WO2021117686A1 - Composé contenant un groupe imide, agent de durcissement contenant un groupe imide, et matériau durci de résine époxydique et matériau électriquement isolant utilisant ledit matériau durci de résine époxydique - Google Patents

Composé contenant un groupe imide, agent de durcissement contenant un groupe imide, et matériau durci de résine époxydique et matériau électriquement isolant utilisant ledit matériau durci de résine époxydique Download PDF

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WO2021117686A1
WO2021117686A1 PCT/JP2020/045513 JP2020045513W WO2021117686A1 WO 2021117686 A1 WO2021117686 A1 WO 2021117686A1 JP 2020045513 W JP2020045513 W JP 2020045513W WO 2021117686 A1 WO2021117686 A1 WO 2021117686A1
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epoxy resin
group
curing agent
imide
imide group
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PCT/JP2020/045513
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English (en)
Japanese (ja)
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あゆみ 谷中
中井　誠
由紀 田窪
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ユニチカ株式会社
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Priority to CN202080080567.8A priority Critical patent/CN114728903B/zh
Priority to JP2021507541A priority patent/JP6960705B1/ja
Priority to KR1020227009990A priority patent/KR20220114525A/ko
Publication of WO2021117686A1 publication Critical patent/WO2021117686A1/fr

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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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B19/00—Apparatus or processes specially adapted for manufacturing insulators or insulating bodies
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

Definitions

  • the present invention relates to an imide group-containing compound, an imide group-containing curing agent, an epoxy resin cured product, and an electrically insulating material using the same.
  • Epoxy resin cured products made of epoxy resin and its curing agent have excellent thermal, mechanical and electrical properties, and are widely used industrially mainly for electrical and electronic materials.
  • the curing agent for producing the epoxy resin cured product for example, a phenol-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent and the like are used.
  • SiC semiconductors can operate under higher temperature conditions than conventional silicon (Si) semiconductors, semiconductor encapsulants used in SiC semiconductors are also required to have higher heat resistance than ever before.
  • Patent Document 1 power devices are used under high temperature and high electric field due to miniaturization and high output, but under high temperature and high electric field, electric charges are accumulated in the insulating material, the electric field inside the semiconductor is distorted, and the resistance of the semiconductor element. Reduce the voltage. Therefore, in order to improve the performance of power devices, it is necessary to develop a material that does not cause charge accumulation under high temperature and high electric field in order to improve the withstand voltage at high temperature.
  • insulators made of pottery or ceramic have been conventionally used, but since the insulators are heavy and brittle, insulators using a polymer as a part have been studied (for example, Patent Document 2). ).
  • the voltage of insulators has been increasing, and along with this, the polymer used for insulators has a lower dielectric constant than conventional products in order to prevent charge accumulation, and can withstand high voltages. Highly insulating materials are required so that they can be used.
  • an insulating electric wire coating material is used for electric wires constituting electric devices such as motors (for example, Patent Document 3).
  • the output of motors has been increased, and the influence of partial discharge due to inverter surges is increasing.
  • the wire coating material used for motors is required to have a lower dielectric constant than conventional products in order to prevent inverter surges from occurring, and a highly insulating material so that it can withstand high output. There is.
  • Japanese Unexamined Patent Publication No. 2007-305962 Japanese Unexamined Patent Publication No. 2013-234311 Japanese Unexamined Patent Publication No. 2012-224714
  • the present invention provides a cured epoxy resin product in which local accumulation of electric charges is sufficiently prevented under a high temperature and high electric field, and a curing agent (particularly an imide group-containing compound) for producing the cured epoxy resin product.
  • a curing agent particularly an imide group-containing compound
  • the present invention is also for producing an epoxy resin cured product, which is sufficiently prevented from locally accumulating electric charges under a high temperature and high electric field, and which is sufficiently excellent in heat resistance and dielectric properties, and the epoxy resin cured product. It is an object of the present invention to provide a curing agent (particularly an imide group-containing compound).
  • the local accumulation of electric charge is the uneven distribution of electric charge generated inside the electrically insulating material under a high temperature and high electric field, and can be observed by measuring the charge density distribution over time. It is an electrical phenomenon that can occur.
  • the high temperature and high electric field is, for example, an environment having a temperature of 120 ° C. or higher (particularly 130 to 150 ° C.) and an electric field of 40 to 120 kV / mm (particularly 80 to 120 kV / mm).
  • Electrical insulation and insulation include the property that local accumulation of electric charge is sufficiently prevented under such a high temperature and high electric field.
  • the dielectric constant and the dielectric loss tangent may be evaluated as being better when they are higher or lower depending on the purpose. In the present invention, the dielectric properties are evaluated as being better. In particular, the performance is such that both the permittivity and the dielectric loss tangent can be sufficiently reduced.
  • the present inventors have obtained a cured product composed of a specific imide group-containing curing agent and an epoxy resin, which has all the properties of heat resistance, dielectric properties and insulating properties. We found it to be excellent and arrived at the present invention.
  • the gist of the present invention is as follows.
  • An imide group-containing compound selected from the group of diimide dicarboxylic acid-based compounds, diimide tetracarboxylic acid-based compounds, and monoimide tricarboxylic acid-based compounds.
  • An imide group-containing curing agent selected from the imide group-containing compounds described in ⁇ 1>.
  • An epoxy resin cured product comprising the imide group-containing curing agent according to ⁇ 2> and an epoxy resin.
  • ⁇ 5> The epoxy resin cured product according to ⁇ 3> or 4, wherein the imide group-containing curing agent has a molecular weight of 200 to 1100.
  • ⁇ 6> The epoxy resin cured product according to any one of ⁇ 3> to ⁇ 5>, wherein the imide group-containing curing agent has a functional group equivalent of 50 to 500.
  • ⁇ 8> A sealing material containing the cured epoxy resin according to any one of ⁇ 3> to ⁇ 6>.
  • ⁇ 9> The encapsulant according to ⁇ 8>, which is for a power semiconductor module.
