WO2018181719A1 - Résine époxy, composition de résine époxy, et objet durci obtenu à partir de celle-ci, son utilisation et procédé de production - Google Patents

Résine époxy, composition de résine époxy, et objet durci obtenu à partir de celle-ci, son utilisation et procédé de production Download PDF

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WO2018181719A1
WO2018181719A1 PCT/JP2018/013257 JP2018013257W WO2018181719A1 WO 2018181719 A1 WO2018181719 A1 WO 2018181719A1 JP 2018013257 W JP2018013257 W JP 2018013257W WO 2018181719 A1 WO2018181719 A1 WO 2018181719A1
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epoxy resin
carbon
atom
carbon atoms
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PCT/JP2018/013257
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Japanese (ja)
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矩章 福田
良太 針▲崎▼
山本　勝政
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住友精化株式会社
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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
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen

Definitions

  • the present invention relates to an epoxy resin, an epoxy resin composition, and a cured product, application, and manufacturing method thereof.
  • thermosetting resins such as epoxy resins are widely used as substrate materials and sealing materials.
  • Patent Documents 1 and 2 disclose a dicyclopentadiene type epoxy resin and a composition having the resin.
  • Patent Document 3 discloses an epoxy resin composition comprising an epoxy resin, an active ester compound, and a triazine-containing cresol novolak resin.
  • these low inductive properties are not sufficient.
  • the present invention is excellent in low dielectric characteristics, and a cured product excellent in adhesion to metals, and to provide an epoxy resin composition capable of forming.
  • the present inventor has found that the above object can be achieved by using a hydrosilylated epoxy resin having a specific structure. It came to be completed.
  • the present invention includes, for example, the subject matters described in the following sections.
  • Item 1 (A) a structural unit derived from an organic compound having a hydrosilyl group, formed by removing a hydrogen atom of the hydrosilyl group; (B) a structural unit formed by converting a carbon-carbon unsaturated bond into a C ⁇ C bond or a C—C bond derived from a compound having a carbon-carbon unsaturated bond and not having an epoxy group; , (C) An epoxy resin having a structural unit derived from a compound having a carbon-carbon unsaturated bond and an epoxy group and formed by converting the carbon-carbon unsaturated bond into a C ⁇ C bond or a C—C bond.
  • the organic compound having a hydrosilyl group has the formula (0): (Wherein R 1 s are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
  • Ring X is a ring having a structure in which 2 to 6 saturated hydrocarbon rings, unsaturated hydrocarbon rings, saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed, or saturated hydrocarbon ring and / or unsaturated N represents a ring having a structure in which two hydrocarbon rings are linked, and n X represents 1, 2, 3, or 4.
  • R 2 represents an alkylene group having 1 to 8 carbon atoms, and this group may have a part of carbon atoms substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom.
  • R 3 represents * —COO— or * —OCO— (wherein “*” represents the side bonded to R 2 or L.)
  • R 4 represents an alkylene group having 1 to 4 carbon atoms, In this group, a part of carbon atoms may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom, R 5 represents a methyl group or a hydrogen atom, and L is a k valence. Each independently represents 0 or 1.
  • m represents each independently 0 or 1.
  • n represents each independently 0 or 1.
  • k represents an integer of 1 to 6.
  • R 2 when R 2 is the plurality of may be each the same group, Oh There are, .R 3 which may be a part or all different groups when there are a plurality, it is possible to make each the same group, or may be different based on part or all.
  • R 4 When a plurality of R 4 are present, each may be the same group, or some or all may be different groups.
  • R 6A represents an alkenyl group or alkynyl group having 2 to 18 carbon atoms, and this group is at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom.
  • R 7 represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group, and these groups are a part of carbon atoms.
  • R 6 represents an alkylene group having 2 to 18 carbon atoms, and this group is selected from the group consisting of an oxygen atom and a nitrogen atom, with some carbon atoms excluding the carbon atom directly bonded to the silicon atom.
  • L 2 may be a linear or branched alkane, a saturated hydrocarbon ring or an unsaturated carbon, in which some of the carbon atoms may be substituted with oxygen atoms
  • Two hydrogen atoms from a ring having a structure in which 2 to 6 condensed hydrogen rings, nitrogen-containing heterocycles, or saturated hydrocarbon rings and / or unsaturated hydrocarbon rings or a structure having two linked structures are connected.
  • q represents a positive number greater than 0 and not greater than 20.
  • X 2 represents a divalent group obtained by removing two hydrogen atoms from the X ring. shown .R 1, R 2, R 3 , R 4, R 5, R 7, l, m n, o, and p are as defined above.) Item 5.
  • the epoxy resin according to item 4 which is subordinate to all of items 1, 2, and 3 represented by: Item 6.
