WO2022118723A1 - Résine époxyde, composition durcissable, produit durci, matériau d'étanchéité semi-conducteur, dispositif semi-conducteur, préimprégné, carte de circuit imprimé et film d'accumulation - Google Patents

Résine époxyde, composition durcissable, produit durci, matériau d'étanchéité semi-conducteur, dispositif semi-conducteur, préimprégné, carte de circuit imprimé et film d'accumulation Download PDF

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WO2022118723A1
WO2022118723A1 PCT/JP2021/043092 JP2021043092W WO2022118723A1 WO 2022118723 A1 WO2022118723 A1 WO 2022118723A1 JP 2021043092 W JP2021043092 W JP 2021043092W WO 2022118723 A1 WO2022118723 A1 WO 2022118723A1
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group
epoxy resin
compound
hydroxyl group
resin
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PCT/JP2021/043092
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English (en)
Japanese (ja)
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和賢 青山
和久 矢本
源祐 秋元
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Dic株式会社
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Priority to JP2022566870A priority Critical patent/JP7290205B2/ja
Priority to KR1020237011018A priority patent/KR20230059829A/ko
Priority to CN202180081331.0A priority patent/CN116583943A/zh
Publication of WO2022118723A1 publication Critical patent/WO2022118723A1/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
    • C08G59/20—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 epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

  • the present invention relates to an epoxy resin, a curable composition, a cured product, a semiconductor encapsulating material, a semiconductor device, a prepreg, a circuit board, and a build-up film.
  • Epoxy resin compositions containing epoxy resin and its curing agent as essential components are excellent in various physical properties such as high heat resistance, moisture resistance, and low viscosity, and thus are excellent in various physical properties such as semiconductor encapsulation materials, electronic parts such as printed circuit boards, and conductive pastes. It is widely used in conductive adhesives such as, other adhesives, matrices for composite materials, paints, photoresist materials, and color-developing materials.
  • the semiconductor encapsulation material is used by filling the resin material with an inorganic filler such as silica, the resin material has a low viscosity and excellent fluidity in order to increase the filling rate of the filler. It is also required.
  • Patent Document 1 As a semiconductor encapsulating material that meets the required characteristics, for example, it is disclosed that an aralkyl-modified poly (oxynaphthalethylene) type epoxy resin is used (see Patent Document 1).
  • Patent Document 1 Although the epoxy resin disclosed in Patent Document 1 is excellent in heat resistance of the obtained cured product, the melt viscosity of the epoxy resin itself is high, and the epoxy resin composition containing the epoxy resin has fluidity and moldability. It is inferior to the above, and the reduction of warpage has not been clarified.
  • an epoxy resin composition having a particularly low viscosity and excellent fluidity and moldability and the epoxy resin composition can be obtained, and have high heat resistance and sufficient toughness.
  • an epoxy resin composition for encapsulating a semiconductor, which can obtain a cured product has not been obtained.
  • the problem to be solved by the present invention is obtained by using an epoxy resin having a low melt viscosity and contributing to fluidity and moldability, a curable composition containing the epoxy resin, and the curable composition. It is an object of the present invention to provide a cured product having high heat resistance and high toughness, a semiconductor encapsulating material, a semiconductor device, a prepreg, a circuit board, and a build-up film.
  • the present inventors have conducted an epoxy resin that can contribute to excellent fluidity and moldability, a curable composition containing the epoxy resin, and the curable composition.
  • a cured product, a semiconductor encapsulant, a semiconductor device, a prepreg, a circuit board, and a build-up film which are obtained by using a material and have excellent heat resistance and high toughness, and have completed the present invention. ..
  • the present invention comprises a glycidyl etherified product (E1) of a biphenol compound (P1), a dihydroxyarene compound ( ⁇ ), and an aralkylating agent represented by the following general formula (1-1) or (1-2).
  • the present invention relates to an epoxy resin containing a glycidyl etherified product (E2) of a phenolic hydroxyl group-containing resin (P2) using ⁇ ) as a reaction raw material.
  • X represents any of a halogen atom, a hydroxyl group, and an alkoxy group.
  • R 1 independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 2 independently represents a hydrogen atom or a methyl group.
  • Ar 1 represents any of a phenyl group, a naphthyl group, and a structural moiety having one or more halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups on these aromatic nuclei.
  • a biphenol compound (P1) and a dihydroxyarene compound ( ⁇ ) and an aralkylating agent ( ⁇ ) represented by the following general formula (1-1) or (1-2) are used as reaction raw materials.
  • the present invention relates to an epoxy resin containing a glycidyl etherified compound (E3) of a mixture of a phenolic hydroxyl group-containing resin (P2).
  • X represents any of a halogen atom, a hydroxyl group, and an alkoxy group.
  • R 1 independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 2 independently represents a hydrogen atom or a methyl group.
  • Ar 1 represents any of a phenyl group, a naphthyl group, and a structural moiety having one or more halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups on these aromatic nuclei.
  • the ratio of the biphenol compound (P1) to the total mass of the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2) is 0.5% by mass or more and 40% by mass or less. It is preferable to have.
  • the epoxy resin of the present invention preferably contains the compound (A) in which the phenolic hydroxyl group-containing resin (P2) has three naphthalene ring structures in one molecule.
  • the content of the compound (A) in the phenolic hydroxyl group-containing resin (P2) is 5 to 50 as a value calculated from the area ratio of the gel permeation chromatography (GPC) chart. % Is preferable.
  • the epoxy resin of the present invention preferably has a melt viscosity at 150 ° C. measured by an ICI viscometer of 0.01 to 5 dPa ⁇ s.
  • the present invention relates to a curable composition containing the epoxy resin and a curing agent for an epoxy resin.
  • the present invention relates to a cured product of the curable composition.
  • the present invention relates to a semiconductor encapsulating material containing the curable composition.
  • the present invention relates to a semiconductor device containing a cured product of the semiconductor encapsulating material.
  • the present invention relates to a prepreg having a reinforcing base material and a semi-cured product of the curable composition impregnated in the reinforcing base material.