  • ⁇ 10> An insulator containing the epoxy resin cured product according to any one of ⁇ 3> to ⁇ 6>. ⁇ 11> The insulator according to ⁇ 10> for a power transmission line. ⁇ 12> An electric wire coating material containing the cured epoxy resin according to any one of ⁇ 3> to ⁇ 6>. ⁇ 13> The electric wire coating material according to ⁇ 12> for electric vehicles. ⁇ 14> A printed wiring board containing the epoxy resin cured product according to any one of ⁇ 3> to ⁇ 6>.
  • an electrically insulating epoxy resin cured product having excellent heat resistance, dielectric properties and insulating properties and suitable for use in, for example, encapsulants (particularly semiconductor encapsulants), insulators, electric wire coating materials, etc. And a curing agent (particularly an imide group-containing compound) for producing the epoxy resin cured product can be provided.
  • the electrically insulating epoxy resin cured product of the present invention has sufficiently excellent insulating properties that local accumulation of electric charges is sufficiently prevented, especially under a high temperature and high electric field.
  • FIG. 1 is a chart showing changes over time in the charge density distribution of the cured epoxy resin products of Examples A-1, B-1, B-2 and C-1.
  • FIG. 2 is a chart showing changes over time in the charge density distribution of the cured epoxy resin products of Comparative Examples 1 to 3.
  • the imide group-containing compound of the present invention is useful as a curing agent (particularly an epoxy resin curing agent).
  • the imide group-containing compound of the present invention is also referred to as an "imide group-containing curing agent".
  • the cured product of the electrically insulating epoxy resin of the present invention will be described in detail, and in the above description, the imide group-containing compound will be described in detail as an imide group-containing curing agent.
  • the electrically insulating epoxy resin cured product of the present invention is composed of an imide group-containing curing agent and an epoxy resin.
  • imide group-containing curing agent examples include imide group-containing compounds such as diimide dicarboxylic acid-based compounds, diimide tetracarboxylic acid-based compounds, and monoimide tricarboxylic acid-based compounds.
  • the imide group-containing curing agent may be one or more imide group-containing curing agents selected from these groups.
  • a preferable imide group-containing curing agent is one or more imide group-containing curing agents selected from the group consisting of diimide dicarboxylic acid compounds.
  • the molecular weight of the imide group-containing curing agent is not particularly limited, and is preferably 200 to 1100, more preferably 300 to 1000, and further preferably 300 to 300, from the viewpoint of further improving heat resistance, dielectric properties, and insulating properties. It is 700, most preferably 400 to 600.
  • the functional group equivalent of the imide group-containing curing agent is not particularly limited, and is preferably 50 to 500, more preferably 800 to 400, still more preferably 800 to 400, from the viewpoint of further improving heat resistance, dielectric properties and insulating properties. It is 100 to 400, most preferably 200 to 350.
  • the functional group equivalent is a value calculated by dividing the molecular weight by the number of functional groups (for example, carboxyl groups) that the imide group-containing curing agent has per molecule.
  • the blending amount of the imide group-containing curing agent contained in the curing agent is not particularly limited, and is preferably 50% by mass or more with respect to the total amount of the curing agent from the viewpoint of further improving heat resistance, dielectric properties and insulating properties. It is more preferably 80% by mass or more, further preferably 90% by mass or more, and most preferably 100% by mass.
  • the blending amount of the imide group-containing curing agent is 100% by mass with respect to the total amount of the curing agent, it means that the curing agent is composed of only the imide group-containing curing agent.
  • the total blending amount thereof may be within the above range.
  • a diimide dicarboxylic acid compound is a compound having two imide groups and two carboxyl groups in one molecule. Diimide dicarboxylic acid compounds do not have an amide group.
  • a tricarboxylic acid anhydride component and a diamine component as raw material compounds, it is possible to produce an amidoic acid-based compound by reacting functional groups with each other, and to produce a diimidedicarboxylic acid-based compound by advancing the imidization reaction. it can.
  • the reaction between the functional groups may be carried out in a solution or in a solid phase state, and the production method is not particularly limited.
  • a diimide dicarboxylic acid-based compound using a tricarboxylic acid anhydride component and a diamine component is a compound formed by reacting one molecule of the diamine component with two molecules of the tricarboxylic acid anhydride component to form two imide groups. ..
  • the diamine component is usually about 0.5 times the molar amount of the tricarboxylic acid anhydride component, for example 0.1 to 0.7 times. It is used in a molar amount, preferably 0.3 to 0.7 times molar amount, more preferably 0.4 to 0.6 times molar amount, still more preferably 0.45 to 0.55 times molar amount.
  • the tricarboxylic acid anhydride component that can constitute the diimide dicarboxylic acid compound is not particularly limited, and for example, the heat resistance, dielectric property and insulating property of the diimide dicarboxylic acid compound and the epoxy resin cured product obtained by using the diimide dicarboxylic acid compound are further improved. From the viewpoint of improvement, an aromatic tricarboxylic acid anhydride component containing an aromatic ring, particularly trimellitic anhydride, is preferable.
  • the tricarboxylic acid anhydride component that can constitute a diimide dicarboxylic acid compound one type may be used alone, or two or more types may be used as a mixture.
  • the diamine component that can constitute the diimide dicarboxylic acid compound is not particularly limited, and for example, the heat resistance, dielectric property, insulating property, and solubility of the diimide dicarboxylic acid compound and the epoxy resin cured product obtained by using the diimide dicarboxylic acid compound are not particularly limited. From the viewpoint of further improvement of the above, aromatic diamine components containing an aromatic ring, particularly m-xylylenediamine, p-xylylenediamine, 4,4'-diaminodiphenyl ether, and dimerdiamine are preferable.
  • the diamine component that can constitute a diimide dicarboxylic acid compound one kind may be used alone, or two or more kinds may be used as a mixture.
  • the diimide tetracarboxylic dian compound is a compound having two imide groups and four carboxyl groups in one molecule.
  • a tetracarboxylic acid dianhydride component and a monoaminodicarboxylic acid component as a raw material compound, an amidic acid-based compound is produced by reacting functional groups with each other, and a diimidetetracarboxylic acid is promoted by advancing the imidization reaction.
  • a system compound can be produced.
  • the reaction between the functional groups may be carried out in a solution or in a solid phase state, and the production method is not particularly limited.
