including the sealed element include a support (lead frame, wired tape carrier, wiring board).
  • Mounting elements active elements such as semiconductor chips, transistors, diodes, thyristors, passive elements such as capacitors, resistors, coils, etc.
  • An electronic component device in which necessary portions are sealed with the resin composition of the present embodiment is exemplified.
  • Example 1 to 5 and Comparative Examples 1 to 5 epoxy resin 1 and magnesium oxide were used.
  • Examples 6 to 7 and Comparative Examples 6 to 7 epoxy resin 1 and alumina were used.
  • Examples 8 to 9 and Comparative Example 8 were used.
  • 9 to 9 are epoxy resin 2 prepolymer and alumina
  • Example 10 and Comparative Example 10 are epoxy resin 1 and epoxy resin 3 (combined use) and alumina
  • Example 11 and Comparative Example 11 are epoxy resin 3 and alumina. Are common components.
  • the epoxy resin molding materials of Examples 1 to 11 and Comparative Examples 1 to 11 were all in the A-stage state. Further, when the epoxy resin molding materials of Examples 1 to 11 and Comparative Examples 1 to 11 were heated at 180 ° C. for 1 hour, the mass reduction ratios were all 0.1% by mass or less.
  • Epoxy resin 1 YL6121H (Mitsubishi Chemical Co., Ltd., a mixture containing a compound in which R is H in the following formula and a compound in which R is CH 3 in the following formula in an approximately 1: 1 ratio, epoxy equivalent: 172 g / eq)
  • Epoxy resin 2 trans-4- ⁇ 4- (2,3-epoxypropoxy) phenyl ⁇ cyclohexyl 4- (2,3-epoxypropoxy) benzoate (compound represented by the following structure, see Japanese Patent No. 5471975, epoxy equivalent: 212 g / Eq)
  • Epoxy resin 3 bisphenol F type epoxy resin without mesogenic skeleton
  • YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent: 195 g / eq
  • Curing agent 1 Tetrahydroxydibenzo [g, p] chrysene (compound represented by the following structure, see JP 2014-152164 A, hydroxyl equivalent: 98 g / eq)
  • KBM-202SS diphenyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 244
  • KBM-573 (3-phenylaminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 255)
  • KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 236)
  • TPP Triphenylphosphine, manufactured by Hokuko Chemical Co., Ltd.
  • the epoxy resin 2 prepolymer includes a part of propylene glycol monomethyl ether and an unreacted epoxy resin 2 that is not a prepolymer.
  • Solid content (%) (Measured amount after standing for 30 minutes (g) / Measured amount before heating (g)) ⁇ 100
  • the number average molecular weight of the epoxy resin 2 prepolymer was measured by gel permeation chromatography (GPC), the number average molecular weight of the polymer component newly produced by synthesis was 1520, and the number average of the range including the unreacted epoxy resin monomer The molecular weight was 607. It was 275 g / eq when the epoxy equivalent of the epoxy resin 2 prepolymer was measured by the perchloric acid titration method. When the softening point of the epoxy resin 2 prepolymer was measured by the ring and ball method, it was 95 ° C to 105 ° C.
  • the adhesion amount of silicon atoms derived from the silane coupling agent per specific surface area of the inorganic filler was measured by the following method. First, the specific surface area of the inorganic filler was measured by the BET method using a specific surface area pore distribution measuring device (for example, SA3100, manufactured by Beckman Coulter).
  • the molded product or the cured product was cut to produce a 10 mm square cube, and the density (g / cm 3 ) was measured by the Archimedes method.
  • the molded product or the cured product was cut to prepare a 10 mm square cube, and blackened with a graphite spray. Thereafter, the thermal diffusivity was evaluated by a xenon flash method (using LFA447 nanoflash manufactured by NETZSCH). From the product of this value, the density measured by the Archimedes method, and the specific heat measured by DSC (using Pyris 1 manufactured by PerkinElmer), the thermal conductivity (W / (m ⁇ K)) of the molded product or cured product. Asked.
  • the glass transition point (Tg) of the molded product or the cured product exceeds 260 ° C, whereas the curing agent does not contain the specific curing agent.
  • the glass transition point (Tg) of the molded product or cured product was less than 180 ° C. From this, it was found that a molded product or a cured product having a high glass transition point (Tg) and excellent heat resistance can be obtained in the present embodiment.
  • Example 10 in which the epoxy resin includes an epoxy resin (epoxy resin 1) having a mesogenic skeleton, the cured product has a thermal conductivity of 9.1 W / (m ⁇ K), and the epoxy resin has a mesogenic skeleton. It was higher than 7.2 W / (m ⁇ K) of Example 11 which does not contain an epoxy resin. From this, in this Embodiment, it turned out that the heat conductivity after shaping
  • epoxy resin includes an epoxy resin (epoxy resin 1) having a mesogenic skeleton.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne une matière à mouler à base de résine époxy contenant une résine époxy, un agent de durcissement et une charge inorganique, ledit agent de durcissement comprenant du dibenzo [g, p]chrysène ayant au moins deux substituants qui sont indépendamment un groupe hydroxyle ou un groupe amino.
PCT/JP2016/070167 2015-07-10 2016-07-07 Matière à mouler à base de résine époxy, produit moulé et produit durci Ceased WO2017010403A1 (fr)

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JP2023042690A (ja) * 2021-09-15 2023-03-28 住友ベークライト株式会社 熱硬化性樹脂組成物および電子装置
JPWO2023149521A1 (fr) * 2022-02-03 2023-08-10

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JPWO2019106813A1 (ja) * 2017-11-30 2021-01-21 昭和電工マテリアルズ株式会社 コンパウンド及びタブレット
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WO2023149521A1 (fr) * 2022-02-03 2023-08-10 味の素株式会社 Composition de résine, produit durci, matériau stratifié de type feuille, feuille de résine, carte de circuit imprimé et dispositif à semi-conducteur
JP7647942B2 (ja) 2022-02-03 2025-03-18 味の素株式会社 樹脂組成物、硬化物、シート状積層材料、樹脂シート、プリント配線板、及び半導体装置

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JPWO2017010403A1 (ja) 2018-02-15

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