  • the present invention relates to the circuit board which is a laminated body of the prepreg and copper foil.
  • the present invention relates to a build-up film containing the curable composition.
  • the epoxy resin of the present invention has a low viscosity and is excellent in fluidity and moldability, and the cured product of the curable composition containing the epoxy resin is excellent in high heat resistance and high toughness.
  • it is useful as a resin material for electrical materials such as semiconductor encapsulation materials.
  • 6 is a GPC chart of the phenolic hydroxyl group-containing resin (P2-1) obtained in Synthesis Example 1.
  • 6 is a GPC chart of the epoxy resin (1) obtained in Example 1.
  • 6 is a GPC chart of the epoxy resin (2) obtained in Example 2.
  • 6 is a GPC chart of the epoxy resin (3) obtained in Example 3.
  • the present invention comprises a glycidyl etherified product (E1) of a biphenol compound (P1), a dihydroxyarene compound ( ⁇ ), and an aralkylating agent ( ⁇ ) represented by the following general formula (1-1) or (1-2).
  • E1 a reaction raw material
  • the present invention relates to an epoxy resin containing a glycidyl etherified product (E2) of a phenolic hydroxyl group-containing resin (P2).
  • X represents any of a halogen atom, a hydroxyl group, and an alkoxy group.
  • R 1 independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 2 independently represents a hydrogen atom or a methyl group.
  • Ar 1 represents any of a phenyl group, a naphthyl group, and a structural moiety having one or more halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups on these aromatic nuclei.
  • a biphenol compound (P1) and a dihydroxyarene compound ( ⁇ ) and an aralkylating agent ( ⁇ ) represented by the following general formula (1-1) or (1-2) are used as reaction raw materials.
  • the present invention relates to an epoxy resin containing a glycidyl etherified compound (E3) of a mixture of a phenolic hydroxyl group-containing resin (P2).
  • X represents any of a halogen atom, a hydroxyl group, and an alkoxy group.
  • R 1 independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 2 independently represents a hydrogen atom or a methyl group.
  • Ar 1 represents any of a phenyl group, a naphthyl group, and a structural moiety having one or more halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups on these aromatic nuclei.
  • the biphenol compound (P1) is not particularly limited, and is, for example, 2,2'-biphenol, 2,4'-biphenol, 3,3'-biphenol, 4,4'-biphenol, and on the aromatic ring thereof. Examples thereof include various compounds in which one or a plurality of aliphatic hydrocarbon groups, alkoxy groups, halogen atoms and the like are substituted.
  • the biphenol compound (P1) may be used alone or in combination of two or more.
  • the aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in the structure. Of these, those having 1 to 4 carbon atoms are preferable, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, because the effect of excellent heat resistance in the cured product becomes more remarkable. , T-butyl group, isobutyl group, vinyl group, allyl group and the like.
  • the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group and the like.
  • halogen atom examples include a fluorine atom, a chlorine atom and a bromine atom.
  • a substituent on 4,4'-biphenol and its aromatic ring since it is easy to adjust the melt viscosity of the finally obtained epoxy resin to a preferable value, it is preferable to have a substituent on 4,4'-biphenol and its aromatic ring, and 4,4'-biphenol is more preferable. ..
  • phenolic hydroxyl group-containing resin (P2) uses a dihydroxyarene compound ( ⁇ ) and an aralkylating agent ( ⁇ ) represented by the following general formula (1-1) or (1-2) as reaction raw materials.
  • X represents any of a halogen atom, a hydroxyl group, and an alkoxy group.
  • R 1 independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 2 independently represents a hydrogen atom or a methyl group.
  • Ar 1 represents any of a phenyl group, a naphthyl group, and a structural moiety having one or more halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups on these aromatic nuclei.
  • X represents any one of a halogen atom, a hydroxyl group, and an alkoxy group.
  • R 1 independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 2 independently represents a hydrogen atom or a methyl group.
  • Ar 1 represents any of a phenyl group, a naphthyl group, and a structural moiety having one or more halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups on these aromatic nuclei.
  • the phenolic hydroxyl group-containing resin (P2) contains a component having a (poly) arylene ether structure generated by an intramolecular dehydration reaction of the dihydroxyarene compound ( ⁇ ). Further, the olerousyl group is introduced into a part or all of the aromatic ring in the phenolic hydroxyl group-containing resin (P2) by the oleresin agent ( ⁇ ). As a result, the glycidyl etherified product (E2) of the phenolic hydroxyl group-containing resin (P2) has a relatively long distance between the glycidyl ether groups in the molecule and a high aromatic ring concentration, so that the curing can be obtained. It is possible to combine heat resistance and toughness in an object at a high level.
  • the dihydroxyarene compound ( ⁇ ) may be any compound having two hydroxy groups on the aromatic ring, and its specific structure is not particularly limited, and a wide variety of compounds can be used. Specific examples include dihydroxybenzene, dihydroxynaphthalene, and compounds having one or more substituents such as a halogen atom, an aliphatic hydrocarbon group, and an alkoxy group on their aromatic rings. In the present invention, one type of the dihydroxyarene compound ( ⁇ ) may be used alone, or two or more types may be used in combination.
  • the substitution position of the two hydroxy groups is not particularly limited, and may be any of the ortho position, the para position, and the meta position. Further, in the dihydroxynaphthalene, the substitution positions of the two hydroxy groups are not particularly limited, and are, for example, 1,2-position, 1,4-position, 1,5-position, 1,6-position and 1,7-position. , 2,3-position, 2,6-position, 2,7-position.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and the like.
  • the aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in the structure. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group and the like.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propyloxy group, a butyloxy group and the like.
  • dihydroxyarene compounds ( ⁇ ) a halogen atom, an aliphatic hydrocarbon group, and an alkoxy group are placed on the dihydroxynaphthalene and its aromatic ring because the obtained cured product has more remarkable effects on heat resistance and toughness.
  • the position of the hydroxy group on the dihydroxynaphthalene is preferably 1,6-position or 2,7-position, and more preferably 2,7-position.