  • a diimide tetracarboxylic acid compound using a tetracarboxylic dianhydride component and a monoaminodicarboxylic acid component two molecules of the monoaminodicarboxylic acid component react with one molecule of the tetracarboxylic dianhydride component. It is a compound in which two imide groups are formed.
  • the monoaminodicarboxylic acid component is usually about twice as much as that of the tetracarboxylic acid dianhydride component.
  • the molar amount for example, 1.5 to 10.0 times molar amount, preferably 1.8 to 2.2 times molar amount, more preferably 1.9 to 2.1 times molar amount, still more preferably 1.95 to 2 times molar amount. Used in 0.05 times the molar amount.
  • the tetracarboxylic dianhydride component that can constitute the diimide tetracarboxylic dian compound is not particularly limited, and for example, the heat resistance and dielectric properties of the diimide tetracarboxylic dian compound and the cured epoxy resin obtained by using the diimide tetracarboxylic dian compound.
  • Anhydrous components especially 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-(hexafluoroisopropyridene) diphthalic dianhydride, 1,2,3,4-butanetetracarboxylic Acid dianhydride is preferred.
  • the tetracarboxylic dianhydride component that can constitute a diimide tetracarboxylic acid compound one type may be used alone, or two or more types may be used as a mixture.
  • the monoaminodicarboxylic acid component that can constitute the diimidetetracarboxylic acid-based compound is not particularly limited, and for example, the heat resistance, dielectric properties, and insulation of the diimidetetracarboxylic acid-based compound and the cured epoxy resin obtained by using the diimidetetracarboxylic acid-based compound are not particularly limited. From the viewpoint of further improving the property and solubility, aromatic monoaminodicarboxylic acid components containing an aromatic ring, particularly 2-aminoterephthalic acid, 2-aminoisophthalic acid, 4-aminoisophthalic acid, 5-aminoisophthalic acid, 3-Aminophthalic acid and 4-aminophthalic acid are preferable.
  • the monoaminodicarboxylic acid component that can constitute a diimidetetracarboxylic acid compound one kind may be used alone, or two or more kinds may be used as a mixture.
  • a monoimide tricarboxylic acid compound is a compound having one imide group and three carboxyl groups in one molecule.
  • a tricarboxylic acid anhydride component and a monoaminodicarboxylic acid component as a raw material compound, an amidic acid-based compound is produced by reacting functional groups with each other, and a monoimide tricarboxylic acid-based compound is produced by advancing the imidization reaction.
  • the reaction between the functional groups may be carried out in a solution or in a solid phase state, and the production method is not particularly limited.
  • a monoimide tricarboxylic acid compound using a tricarboxylic acid anhydride component and a monoaminodicarboxylic acid component
  • one molecule of the triaminodicarboxylic acid component reacts with one molecule of the tricarboxylic acid anhydride component, and one imide group is formed. It is a compound formed.
  • the monoaminodicarboxylic acid component is usually about 1 times the molar amount of the tricarboxylic acid anhydride component, for example, 0. 5 to 5.0 times the molar amount, preferably 0.8 to 1.2 times the molar amount, more preferably 0.9 to 1.1 times the molar amount, still more preferably 0.95 to 1.05 times the molar amount. used.
  • the tricarboxylic acid anhydride component that can constitute the monoimide tricarboxylic acid compound is not particularly limited, and for example, the heat resistance, dielectric property and insulating property of the monoimide tricarboxylic acid compound and the epoxy resin cured product obtained by using the monoimide tricarboxylic acid compound are not particularly limited. From the viewpoint of further improvement, an aromatic tricarboxylic acid anhydride component containing an aromatic ring, particularly trimellitic anhydride, is preferable.
  • the tricarboxylic acid anhydride component that can constitute a monoimide tricarboxylic acid compound one type may be used alone, or two or more types may be used as a mixture.
  • the monoaminodicarboxylic acid component that can constitute the monoimide tricarboxylic acid compound is not particularly limited, and for example, the heat resistance, dielectric properties and insulation of the monoimide tricarboxylic acid compound and the cured epoxy resin obtained by using the monoimide tricarboxylic acid component are not particularly limited. From the viewpoint of further improving the properties, aromatic monoaminodicarboxylic acid components containing an aromatic ring, particularly 2-aminoterephthalic acid, 2-aminoisophthalic acid, 4-aminoisophthalic acid, 5-aminoisophthalic acid, 3-aminophthalic acid Acids and 4-aminophthalic acids are preferred.
  • the monoaminodicarboxylic acid component that can constitute a monoimide tricarboxylic acid compound one kind may be used alone, or two or more kinds may be used as a mixture.
  • the imide group-containing curing agent can be produced in a solvent or in the absence of a solvent, but the production method is not particularly limited.
  • a predetermined raw material for example, tricarboxylic acid anhydride component, diamine component, tetracarboxylic acid dianhydride component, monoaminodicarboxylic acid
  • an aprotic solvent such as N-methyl2-pyrrolidone
  • the imidization method is not particularly limited, for example, a heating imidization method performed by heating to 250 ° C. to 300 ° C. in a nitrogen atmosphere, a dehydration cyclization reagent such as a mixture of a carboxylic acid anhydride and a tertiary amine. It may be a chemical imidization method performed by treating with.
  • the method utilizing the mechanochemical effect is a method for obtaining an organic compound by expressing the mechanochemical effect by utilizing the mechanical energy generated when the raw material compound used for the reaction is pulverized.
  • the mechanochemical effect is formed by crushing a raw material compound that is in a solid state under a reaction environment by applying mechanical energy (compressive force, shearing force, impact force, grinding force, etc.) to the raw material compound. It is an effect (or phenomenon) that activates the grinding interface. This causes a reaction between the functional groups.
  • Reactions between functional groups usually occur between two or more source compound molecules.
  • the reaction between functional groups may occur between two raw material compound molecules having different chemical structures, or may occur between two raw material compound molecules having the same chemical structure. Reactions between functional groups do not occur only between a limited set of two source compound molecules, but usually also occur between another set of two source compound molecules.
  • a new reaction between functional groups may occur between the compound molecule generated by the reaction between the functional groups and the raw material compound molecule.