  • dihydroxyarene compound ( ⁇ ) When a plurality of types of the dihydroxyarene compound ( ⁇ ) are used in combination, dihydroxynaphthalene occupying the dihydroxyarene compound ( ⁇ ) and a halogen atom, an aliphatic hydrocarbon group, an alkoxy group or the like on the aromatic ring thereof.
  • the ratio of the compound having one or a plurality of substituents is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 95% by mass or more.
  • the aralkylating agent ( ⁇ ) has a molecular structure represented by the general formula (1-1) or (1-2).
  • the aralkylating agent ( ⁇ ) one type may be used alone, or two or more types may be used in combination.
  • the X represents any one of a halogen atom, a hydroxyl group, and an alkoxy group.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like.
  • the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a butyloxy group and the like.
  • a halogen atom or a hydroxyl group is preferable, and a hydroxyl group is particularly preferable, from the viewpoint of excellent reactivity.
  • the R 1 independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Of these, a hydrogen atom is preferable because of its excellent reactivity.
  • the R 2 independently represents a hydrogen atom or a methyl group, respectively. Of these, a hydrogen atom is preferable because of its excellent reactivity.
  • the Ar 1 has a phenyl group, a naphthyl group, and one or more halogen atoms, an aliphatic hydrocarbon group, and an alkoxy group on these aromatic nuclei. It is one of the structural parts.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and the like.
  • the aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in the structure. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group and the like.
  • the alkoxy group examples include a methoxy group, an ethoxy group, a propyloxy group, a butyloxy group and the like.
  • the Ar 1 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group, because the effect of excellent heat resistance and toughness in the cured product becomes more remarkable.
  • the ratio of the compound in which Ar 1 is a phenyl group to the aralkylating agent ( ⁇ ) is preferably 50% by mass or more, and is 80%. It is more preferably mass% or more, and particularly preferably 95% by mass or more.
  • the phenolic hydroxyl group-containing resin (P2) may use a component other than the dihydroxyarene compound ( ⁇ ) and the aralkylating agent ( ⁇ ) as a part of the reaction raw material.
  • the total mass of the dihydroxyarene compound ( ⁇ ) and the aralkylating agent ( ⁇ ) in the total mass of the reaction raw material of the phenolic hydroxyl group-containing resin (P2) is preferably 80% by mass or more. It is more preferably 95% by mass or more.
  • Examples of the method for producing the phenolic hydroxyl group-containing resin (P2) include a method in which a reaction raw material containing the dihydroxyarene compound ( ⁇ ) and the aralkylating agent ( ⁇ ) is reacted under acid catalyst conditions. Further, the reaction may be carried out in a solvent if necessary.
  • the reaction ratio between the dihydroxyarene compound ( ⁇ ) and the aralkylating agent ( ⁇ ) is an epoxy resin having excellent fluidity
  • the molar ratio [( ⁇ ) / ( ⁇ )] of the two is 1/0. It is preferably in the range of 1 to 1/10, and more preferably in the range of 1 / 0.1 to 1/1.
  • the acid catalyst includes, for example, inorganic acids such as phosphoric acid, sulfuric acid and hydrochloric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid and fluoromethanesulfonic acid, aluminum chloride, zinc chloride and chloride.
  • inorganic acids such as phosphoric acid, sulfuric acid and hydrochloric acid
  • organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid and fluoromethanesulfonic acid
  • aluminum chloride zinc chloride and chloride
  • Examples thereof include Friedelcraft catalysts such as ditin, ferric chloride and diethylsulfuric acid. These may be used alone or in combination of two or more.
  • an inorganic acid or an organic acid is used as the acid catalyst, it is preferably used in the range of 0.01 to 3 parts by mass with respect to 100 parts by mass of the dihydroxyarene compound ( ⁇ ).
  • a Friedel-Crafts catalyst is used as the acid catalyst, it is preferably used in the range of 0.5 to 2 mol with respect to 1 mol of the dihydroxyarene compound ( ⁇ ).
  • the solvent is, for example, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol.
  • the reaction between the dihydroxyarene compound ( ⁇ ) and the aralkylating agent ( ⁇ ) can be carried out under temperature conditions of about 60 to 180 ° C., and the reaction time is about 1 to 24 hours.
  • the reaction can be promoted more efficiently by appropriately distilling off water or the like generated during the reaction.
  • the inside of the reaction system is neutralized with an alkaline compound such as an alkali metal hydroxide, or water is recommended and then dried to obtain the phenolic hydroxyl group-containing resin (P2). Can be done.
  • the hydroxyl group equivalent of the phenolic hydroxyl group-containing resin (P2) is preferably in the range of 100 to 400 g / equivalent, and 110 to 300 g / equivalent, because the effect of excellent heat resistance and toughness in the cured product becomes more remarkable. It is preferably in the range of.
  • the softening point is preferably in the range of 60 to 140 ° C.
  • the phenolic hydroxyl group-containing resin (P2) for example, when 2,7-dihydroxynaphthalene is used as the dihydroxyarene compound ( ⁇ ) and benzyl alcohol is used as the aralkylating agent ( ⁇ ), the phenolic property is used.
  • Specific examples of the specific structure of each component contained in the hydroxyl group-containing resin (P2) include those represented by any of the following structural formulas (2-1) to (2-18).
  • the structural formulas (2-6) to (2-8) and (2-10) It is preferable to contain the compound (A) having three naphthalene ring structures in one molecule as represented by (2-11).
  • the content of the compound (A) in the phenolic hydroxyl group-containing resin (P2) is 5 to 50% as a value calculated from the area ratio of the chart diagram of gel permeation chromatography (GPC). It is preferably 10 to 45%, more preferably 10 to 45%.
  • GPC gel permeation chromatography
  • the production method thereof may be as follows. It is not particularly limited, and may be manufactured in any way.
  • an epoxy resin of the present invention for example, (1) a glycidyl etherified product (E1) obtained by reacting the biphenol compound (P1) with epihalohydrin to form a glycidyl etherified product is synthesized, and the phenolic hydroxyl group-containing resin is separately prepared.
  • the epoxy resin of the present invention can be obtained by reacting (P2) with epihalohydrin to synthesize a glycidyl etherified product (E2) that has been glycidyl etherified, and mixing (containing) these.
  • (2) epihalohydrin is added to a mixture of the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2), and the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2) are combined with each other.
  • epihalohydrin a glycidyl ether compound (E3) containing the glycidyl ether compound (E1) and the glycidyl ether compound (E2) is synthesized, and the one containing the glycidyl ether compound (E3) is used as the epoxy resin of the present invention. Can be done.
  • the manufacturing method of (2) above is preferable because it is excellent in convenience and workability.
  • the reaction between the biphenol compound (P1) and epihalohydrin and the reaction between the phenolic hydroxyl group-containing resin (P2) and epihalohydrin are carried out, for example, in the presence of a basic catalyst.
  • a basic catalyst examples thereof include a method of reacting at 20 to 150 ° C., preferably 30 to 80 ° C. for 0.5 to 10 hours.
  • epichlorohydrin examples include epichlorohydrin, epibromohydrin, ⁇ -methylepichlorohydrin and the like.
  • the amount of epihalohydrin added is excessively used with respect to a total of 1 mol of the hydroxyl groups of the biphenol compound (P1) or the phenolic hydroxyl group-containing resin (P2), but is usually 1.5 to 30 mol. Yes, preferably in the range of 2 to 15 mol.
  • the basic catalyst examples include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. Of these, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity, and specifically, sodium hydroxide, potassium hydroxide and the like are more preferable. Further, these basic catalysts may be used in a solid state or in an aqueous solution state. The amount of the basic catalyst added may be in the range of 0.9 to 2 mol with respect to a total of 1 mol of the hydroxyl groups of the biphenol compound (P1) or the phenolic hydroxyl group-containing resin (P2). preferable.
  • the reaction between the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2) and epihalohydrin may be carried out in an organic solvent.
  • organic solvent include ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol and tertiary butanol, methyl cellosolve and ethyl cellosolve.
  • Examples thereof include cellosolves, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotonic polar solvents such as acetonitrile, dimethylsulfoxide and dimethylformamide.
  • ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane
  • aprotonic polar solvents such as acetonitrile, dimethylsulfoxide and dimethylformamide.
  • a crude product can be obtained by distilling off the excess epihalohydrin. If necessary, the hydrolyzable halogen may be reduced by dissolving the obtained crude product in an organic solvent again, adding a basic catalyst and reacting again.
  • the salt generated in the reaction can be removed by filtration, washing with water, or the like.
  • an organic solvent it may be distilled off to take out only the resin solid content, or it may be used as it is as a solution.
  • the mass ratio of the glycidyl etherified product (E1) to the glycidyl etherified product (E2) is not particularly limited, but the fluidity is excellent and the toughness property of the cured product is high.
  • the ratio of the glycidyl etherified product (E1) to the total mass of both is preferably 0.5% by mass or more, and preferably 1% by mass or more, because the epoxy resin has excellent low moisture absorption. It is more preferably 5% by mass or more, and particularly preferably 15% by mass or more.
  • the upper limit thereof is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the mass ratio of both in the mixture of the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2) is excellent in fluidity and in the cured product. Since the epoxy resin has high toughness and low moisture absorption, the ratio of the biphenol compound (P1) to the total mass of both is preferably 0.5% by mass or more, preferably 1% by mass or more. Is preferable, 5% by mass or more is more preferable, and 15% by mass or more is particularly preferable. The upper limit thereof is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the reaction of the mixture of the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2) with epihalohydrin can be carried out by the same method as the method for producing the epoxy resin of (1).
  • the amount of the epihalohydrin added is excessively used with respect to a total of 1 mol of the hydroxyl groups of the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2), but is usually 1.5 to 30 mol, preferably 1.5 to 30 mol. It ranges from 2 to 15 mol.
  • a basic catalyst can be used, and the amount of the basic catalyst added is the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2). It is preferably in the range of 0.9 to 2 mol with respect to 1 mol of the total hydroxyl group contained in.
  • the epoxy equivalent of the epoxy resin of the present invention is preferably 140 to 400 g / equivalent, more preferably 140 to 350 g / equivalent.
  • the measurement of the epoxy equivalent here is based on JIS K7236.
  • the epoxy resin of the present invention preferably has a melt viscosity at 150 ° C. measured by an ICI viscometer of 0.01 to 5 dPa ⁇ s, more preferably 0.01 to 2 dPa ⁇ s, and 0.01. It is more preferably ⁇ 1 dPa ⁇ s.
  • the melt viscosity here is based on ASTM D4287 and is measured by an ICI viscometer.
  • the number average molecular weight (Mn) is preferably in the range of 200 to 1500, more preferably in the range of 200 to 800.
  • the weight average molecular weight (Mw) is preferably in the range of 250 to 2000, more preferably in the range of 250 to 800.
  • the dispersity (Mw / Mn) is preferably in the range of 1 to 3.
  • the molecular weight and the degree of dispersion of the epoxy resin are measured by gel permeation chromatography (GPC) under the measurement conditions described in Examples described later.
  • epoxy resin of the present invention include epoxy resins represented by the following structural formulas.
  • n is an integer of 0 to 10.
  • the present invention relates to a curable composition containing the epoxy resin and a curing agent for an epoxy resin.
  • the curable composition contains the epoxy resin, the obtained cured product has excellent heat resistance and toughness, which is preferable.
  • an epoxy resin curing agent capable of cross-linking reaction with the epoxy group of the epoxy resin can be used without particular limitation.
  • the curing agent include a phenol curing agent, an amine curing agent, an acid anhydride curing agent, an active ester resin, and a cyanate ester resin.
  • the curing agent may be used alone or in combination of two or more.
  • phenol curing agent examples include phenol novolac resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin (Zyroc resin), naphthol aralkyl resin, and triphenylol.
  • Biphenyl-modified naphthol resin polyvalent naphthol compound in which phenol nuclei are linked by bismethylene groups
  • aminotriazine-modified phenol resin polyvalent phenolic hydroxyl group-containing compound in which phenol nuclei are linked by melamine, benzoguanamine, etc.