  • the reaction between the functional groups is usually a chemical reaction, whereby a binding group (particularly a covalent bond) is formed between the two raw material compound molecules by the functional group of each raw material compound molecule, and another one is formed. Compound molecules are produced.
  • the reaction environment means an environment in which the raw material compound is placed for the reaction, that is, an environment in which mechanical energy is applied, and may be, for example, an environment inside the apparatus.
  • Being in a solid state in a reaction environment means being in a solid state in an environment where mechanical energy is applied (eg, under temperature and pressure in an apparatus).
  • the raw material compound in the solid state under the reaction environment may usually be in the solid state at normal temperature (25 ° C.) and normal pressure (101.325 kPa).
  • the raw material compound that is in the solid state under the reaction environment may be in the solid state at the start of applying mechanical energy.
  • a raw material compound that is in a solid state under a reaction environment is in a liquid state (for example, in a molten state) during the reaction (or processing) due to an increase in temperature and / or pressure accompanying the continuation of mechanical energy application. ), but from the viewpoint of improving the reaction rate, it is preferable that the solid state is continuously maintained during the reaction (or treatment).
  • the new surface state formed by surface renewal is not particularly limited as long as the crushing interface is activated by crushing, and may be in a dry state or in a wet state. May be good.
  • the new surface wet state due to surface renewal is due to the raw material compound in a liquid state different from the raw material compound in the solid state.
  • the state of the raw material mixture is not particularly limited as long as the raw material compound in the solid state is pulverized by applying mechanical energy.
  • the raw material mixture may be in a dry state due to the fact that all the raw material compounds contained in the raw material mixture are in a solid state.
  • the raw material mixture may be in a wet state due to the fact that at least one raw material compound contained in the raw material mixture is in a solid state and the remaining raw material compounds are in a liquid state.
  • the raw material mixture contains only one kind of raw material compound, the one kind of raw material compound is in a solid state.
  • both of the two kinds of raw material compounds may be in a solid state, or one raw material compound is in a solid state and the other raw material compound is a liquid. It may be in a state.
  • a functional group is a monovalent group (atomic group) that can cause reactivity in the molecular structure, and is not a carbon-carbon double bond, a carbon-carbon triple bond, or the like. It shall be used in the concept excluding saturated bond groups (for example, radically polymerizable groups).
  • a functional group is a group containing a carbon atom and a hetero atom. Heteroatoms are one or more atoms selected from the group consisting of oxygen atoms, nitrogen atoms and sulfur atoms, particularly the group consisting of oxygen atoms and nitrogen atoms.
  • the functional group may further contain a hydrogen atom.
  • the functional groups subjected to the reaction are usually two functional groups, and the structure of the raw material compound molecule having one functional group and the raw material compound molecule having the other functional group may be different from each other. , Or they may be the same.
  • the reaction forms a bond (particularly a covalent bond) between the two source compound molecules, and monomolecularization of them is achieved.
  • Small molecules such as water, carbon dioxide, and / or alcohol may or may not be by-produced by the reaction between the functional groups.
  • the reaction between the functional groups may be a reaction between any functional group (particularly a monovalent functional group) capable of chemically reacting with each other, for example, a carboxyl group and its halide (group), an acid anhydride group, an amino group. , An isocyanate group, a hydroxyl group, and the like, which is a reaction of two functional groups selected from the group.
  • the two functional groups are not particularly limited as long as a chemical reaction occurs, and may be, for example, two functional groups having different chemical structures or two functional groups having the same chemical structure.
  • reaction between functional groups examples include a condensation reaction, an addition reaction, or a composite reaction thereof.
  • the condensation reaction is a reaction in which a bond or link between the raw material compound molecules is achieved with the elimination of small molecules such as water, carbon dioxide, and alcohol between the raw material compound molecules.
  • Examples of the condensation reaction include a reaction in which an amide group is formed (amidization reaction), a reaction in which an imide group is formed (imidization reaction), a reaction in which an ester group is formed (esterification reaction), and the like.
  • the addition reaction is an addition reaction between functional groups, and is a reaction in which binding or ligation between the raw material compound molecules is achieved without involving the elimination of small molecules between the raw material compound molecules.
  • Examples of the addition reaction include a reaction in which a urea group is formed, a reaction in which a urethane group is formed, and a reaction in which a cyclic structure is ring-opened (that is, a ring-opening reaction).
  • a part of the cyclic structure is cleaved, and the cleaved site and other compounds are cleaved.
  • a reaction in which a bond or linkage with a functional group of a raw material compound is achieved.
  • the ring-opening reaction produces, for example, an amide group, a carboxyl group, an ester group, and an ether group.
  • reaction between functional groups may be, for example, one or more reactions selected from the group consisting of the following reactions: A reaction in which (A) an acid anhydride group reacts with an amino group to form (a1) an amide group and a carboxyl group, (a2) an imide group, (a3) an isoimide group, or (a4) a mixed group thereof; (B) A reaction in which an imide group is formed by a reaction between an acid anhydride group and an isocyanate group; (C) A reaction in which an amide group is produced by a reaction between a carboxyl group or a halide (group) thereof and an amino group or an isocyanate group; (D) A reaction in which an ester group is formed by a reaction between a carboxyl group or a halide (group) thereof and a hydroxyl group; (E) A reaction in which a urea group is produced by a reaction between an isocyanate group and an amino group; (F) A reaction in which a urea group is
  • the reaction between the functional groups corresponds to the above-mentioned reaction (A).
  • imidization may be carried out by the same method as the imidization method in the method of producing in a solvent.
  • the epoxy resin used in the present invention is not particularly limited as long as it is an organic compound having two or more epoxy groups in one molecule.
  • Specific examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, bisphenyl type epoxy resin, and dicyclopentadiene type epoxy. Examples thereof include resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, isocyanurate type epoxy resins, alicyclic epoxy resins, acrylic acid modified epoxy resins, polyfunctional epoxy resins, brominated epoxy resins, and phosphorus modified epoxy resins.
  • the epoxy resin may be used alone or in combination of two or more.
  • the epoxy group may be a glycidyl group. Epoxy resins are available as commercial products.
  • the epoxy equivalent of the epoxy resin is usually 100 to 3000, preferably 150 to 300.
  • the epoxy resin cured product of the present invention may further contain additives such as a curing accelerator, a thermosetting resin, an inorganic filler, an antioxidant, and a flame retardant.
  • the curing accelerator is not particularly limited, but for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole.
  • Tertiary amines such as phenol, 2,4,6-tris (dimethylaminomethyl) phenol; organic phosphines such as triphenylphosphine and tributylphosphine.
  • the curing accelerator may be used alone or in combination of two or more.
  • the amount of the curing accelerator to be blended is not particularly limited, and is, for example, 0.01 to 2% by mass with respect to the total amount of the epoxy resin solution described later, further improving the heat resistance, dielectric properties and insulating properties of the epoxy resin cured product. From the viewpoint of the above, it is preferably 0.01 to 1% by mass, and more preferably 0.05 to 0.5% by mass.
  • thermosetting resin is not particularly limited, and examples thereof include cyanate resin, isocyanate resin, maleimide resin, polyimide resin, urethane resin, and phenol resin.
  • the thermosetting resin may be used alone or in combination of two or more.
  • the inorganic filler examples include silica, glass, alumina, talc, mica, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, titanium oxide, silicon nitride, boron nitride and the like.
  • the inorganic filler may be used alone or in combination of two or more.
  • the inorganic filler is preferably surface-treated with a surface treatment agent such as an epoxy silane coupling agent or an amino silane coupling agent.
  • the inorganic filler may be used alone or in combination of two or more.
  • antioxidants examples include hindered phenolic antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants.
  • the antioxidant may be used alone or in combination of two or more.
  • the flame retardant is not particularly limited, and a non-halogen flame retardant is preferable from the viewpoint of environmental impact.
  • the flame retardant include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, and the like.
  • the flame retardant may be used alone or in combination of two or more.
  • the electrically insulating epoxy resin cured product of the present invention can be produced by heating an epoxy resin solution containing an imide group-containing curing agent and an epoxy resin, which will be described in detail later.
  • the electrically insulating epoxy resin cured product of the present invention can be produced by applying an epoxy resin solution to a base material, drying and curing the substrate by heating. After curing, the cured product may be peeled off from the substrate and used.
  • the method for applying the epoxy resin solution is not particularly limited, and examples thereof include a casting method and a dipping method.
  • a cured epoxy resin can be obtained in the form of a sheet, a film, or the like by applying the epoxy resin solution to the base material, drying and curing the base material, and then peeling the epoxy resin solution from the base material.
  • the electrically insulating epoxy resin cured product of the present invention can be produced by molding, drying and curing the epoxy resin solution while pouring it into a mold.
  • the molding method of the epoxy resin solution is not particularly limited, and examples thereof include a transfer molding method and an injection molding method.
  • the imide group-containing curing agent and the epoxy resin are reacted to complete the curing.
  • the heating temperature is usually 80 to 350 ° C, preferably 130 to 300 ° C.
  • the heating time is usually 1 minute to 20 hours, preferably 5 minutes to 10 hours.
  • the epoxy resin cured product of the present invention may have any size.
  • the thickness of the cured product may be usually 1 ⁇ m to 100 mm.
  • the epoxy resin solution is made by mixing at least an imide group-containing curing agent and an epoxy resin with an organic solvent.
  • the imide group-containing curing agent and the epoxy resin are dissolved in the organic solvent, and at least the imide group-containing curing agent, the epoxy resin and the organic solvent are uniformly mixed at the molecular level.
  • Dissolution means that the solute is uniformly mixed in the solvent at the molecular level.
  • a solution is a state in which a solute is uniformly mixed in a solvent at the molecular level. For example, at normal temperature (25 ° C.) and normal pressure (101.325 kPa), the solute is in the solvent with the naked eye. It is a mixed liquid that is dissolved to the extent that it looks transparent.
  • the epoxy resin solution may further contain the above-mentioned additives.
  • the organic solvent used in the epoxy resin solution is not particularly limited as long as the curing agent and the epoxy resin can be uniformly dissolved, and a non-halogenated solvent is preferable from the viewpoint of the influence on the environment.
  • a non-halogenated solvent include amide compounds such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone. All of these non-halogenated solvents are useful as general purpose solvents.
  • the organic solvent may be used alone or in combination of two or more.
  • the method for producing the epoxy resin solution is not particularly limited, and may be, for example, an individual dissolution method, a batch dissolution method, or the like.
  • the individual dissolution method is preferable from the viewpoint of obtaining a uniform resin solution in a short time.
  • the individual dissolution method is a method in which an imide group-containing curing agent and an epoxy resin are mixed and dissolved in an organic solvent in advance, and then they are mixed.
  • the batch dissolution method is a method in which an imide group-containing curing agent and an epoxy resin are simultaneously mixed with an organic solvent and dissolved.
  • the mixing temperature is not particularly limited and may be, for example, 80 to 180 ° C., particularly 100 to 160 ° C.
  • the heating for achieving the mixing temperature may be, for example, reflux heating of an organic solvent.
  • the amount of the imide group-containing curing agent blended is such that the functional group equivalent of the imide group-containing curing agent is the epoxy resin from the viewpoint of further improving the heat resistance, dielectric properties and insulating properties of the obtained epoxy resin cured product.
  • the amount is preferably 0.5 to 1.5 equivalents, more preferably 0.7 to 1.3 equivalents, relative to the epoxy equivalent.
  • the functional group equivalent of the imide group-containing curing agent corresponds to the equivalent calculated from the content of the hydroxy group or the carboxyl group.
  • the total amount of the imide group-containing curing agent and the epoxy resin is not particularly limited, and from the viewpoint of further improving the heat resistance, dielectric properties and insulating properties of the obtained epoxy resin cured product, the total amount of the epoxy resin solution is used. On the other hand, it is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and further preferably 50 to 70% by mass.
  • the epoxy resin solution usually has a viscosity of 10 to 70 Pa ⁇ s, particularly 30 to 70 Pa ⁇ s, preferably 40 to 60 Pa ⁇ s, and does not have a so-called gel form.