  • alkoxy groups examples thereof include polyvalent phenolic hydroxyl group-containing compounds such as a contained aromatic ring-modified novolak resin (a polyvalent phenolic hydroxyl group-containing compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).
  • phenol novolac trees and the like are more preferable from the viewpoint of moldability.
  • the compound containing the phenolic hydroxyl group may be used alone or in combination of two or more.
  • amine curing agent examples include diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), diproprendamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine and mensendiamine.
  • DTA diethylenetriamine
  • TTA triethylenetetramine
  • TEPA tetraethylenepentamine
  • DPDA diproprendamine
  • DEAPA diethylaminopropylamine
  • mensendiamine examples include diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), diproprendamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine and mensendiamine.
  • MDA Isophorondiamine
  • IPDA 1,3-bisaminomethylcyclohexane
  • piperidine N, N, -dimethylpiperazine, triethylenediamine and other aliphatic amines
  • m-xylenediamine XDA
  • methanephenylenediamine MPDA
  • diaminodiphenylmethane DDM
  • diaminodiphenylsulfone DDS
  • benzylmethylamine 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, etc.
  • Aromatic amines and the like can be mentioned.
  • acid anhydride curing agent examples include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bistrimeritate, glycerol tristrimeritate, maleic anhydride, and tetrahydrophthalic anhydride.
  • the amount of the curing agent used with respect to the amount of the epoxy resin used is not particularly limited as, for example, the functional group equivalent ratio (for example, the hydroxyl group equivalent of the phenol curing agent / the epoxy equivalent of the epoxy resin). Since the mechanical properties of the cured product to be obtained are good, the number of active groups in the curing agent is 0 with respect to a total of 1 equivalent of the epoxy group with the epoxy resin and other epoxy resins used in combination as needed.
  • the amount is preferably 5.5 to 1.5 equivalents, more preferably 0.8 to 1.2 equivalents.
  • epoxy resins other than the epoxy resin maleimide resin, bismaleimide resin, polymaleimide resin, polyphenylene ether resin, polyimide resin, benzoxazine resin, triazine-containing cresol novolak resin, styrene-maleic anhydride resin, diallyl bisphenol and triallyl.
  • epoxy resins other than the epoxy resin maleimide resin, bismaleimide resin, polymaleimide resin, polyphenylene ether resin, polyimide resin, benzoxazine resin, triazine-containing cresol novolak resin, styrene-maleic anhydride resin, diallyl bisphenol and triallyl.
  • examples thereof include an allyl group-containing resin such as isocyanurate, a polyphosphate ester, and a phosphate ester-carbonate copolymer.
  • the curable composition of the present invention may be prepared without a solvent, or may contain a solvent.
  • the solvent has a function of adjusting the viscosity of the curable composition and the like.
  • the solvent are not particularly limited, but are ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ethyl acetate, butyl acetate, cellosolve acetate and propylene glycol monomethyl.
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
  • ether solvents such as diethyl ether and tetrahydrofuran
  • Ester solvents such as ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol, toluene, xylene, ethylbenzene, mecitylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene and the like.
  • Examples thereof include amide-based solvents such as aromatic hydrocarbons, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.
  • the amount of the solvent used is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the curable composition.
  • the amount of the solvent used is 10% by mass or more, it is preferable because the handling property is excellent.
  • the amount of the solvent used is 90% by mass or less, it is preferable from the viewpoint of economy.
  • the curable composition of the present invention contains various additives such as a curing accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a mold release agent, a pigment, a colorant, and an emulsifier, if necessary. Can be done.
  • the curing accelerator is not particularly limited, and examples thereof include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, and a urea-based curing accelerator.
  • the curing accelerator may be used alone or in combination of two or more.
  • Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, triparatrilphosphine, diphenylcyclohexylphosphine and tricyclohexylphosphine; organic phosphite compounds such as trimethylphosphine and triethylphosphine; ethyltriphenyl.
  • organic phosphine compounds such as triphenylphosphine, tributylphosphine, triparatrilphosphine, diphenylcyclohexylphosphine and tricyclohexylphosphine
  • organic phosphite compounds such as trimethylphosphine and triethylphosphine
  • ethyltriphenyl ethyltriphenyl.
  • Phosphonium bromide benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-trilborate, triphenylphosphine triphenylboran, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium disianamide, Examples thereof include phosphonium salts such as butylphenylphosphonium dicyanamide and tetrabutylphosphonium decanoate.
  • Examples of the amine-based curing accelerator include triethylamine, tributylamine, N, N-dimethyl-4-aminopyridine (4-dimethylaminopyridine, DMAP), 2,4,6-tris (dimethylaminomethyl) phenol, 1, Examples thereof include 8-diazabicyclo [5.4.0] -undecene-7 (DBU) and 1,5-diazabicyclo [4.3.0] -Nonen-5 (DBN).
  • DBU 8-diazabicyclo [5.4.0] -undecene-7
  • DBN 1,5-diazabicyclo [4.3.0] -Nonen-5
  • imidazole-based curing accelerator examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl.
  • Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1, 5,7-Triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] deca-5-ene, 1-methylbiguanide , 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide and the like.
  • urea-based curing accelerator examples include 3-phenyl-1,1-dimethylurea, 3- (4-methylphenyl) -1,1-dimethylurea, chlorophenylurea, and 3- (4-chlorophenyl) -1,1. -Dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea and the like can be mentioned.
  • triphenylphosphine and tertiary amines are used as phosphorus compounds because they are excellent in curability, heat resistance, electrical properties, moisture resistance reliability, etc., especially when used as a semiconductor encapsulating material. It is preferable to use 1,8-diazabicyclo- [5.4.0] -undecene (DBU).
  • DBU 1,8-diazabicyclo- [5.4.0] -undecene
  • the amount of the curing accelerator used can be appropriately adjusted in order to obtain the desired curability, but it is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the mixture of the epoxy resin and the curing agent. Is preferable, and 0.1 to 5 parts by mass is more preferable. When the amount of the curing accelerator used is within the above range, the curing property and the insulation reliability are excellent, which is preferable.