  • a gel does not have a viscosity and is generally a solid state having no fluidity.
  • the epoxy resin solutions when mixed with additional solvents, are easily compatible with each other and are uniformly mixed at the molecular level as a whole. However, even when the gel is mixed with a further solvent, the gel remains in a lump without being compatible with each other and is not uniformly mixed at the molecular level as a whole.
  • the "further solvent” is a solvent that is compatible with the solvent contained in the solution or gel, and is, for example, a solvent represented by the same structural formula as the solvent contained in the solution or gel.
  • the viscosity of the epoxy resin solution is the viscosity at 30 ° C. measured by a Brookfield digital viscometer.
  • the epoxy resin solution may have a relatively low viscosity as described above because the epoxy resin is unlikely to react unexpectedly. Therefore, a cured product can be produced with sufficient workability by using the epoxy resin solution.
  • the epoxy resin solution usually has a reaction rate of 10% or less. The reaction rate is the ratio of the number of glycidyl groups reacted in the epoxy resin solution to the total number of glycidyl groups contained in the epoxy resin.
  • the cured epoxy resin product of the present invention is useful in all applications that require at least one of heat resistance, dielectric properties and electrical insulation (preferably properties including at least electrical insulation).
  • the cured epoxy resin of the present invention can be preferably used as any electrically insulating material.
  • electrically insulating materials include, for example, encapsulants (for example, encapsulants for power semiconductor modules), insulators (particularly insulator covering materials) (for example, insulators for power transmission lines (particularly insulator covering materials for power transmission lines)).
  • Electric wire coating materials for example, electric wire coating materials for electric vehicles), insulating materials for printed wiring boards, and the like.
  • the electrically insulating epoxy resin cured product of the present invention is used as a sealing material, for example, after producing a power semiconductor module, the epoxy resin solution is filled in a mold in which the module is set, and dried and cured. Therefore, the cured epoxy resin of the present invention can be used as a sealing material for a power semiconductor module.
  • electrically insulating epoxy resin cured product as insulator coating material
  • an epoxy resin solution is used to coat the outer peripheral portion (particularly the outer peripheral surface) of the insulator core to form a layer, and then dried and dried.
  • the cured epoxy resin of the present invention can be used as an insulator coating material.
  • the core include glass fiber reinforced plastics such as glass fiber reinforced epoxy resin and glass fiber reinforced phenol resin, which are usually formed into various shapes such as a cylindrical shape or a columnar shape.
  • the thickness of the epoxy resin cured product as a coating material formed on the outer peripheral portion of the core can be changed according to the size and shape of the obtained polymer insulator (for example, the presence or absence of a bulk portion and its shape, size, and spacing).
  • the thinnest portion is preferably 1 mm or more, and more preferably 2 mm or more.
  • the thickness of the coating material is usually 1 to 100 mm, preferably 2 to 50 mm.
  • the cured epoxy resin product of the present invention When the cured epoxy resin product of the present invention is used as an insulator coating material, the cured epoxy resin product of the present invention has an insulating property (particularly, an insulating property that more sufficiently prevents dielectric breakdown due to local accumulation of charge). It is especially useful as an insulator covering material for power transmission lines.
  • the epoxy resin cured product of the present invention is obtained by applying an epoxy tree solution to the surface of a conductor and baking (that is, drying and curing). It can be used as an electric wire coating material.
  • the conductor include copper and copper alloys.
  • the coating method and the baking method can be carried out according to the same methods and conditions as the coating method and the baking method in the conventional electric wire coating forming method. The coating and baking may be repeated twice or more.
  • the epoxy resin solution may be mixed with other resins and used.
  • the thickness of the electric wire coating material is preferably 1 to 100 ⁇ m, more preferably 10 to 50 ⁇ m, from the viewpoint of protecting the conductor.
  • the cured epoxy resin of the present invention has an insulating property (particularly, an insulating property that more sufficiently prevents dielectric breakdown due to local accumulation of charges). It is particularly useful as an electric wire coating material for electric vehicles.
  • the printed wiring board usually contains an electrically insulating epoxy resin cured product, and may further contain a glass cloth.
  • the electrically insulating epoxy resin cured product of the present invention is used as an insulating material for a printed wiring board, the epoxy resin cured product of the present invention is dried and cured after impregnating or applying an epoxy resin solution to a glass cloth.
  • the thickness of the printed wiring board is not particularly limited.
  • the epoxy resin cured product of the present invention is an electric / electronic material for other uses, for example, a molding material for a bushing transformer, a molding material for a solid-state insulating switch gear, an electric penetration for a nuclear power plant, an electric / electronic material such as a build-up laminate. Can also be preferably used.
  • Method for producing imide group-containing curing agent 150 g of a sample in which an acid component and an amine component are mixed at the ratios shown in the table is pulverized by Wonder Crusher (Osaka Chemical Co., Ltd.) WC-3C at a rotation speed of about 9000 rpm for 1 minute.
  • the mechanochemical treatment was performed by repeating the mixing and crushing three times.
  • the treated sample was transferred to a glass container, and an imidization reaction was carried out in an inert oven (Yamato Scientific Co., Ltd.) DN411I in a nitrogen atmosphere at a firing temperature of 300 ° C. and a firing time of 2 hours.
  • the identification of the imide group-containing curing agent was performed based on the fact that the molecular weight is the same as the molecular weight of the target structure and that there is absorption derived from the imide group in infrared spectroscopy.
  • reaction rate (%) ⁇ 1- ( ⁇ '/ ⁇ ) ⁇ x 100 ⁇ : 90% or more and 100% or less (best); ⁇ : 80% or more and less than 90% (good); ⁇ : 70% or more and less than 80% (no problem in practical use); X: Less than 70% (there is a problem in practical use).
  • Tg Glass transition temperature
  • DSC differential scanning calorimetry device
  • a commercially available conductive PEEK (polyetheretherketone) sheet was used for the anode, and an aluminum plate was used for the cathode.
  • the epoxy resin cured product (sample) has a film shape and is sandwiched between the anode and the cathode.
  • a DC voltage corresponding to an average electric field of 20 kV / mm is applied for 10 minutes, then short-circuited for 5 minutes, and pulses are applied during and during the short-circuit.
  • a voltage (5 ns, 200 V) was applied at 1 ms intervals (1 kHz), and the obtained waveforms were added and averaged 1000 times to obtain one waveform.
  • the measurement interval is 10 seconds.
  • the DC voltage to be applied is increased so that the average applied electric field becomes 40 kV / mm, and a series of measurements similar to the above are performed.
  • the measurements were sequentially repeated under an average applied electric field corresponding to 60, 80, 100 and 120 kV / mm.
  • the charge density distribution measured over time in this way is shown in FIGS. 1 and 2.
  • FIG. 1 shows changes over time in the charge density distribution of the cured epoxy resin products of Examples A-1, B-1, B-2 and C-1 (particularly the cured epoxy resin products using bisphenol A type epoxy resin). It is a chart which shows.
  • FIG. 2 is a chart showing changes over time in the charge density distribution of the cured epoxy resin products of Comparative Examples 1 to 3 (particularly the cured epoxy resin using bisphenol A type epoxy resin). The smaller the maximum electric field (particularly the ratio of the maximum electric field / applied electric field), the better the insulating property.
  • ⁇ The ratio of the maximum electric field in the sample to the applied electric field was 1.1 or less at the maximum (best); ⁇ : The ratio of the maximum electric field in the sample to the applied electric field was greater than 1.1 and 1.3 or less (good); ⁇ : The ratio of the maximum electric field in the sample to the applied electric field was greater than 1.3 and 1.5 or less (no problem in practical use); X: The ratio of the maximum electric field in the sample to the applied electric field was larger than 1.5 at the maximum (there is a problem in practical use).
  • EOCN-1020-55 o-cresol novolac type epoxy resin manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin
  • ⁇ The ratio of the maximum electric field in the sample to the applied electric field is 1.2 or less at the maximum. (Best); ⁇ : The ratio of the maximum electric field in the sample to the applied electric field was greater than 1.2 and 1.4 or less (good); ⁇ : The ratio of the maximum electric field in the sample to the applied electric field was greater than 1.4 and 1.6 or less (no problem in practical use); X: The ratio of the maximum electric field in the sample to the applied electric field was larger than 1.6 at the maximum (there is a problem in practical use).
  • Dielectric characteristics (dielectric constant, dielectric loss tangent) It was measured and evaluated by an impedance analyzer under the following conditions.
  • Synthesis example B-2 An imide group-containing curing agent was obtained in the same manner as in Synthesis Example B-1 except that the acid dianhydride composition and the monoamine composition were changed.
  • Synthesis example C-1 A monoimide tricarboxylic acid was prepared based on the above-mentioned "Method for producing an imide group-containing curing agent". The details are as follows. 515 parts by mass of granular trimellitic anhydride and 485 parts by mass of 2-aminoterephthalic acid were added to the crushing tank, and mixed pulverization was performed. Then, the mixture was transferred to a glass container and subjected to an imidization reaction at 300 ° C. for 2 hours in a nitrogen atmosphere in an inert oven to prepare an imide group-containing curing agent.
  • Epoxy resin jER828 Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 184 to 194 g / eq EOCN-1020-55: manufactured by Nippon Kayaku Co., Ltd., o-cresol novolac type epoxy resin, epoxy equivalent 195 g / eq
  • Curing agents other than imide-based curing agents-PHENOLITE TD-2131 Novolac-type phenol resin manufactured by DIC, curing agent containing no imide group;
  • the curing agent has the following structural formula.
  • HN-2200 manufactured by Hitachi Chemical Co., Ltd., alicyclic acid anhydride, imide group-free curing agent; the curing agent has the following structural formula.
  • -JERcure113 A curing agent manufactured by Mitsubishi Chemical Corporation that does not contain modified alicyclic amines and imide groups.
  • Example A-1 The curing accelerator (2) was added to 60 parts by mass of the sample obtained by mixing the imide group-containing curing agent obtained in Synthesis Example A-1 and the epoxy resin (jER828) at a ratio of 1.0 / 1.1 (equivalent ratio).
  • -Ethyl-4-methylimidazole manufactured by Tokyo Chemical Industry Co., Ltd.
  • 0.2 parts by mass and 39.8 parts by mass of dimethylformamide (DMF) are mixed at room temperature (that is, 20 ° C.), and 0.5 at 150 ° C.
  • Epoxy resin solution was obtained by reflux heating for a time.
  • the epoxy resin solution obtained in this example had a viscosity of 50 Pa ⁇ s and had sufficiently good workability.
  • the obtained epoxy resin solution was applied to an aluminum substrate to a thickness of 300 ⁇ m, and the produced coating film was dried in an inert oven at 180 ° C. for 2 hours and then at 300 ° C. for 2 hours in a nitrogen atmosphere. Desolvation and curing reactions were performed.
  • the aluminum base material was removed from the obtained sample with an aluminum base material to obtain a cured epoxy resin.
  • the average thickness of the cured epoxy resin (cured epoxy resin using the epoxy resin "jER828”) was 112 ⁇ m. In the present specification, the average thickness is the average value of the thickness at any 10 points.
  • Epoxy resin solution and epoxy resin cured product were prepared.
  • the epoxy resin solution had a viscosity of 50 Pa ⁇ s and had sufficiently good workability.
  • the average thickness of the cured epoxy resin was 103 ⁇ m.
  • Examples B-1, B-2 and C-1 and Comparative Example 1 The epoxy resin is subjected to the same operation as in Example A-1 except that the imide group-containing curing agent or the curing agent "PHENOLITE TD-2131" obtained in Synthesis Example B-1, B-2 or C-1 is used. A solution and a cured epoxy resin were prepared. The imide group-containing curing agent used in each example was obtained in a synthetic example having the same number as that of the example number.
  • the reaction rate of the glycidyl group in the epoxy resin contained in the epoxy resin solutions obtained in Examples B-1, B-2 and C-1 and Comparative Example 1 was 10% or less.
  • the viscosities of the epoxy resin solutions obtained in Examples B-1, B-2 and C-1 and Comparative Example 1 were all 30 to 70 Pa ⁇ s, and they had sufficiently good workability.