  • the flame retardant is not particularly limited, and examples thereof include an inorganic phosphorus flame retardant, an organic phosphorus flame retardant, and a halogen flame retardant.
  • the flame retardant may be used alone or in combination of two or more.
  • the inorganic phosphorus-based flame retardant is not particularly limited, and examples thereof include red phosphorus; ammonium phosphate such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and phosphoric acid amide.
  • the organic phosphorus-based flame retardant is not particularly limited, but is limited to methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, and bis (2-ethylhexyl).
  • Phosphate Monoisodecyl Acid Phosphate, Lauryl Acid Phosphate, Tridecyl Acid Phosphate, Stearyl Acid Phosphate, Isostearyl Acid Phosphate, Oleyl Acid Phosphate, Butyl Pyrophosphate, Tetracosyl Acid Phosphate, Ethylene Glycol Acid Phosphate, (2-Hydroxyethyl) ) Phosphate esters such as methacrylate acid phosphate; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine oxide and the like diphenylphosphine; 10- (2,5-dihydroxyphenyl) -10H- 9-Oxa-10-phosphaphenanthrene-10-oxide, 10- (1,4-dioxynaphthalene) -10H-9-oxa-10-phosphaphenanthrene-10-
  • the halogen-based flame retardant is not particularly limited, but is limited to brominated polystyrene, bis (pentabromophenyl) ethane, tetrabromobisphenol A bis (dibromopropyl ether), 1,2, -bis (tetrabromophthalimide), 2, Examples thereof include 4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine and tetrabromophthalic acid.
  • the amount of the flame retardant used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin.
  • the inorganic filler is not particularly limited, but is silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, and nitrided.
  • silica Boron, aluminum hydroxide, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, barium zirconate , Calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black and the like.
  • silica it is preferable to use silica.
  • the molten silica is preferable because it is possible to add a larger amount of the inorganic filler.
  • the fused silica can be used in either a crushed form or a spherical shape, but in order to increase the blending amount of the fused silica and suppress the increase in the melt viscosity of the curable composition, a spherical one is mainly used. Is preferable. Further, in order to increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica.
  • the inorganic filler may be used alone or in combination of two or more.
  • the inorganic filler may be surface-treated if necessary.
  • the surface treatment agent that can be used is not particularly limited, but is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an organosilazane compound, and a titanate-based cup. Ring agents and the like can be used.
  • the surface treatment agent examples include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and hexamethyldi. Silazan and the like can be mentioned.
  • the amount of the inorganic filler used is preferably 0.5 to 95 parts by mass with respect to 100 parts by mass of the total amount of the mixture of the epoxy resin and the curing agent.
  • the amount of the inorganic filler used is within the above range, flame retardancy and insulation reliability are excellent, which is preferable.
  • organic filler can be blended in addition to the inorganic filler as long as the characteristics of the present invention are not impaired.
  • examples of the organic filler include polyamide particles and the like.
  • the present invention relates to a cured product of the curable composition.
  • the cured product obtained from the curable composition containing the epoxy resin can exhibit high heat resistance and high toughness, which is a preferable embodiment.
  • the heating temperature at the time of heat curing is not particularly limited, but is usually 100 to 300 ° C., and the heating time is 1 to 1 to 1. 24 hours.
  • the cured product of the present invention preferably has a glass transition temperature (Tg) of 160 ° C. or higher.
  • Tg glass transition temperature
  • the method for measuring the glass transition temperature (Tg) is the same as the evaluation method in the examples of the present application.
  • the cured product of the present invention preferably has a Charpy impact strength of 6.5 J / cm 2 or more, more preferably 7.3 J / cm 2 or more, and 7.8 J / cm 2 or more. Is particularly preferable.
  • the method for measuring the Charpy impact strength is the same as the evaluation method in the examples of the present application.
  • the present invention relates to a semiconductor encapsulating material containing the curable composition. Since the semiconductor encapsulation material obtained by using the curable composition uses the epoxy resin, it has a low viscosity and excellent fluidity, and further, the heat resistance and toughness of the cured product are improved, so that in the manufacturing process. It is excellent in processability and moldability, and is a preferable embodiment.
  • the curable composition used for the semiconductor encapsulant material can contain an inorganic filler.
  • the filling rate of the inorganic filler for example, the inorganic filler can be used in the range of 0.5 to 95 parts by mass with respect to 100 parts by mass of the curable composition.
  • the curable composition is further added with an additive as an optional component, if necessary, using an extruder, a feeder, a roll, or the like until the composition becomes uniform.
  • an additive as an optional component, if necessary, using an extruder, a feeder, a roll, or the like until the composition becomes uniform. Examples thereof include a method of sufficiently melting and mixing.
  • the present invention relates to a semiconductor device containing a cured product of the semiconductor encapsulating material. Since the semiconductor device obtained by using the semiconductor encapsulating material obtained by using the curable composition uses the epoxy resin, it has low viscosity and excellent fluidity, and further, heat resistance and toughness in the cured product are obtained. Since it has been improved, it is excellent in processability and molding in the manufacturing process, which is a preferable embodiment.
  • the semiconductor encapsulant material is cast or molded using a transfer molding machine, an injection molding machine, or the like, and further heat-cured in a temperature range of room temperature (20 ° C.) to 250 ° C. There is a way to do it.
  • the present invention relates to a prepreg having a reinforcing base material and a semi-cured product of the curable composition impregnated in the reinforcing base material.
  • a curable composition varnished by blending an organic solvent described later is used as a reinforcing base material (paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass).
  • a method of obtaining the material by impregnating it with a mat, a glass roving cloth, etc.) and then heating it at a heating temperature according to the solvent type used, preferably 50 to 170 ° C. can be mentioned.
  • the mass ratio of the curable composition and the reinforcing base material used at this time is not particularly limited, but it is usually preferable to prepare the resin content in the prepreg to be 20 to 60% by mass.
  • organic solvent used here examples include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate and the like. It can be appropriately selected depending on the application, but for example, when further producing a printed circuit board from prepylene as described below, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, or dimethylformamide. , It is preferable to use the non-volatile content at a ratio of 40 to 80% by mass.