  • the average thickness of the cured epoxy resin was as follows. Average thickness of epoxy resin cured product using epoxy resin "jER828": 116 ⁇ m (Example B-1), 115 ⁇ m (Example B-2), 122 ⁇ m (Example C-1), 112 ⁇ m (Comparative Example 1). Average thickness of epoxy resin cured product using epoxy resin "EOCN-1020-55": 120 ⁇ m (Example B-1), 104 ⁇ m (Example B-2), 114 ⁇ m (Example C-1), 106 ⁇ m (Comparative Example 1).
  • Comparative Example 2 100/80/1 (weight ratio) of alicyclic acid anhydride curing agent HN-2200, epoxy resin (jER828), and curing accelerator (2,4,6-trisdimethylaminomethylphenol, manufactured by Mitsubishi Chemical Co., Ltd.) was mixed at room temperature (that is, 20 ° C.) to obtain an epoxy resin solution.
  • the epoxy resin solution obtained in this comparative example had a viscosity of 50 Pa ⁇ s and had sufficiently good workability.
  • the obtained epoxy resin solution was applied to an aluminum base material to a thickness of 300 ⁇ m, and the produced coating film was dried in an inert oven at 120 ° C. for 5 hours and then at 150 ° C. for 15 hours in a nitrogen atmosphere. A curing reaction was carried out.
  • the aluminum base material was removed from the obtained sample with an aluminum base material to obtain a cured epoxy resin.
  • the average thickness of the cured epoxy resin (cured epoxy resin using the epoxy resin "jER828”) was 133 ⁇ m.
  • Epoxy resin solution and epoxy resin cured product were prepared.
  • the epoxy resin solution had a viscosity of 40 Pa ⁇ s and had sufficiently good workability.
  • the average thickness of the cured epoxy resin was 140 ⁇ m.
  • Comparative Example 3 The modified alicyclic amine curing agent jERcure113 and the epoxy resin (jER828) were mixed at a ratio of 100/10 (weight ratio) at room temperature (that is, 20 ° C.) to obtain an epoxy resin solution.
  • the epoxy resin solution obtained in this comparative example had a viscosity of 50 Pa ⁇ s and had sufficiently good workability.
  • the obtained epoxy resin solution was applied to an aluminum base material to a thickness of 300 ⁇ m, and the produced coating film was dried in an inert oven at 80 ° C. for 1 hour and then at 150 ° C. for 3 hours in a nitrogen atmosphere. A curing reaction was carried out.
  • the aluminum base material was removed from the obtained sample with an aluminum base material to obtain a cured epoxy resin.
  • the average thickness of the cured epoxy resin (cured epoxy resin using the epoxy resin "jER828”) was 139 ⁇ m.
  • Epoxy resin solution and epoxy resin cured product were prepared.
  • the epoxy resin solution had a viscosity of 40 Pa ⁇ s and had sufficiently good workability.
  • the average thickness of the cured epoxy resin was 123 ⁇ m.
  • Tables 1 to 4 show the characteristic values of the curing agent and the characteristic values of the epoxy resin cured product in each of the examples and the comparative examples.
  • Example A-1 using the diimide dicarboxylic acid compound, all the evaluation results of heat resistance, dielectric properties and insulating properties achieved ⁇ .
  • the cured epoxy resin of Comparative Examples 1 to 3 used a curing agent containing no imide group, it was inferior in at least one of heat resistance, dielectric property and insulating property.
  • the following items are clear from the ratio of the maximum electric field / applied electric field in each of the cured epoxy resin products of Examples and Comparative Examples and the time-dependent change charts of the charge density distributions in FIGS. 1 and 2. -In the epoxy resin cured products of Examples A-1, B-1, B-2 and C-1, local accumulation of electric charges was sufficiently prevented under high temperature and high electric field; -In the epoxy resin cured products of Comparative Examples 1 to 3, local accumulation of electric charges occurred under a high temperature and high electric field.
  • the cured epoxy resin of the present invention has sufficiently excellent heat resistance, dielectric properties and insulating properties. Therefore, the cured epoxy resin of the present invention includes encapsulants for power semiconductor modules (particularly semiconductor encapsulants), mold materials for bushing transformers, mold materials for solid-state insulated switch gears, insulators for power transmission lines, and the like. It can be suitably used for electric wire coating materials for electric vehicles, electric penetrations for nuclear power plants, insulating materials for printed wiring boards, and electrical and electronic materials such as build-up laminated boards.

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Abstract

La présente invention concerne un agent de durcissement (en particulier un composé contenant un groupe imide) permettant de fabriquer un matériau durci à base de résine époxydique électriquement isolant qui présente une résistance à la chaleur et des caractéristiques diélectriques suffisamment excellentes, et dans lequel l'accumulation locale de charge dans un environnement à haute température et à champ électrique élevé est suffisamment empêchée. La présente invention concerne un composé contenant un groupe imide choisi dans le groupe constitué par un composé d'acide dicarboxylique de diimide, un composé d'acide tétracarboxylique de diimide et un composé d'acide tricarboxylique de monoimide.
PCT/JP2020/045513 2019-12-10 2020-12-07 Composé contenant un groupe imide, agent de durcissement contenant un groupe imide, et matériau durci de résine époxydique et matériau électriquement isolant utilisant ledit matériau durci de résine époxydique WO2021117686A1 (fr)

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JP2021507541A JP6960705B1 (ja) 2019-12-10 2020-12-07 電気絶縁性エポキシ樹脂硬化物およびそれを用いた電気絶縁性材料
KR1020227009990A KR20220114525A (ko) 2019-12-10 2020-12-07 이미드기 함유 화합물, 이미드기 함유 경화제, 및 에폭시 수지 경화물 및 그것을 이용한 전기절연성 재료

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CN113861384A (zh) * 2021-10-28 2021-12-31 北京中科纳通电子技术有限公司 一种新型环氧树脂及其应用
CN114213629A (zh) * 2021-11-04 2022-03-22 道生天合材料科技(上海)股份有限公司 固化剂、固化剂组合物及其制备方法
JP7431292B2 (ja) 2021-10-14 2024-02-14 財團法人工業技術研究院 パッケージング構造

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