  • the present invention relates to the circuit board which is a laminated body of the prepreg and a copper foil.
  • the prepregs are laminated by a conventional method, copper foils are appropriately laminated, and the pressure is 170 to 300 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.
  • An example is a method of heat-bonding.
  • the present invention relates to a build-up film containing the curable composition.
  • the curable composition is applied onto a support film to form a curable composition layer to form an adhesive film for a multilayer printed wiring board. The method can be mentioned.
  • the film When a build-up film is produced from a curable composition, the film is softened under the temperature conditions of laminating (usually 70 to 140 ° C.) in the vacuum laminating method, and at the same time as laminating the circuit board, via holes existing in the circuit board. Alternatively, it is important to show fluidity (resin flow) capable of filling the through hole with the resin, and it is preferable to blend each of the above components so as to exhibit such characteristics.
  • the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to enable resin filling in this range. .. When laminating both sides of the circuit board, it is desirable to fill about 1/2 of the through hole.
  • the varnish-like composition is applied to the surface of the support film (Y), and further heated.
  • it can be produced by drying an organic solvent by blowing hot air or the like to form a composition layer (X) made of a curable composition.
  • the thickness of the composition layer (X) to be formed is usually preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 ⁇ m, the thickness of the resin composition layer is preferably 10 to 100 ⁇ m.
  • composition layer (X) in the present invention may be protected by a protective film described later.
  • a protective film By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches.
  • the above-mentioned support film and protective film include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and further.
  • PET polyethylene terephthalate
  • polyesters such as polyethylene naphthalate, polycarbonate, polyimide
  • metal foils such as patterns, copper foils, and aluminum foils.
  • the support film and the protective film may be subjected to a mold release treatment in addition to the mud treatment and the corona treatment.
  • the thickness of the support film is not particularly limited, but is usually 10 to 150 ⁇ m, and is preferably used in the range of 25 to 50 ⁇ m.
  • the thickness of the protective film is preferably 1 to 40 ⁇ m.
  • the above-mentioned support film (Y) is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the adhesive film is heat-cured, it is possible to prevent dust and the like from adhering in the curing step. When peeling after curing, the support film is usually subjected to a mold release treatment in advance.
  • the cured product obtained by the curable composition of the present invention is excellent in heat resistance and toughness in the cured product, it can be used only for applications such as semiconductor encapsulation materials, semiconductor devices, prepregs, circuit boards, and build-up films. However, it can be suitably used for various applications such as build-up substrates, adhesives, resist materials, and matrix resins of fiber-reinforced resins, and the applications are not limited to these.
  • the softening point (° C.) was measured according to JIS K7234 (ring ball method).
  • GPC gel permeation chromatography
  • Measuring device "HLC-8320 GPC” manufactured by Tosoh Corporation, Column: Guard column “HXL-L” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G3000HXL” manufactured by Tosoh Corporation + “TSK-GEL G4000HXL” manufactured by Tosoh Corporation Detector: RI (Differential Refractometer) Data processing: "GPC Workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation Measurement conditions: Column temperature 40 ° C Developing solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of the above-mentioned "GPC workstation EcoSEC-WorkStation".
  • phenolic hydroxyl group-containing resin (P2-1) had a softening point of 97 ° C. and a hydroxyl group equivalent of 146 g / equivalent.
  • the content of the compound (A) having three naphthalene ring structures in one molecule of the phenolic hydroxyl group-containing resin (P2-1) was 33%.
  • the GPC chart of the phenolic hydroxyl group-containing resin (P2-1) is shown in FIG.
  • the content of the compound (A) was calculated from the area ratio of the GPC chart.
  • the compound (A) contained in the phenolic hydroxyl group-containing resin (P2-1) obtained above was represented by the following structural formula.
  • Example 1 Synthesis of epoxy resin (1)
  • 60.0 g, epichlorhydrin 1157 g, n-butanol 347 g, and water 58 g were charged and dissolved.
  • After raising the temperature to 60 ° C. 480 g of a 20 mass% sodium hydroxide aqueous solution was added dropwise over 5 hours. Then, stirring was continued for 0.5 hours under the same conditions.
  • the obtained epoxy resin (1) has an epoxy equivalent of 197 g / equivalent, a melt viscosity at 150 ° C. of 0.2 dPa ⁇ s, a number average molecular weight (Mn) of 314, a weight average molecular weight (Mw) of 372, and a degree of dispersion (Mw). / Mn) was 1.2.
  • the GPC chart of the epoxy resin (1) is shown in FIG.
  • the epoxy resin (1) obtained above contained an epoxy resin represented by the following structural formula.
  • n is an integer of 0 to 10.
  • Example 2 Synthesis of epoxy resin (2)
  • the reaction was carried out in the same manner as in Example 1 except that the phenolic hydroxyl group-containing resin (P2-1) was changed to 192.0 g and 4,4'-biphenol 48.0 g, and the epoxy resin (2) was used. Obtained.
  • the obtained epoxy resin (2) has an epoxy equivalent of 203 g / equivalent, a melt viscosity at 150 ° C. of 0.3 dPa ⁇ s, a number average molecular weight (Mn) of 319, a weight average molecular weight (Mw) of 381, and a degree of dispersion (Mw). / Mn) was 1.2.
  • the GPC chart is shown in FIG.
  • the epoxy resin (2) obtained above contained an epoxy resin represented by the following structural formula.
  • n is an integer of 0 to 10.
  • Example 3 Synthesis of epoxy resin (3)
  • the reaction was carried out in the same manner as in Example 1 except that the phenolic hydroxyl group-containing resin (P2-1) was changed to 232.8 g and 4,4'-biphenol 7.2 g, and the epoxy resin (3) was used. Obtained.
  • the obtained epoxy resin (3) has an epoxy equivalent of 213 g / equivalent, a melt viscosity at 150 ° C. of 0.4 dPa ⁇ s, a number average molecular weight (Mn) of 336, a weight average molecular weight (Mw) of 412, and a degree of dispersion (Mw). / Mn) was 1.2.
  • the GPC chart is shown in FIG.
  • the epoxy resin (3) obtained above contained an epoxy resin represented by the following structural formula.
  • n is an integer of 0 to 10.
  • the inside of the system was azeotropically boiled to dehydrate, and after undergoing microfiltration, the solvent was distilled off under reduced pressure conditions to obtain 176 g of epoxy resin (1').
  • the obtained epoxy resin (1') has an epoxy equivalent of 230 g / equivalent, a melt viscosity at 150 ° C. of 0.3 dPa ⁇ s, a number average molecular weight (Mn) of 426, a weight average molecular weight (Mw) of 666, and a degree of dispersion (Mw).
  • Mw / Mn) was 1.6.
  • the epoxy resins obtained in all the examples have low viscosity, excellent high fluidity, can contribute to good moldability, and are epoxy resins containing the epoxy resin.
  • the cured product obtained by using the composition (curable composition) has a high glass transition temperature, high heat resistance, shows a high value even in a Charpy impact test, and can be confirmed to have high toughness. It was confirmed that both heat resistance and high toughness were achieved.
  • Comparative Example 1 an epoxy resin (1') was synthesized without using a desired phenolic hydroxyl group-containing resin, and an epoxy resin composition using this was synthesized.
  • Comparative Example 2 using (curable composition) the results were inferior in heat resistance and toughness as compared with Examples.

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Abstract

La présente invention concerne une résine époxyde qui contient : un produit glycidyle éthérifié (E1) d'un composé biphénolique (P1) ; et un produit glycidyle éthérifié (E2) d'une résine contenant un groupe hydroxyle phénolique (P2) qui utilise, en tant que matériaux réactifs, un composé dihydroxyarène (α) et un agent d'aralkylation (β) qui est représenté par la formule générale (1-1) ou (1-2). (Dans les formules générales (1-1) et (1-2), X représente un atome d'halogène, un groupe hydroxyle ou un groupe alcoxy ; chaque R1 représente indépendamment un atome d'hydrogène ou un groupe alkyle ayant de 1 à 4 atomes de carbone ; chaque R2 représente indépendamment un atome d'hydrogène ou un groupe méthyle ; et Ar1 représente un groupe phényle, un groupe naphtyle ou une fraction structurale qui comprend un ou plusieurs atomes d'halogène, un ou plusieurs groupes hydrocarbures aliphatiques, ou un ou plusieurs groupes alcoxy sur l'un de ces noyaux aromatiques).
PCT/JP2021/043092 2020-12-03 2021-11-25 Résine époxyde, composition durcissable, produit durci, matériau d'étanchéité semi-conducteur, dispositif semi-conducteur, préimprégné, carte de circuit imprimé et film d'accumulation WO2022118723A1 (fr)

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JP2022566870A JP7290205B2 (ja) 2020-12-03 2021-11-25 エポキシ樹脂、硬化性組成物、硬化物、半導体封止材料、半導体装置、プリプレグ、回路基板、及び、ビルドアップフィルム
KR1020237011018A KR20230059829A (ko) 2020-12-03 2021-11-25 에폭시 수지, 경화성 조성물, 경화물, 반도체 봉지 재료, 반도체 장치, 프리프레그, 회로 기판, 및, 빌드업 필름
CN202180081331.0A CN116583943A (zh) 2020-12-03 2021-11-25 环氧树脂、固化性组合物、固化物、半导体密封材料、半导体装置、预浸料、电路基板、及积层薄膜

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0212225B2 (fr) * 1981-09-02 1990-03-19 Mitsubishi Petrochemical Co
JPH1160681A (ja) * 1997-08-14 1999-03-02 Jsr Corp ビフェノール型エポキシ樹脂およびその組成物
JP2000044775A (ja) * 1998-07-28 2000-02-15 Yuka Shell Epoxy Kk 半導体封止用エポキシ樹脂組成物
JP2007039551A (ja) * 2005-08-03 2007-02-15 Dainippon Ink & Chem Inc エポキシ樹脂，エポキシ樹脂組成物，硬化物，半導体装置，エポキシ樹脂の製造法
JP2011026385A (ja) * 2009-07-22 2011-02-10 Dic Corp エポキシ樹脂組成物、その硬化物、半導体封止材料、半導体装置、及びエポキシ樹脂
JP2014037487A (ja) * 2012-08-16 2014-02-27 Dic Corp 硬化性樹脂組成物、硬化物、及びプリント配線基板
WO2015037584A1 (fr) * 2013-09-10 2015-03-19 日本化薬株式会社 Mélange de résines époxy, composition de résine époxy, produit durci et dispositif semi-conducteur
JP2018138681A (ja) * 2016-04-04 2018-09-06 Dic株式会社 エポキシ樹脂組成物の製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0212225B2 (fr) * 1981-09-02 1990-03-19 Mitsubishi Petrochemical Co
JPH1160681A (ja) * 1997-08-14 1999-03-02 Jsr Corp ビフェノール型エポキシ樹脂およびその組成物
JP2000044775A (ja) * 1998-07-28 2000-02-15 Yuka Shell Epoxy Kk 半導体封止用エポキシ樹脂組成物
JP2007039551A (ja) * 2005-08-03 2007-02-15 Dainippon Ink & Chem Inc エポキシ樹脂，エポキシ樹脂組成物，硬化物，半導体装置，エポキシ樹脂の製造法
JP2011026385A (ja) * 2009-07-22 2011-02-10 Dic Corp エポキシ樹脂組成物、その硬化物、半導体封止材料、半導体装置、及びエポキシ樹脂
JP2014037487A (ja) * 2012-08-16 2014-02-27 Dic Corp 硬化性樹脂組成物、硬化物、及びプリント配線基板
WO2015037584A1 (fr) * 2013-09-10 2015-03-19 日本化薬株式会社 Mélange de résines époxy, composition de résine époxy, produit durci et dispositif semi-conducteur
JP2018138681A (ja) * 2016-04-04 2018-09-06 Dic株式会社 エポキシ樹脂組成物の製造方法

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KR20230059829A (ko) 2023-05-03

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