  • Item 6. An epoxy resin composition comprising the epoxy resin according to any one of Items 1 to 5, and a curing catalyst and / or a curing agent.
  • Item 7. Item 7. A cured product of the epoxy resin composition according to item 6.
  • Item 8. A semiconductor encapsulant, a liquid encapsulant, a potting material, a sealing material, a printed circuit board material, or a composite material comprising the epoxy resin composition according to item 6 or the cured product according to claim 7 as a constituent element.
  • the epoxy resin composition according to the present invention can form a cured product having excellent low dielectric properties and excellent adhesion to metals.
  • the epoxy resin of the present invention comprises (A) a structural unit derived from an organic compound having a hydrosilyl group, formed by removing a hydrogen atom of the hydrosilyl group, and (B) a carbon-carbon unsaturated bond not containing an epoxy group. Formed by converting a carbon-carbon unsaturated bond into a C ⁇ C bond or a C—C bond derived from a compound having a carbon atom (ie, a compound having a carbon-carbon unsaturated bond and no epoxy group) A structural unit and (C) a structural unit derived from a compound having a carbon-carbon unsaturated bond and an epoxy group and formed by converting the carbon-carbon unsaturated bond into a C ⁇ C bond or a C—C bond. .
  • the epoxy resin is, for example, (A) an organic compound having a hydrosilyl group, (B) a compound having a carbon-carbon unsaturated bond not containing an epoxy group, and (C) It can be obtained by subjecting a compound having a carbon-carbon unsaturated bond and an epoxy group to a hydrosilylation reaction.
  • (A) an organic compound having a hydrosilyl group, (B) a compound having a carbon-carbon unsaturated bond not containing an epoxy group, and (C) a compound having a carbon-carbon unsaturated bond and an epoxy group May be abbreviated as “A component”, “B component” and “C component”, respectively.
  • a structural unit formed by converting a bond to a C ⁇ C bond or a C—C bond may be abbreviated as an A component structural unit, a B component structural unit, or a C component structural unit, respectively.
  • the epoxy resin of the present invention is obtained by subjecting component A to a hydrosilylation reaction with component B and component C. Therefore, the epoxy resin of the present invention is an epoxy resin having a structure in which a carbon-carbon unsaturated bond site is hydrosilylated, and can be referred to as a hydrosilylated epoxy resin.
  • the compound mentioned as A component, the compound mentioned as B component, and the compound mentioned as C component are various.
  • the epoxy resin of this invention includes all the combinations of A component, B component, and C component described in this specification. That is, the epoxy resin of the present invention includes all the various epoxy resins obtained from any combination of compounds corresponding to the components A to C described in this specification.
  • the component A is an organic compound having a hydrosilyl (Si—H) group and undergoing a hydrosilylation reaction with a carbon-carbon unsaturated bond.
  • the number of hydrosilyl groups is 1 or more, for example, 1 to 12 (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) is preferable, and 2, 3, or 4 is More preferred.
  • the component A is hydrosilylated with the component B and the component C, and a hydrogen atom is removed by the reaction, thereby forming an A component constituent unit.
  • a compound having a structure in which a hydrosilyl group is bonded to a ring is preferable.
  • the compound shown by following formula (0) is mentioned. (Wherein R 1 s are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
  • Ring X is a ring having a structure in which 2 to 6 saturated hydrocarbon rings, unsaturated hydrocarbon rings, saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed, or saturated hydrocarbon ring and / or unsaturated N represents a ring having a structure in which two hydrocarbon rings are linked, and n X represents 1, 2, 3, or 4.
  • examples of the component A include compounds having structures of formulas (1) to (4).
  • R 1 and the X ring are the same as defined above. That is, R 1 is the same or different and represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group.
  • the carbon atoms may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom
  • the ring X is a saturated hydrocarbon ring, an unsaturated hydrocarbon ring, a saturated hydrocarbon ring and / or a ring having a structure in which 2 to 6 unsaturated hydrocarbon rings are condensed, or a saturated hydrocarbon ring and / or Alternatively, a ring having a structure in which two unsaturated hydrocarbon rings are connected is shown.
  • R 1 may not represent a hydrogen atom (that is, R 1 may be the same or different and represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group).
  • R 1 may be the same or different and represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
  • one R 1 represents a hydrogen atom
  • the other R 1 represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. Is also preferable.
  • equation (1) is in the (sometimes referred to as X 1) 1 monovalent group obtained by removed is one hydrogen atom from X ring, two hydrogen from X is X ring in formula (2) A divalent group obtained by removing an atom (sometimes referred to as X 2 ), X in the formula (3) is a trivalent group obtained by removing three hydrogen atoms from the X ring (X 3 and is called that it is), the equation (X in 4) may be referred to as tetravalent group (X 4 obtained by removed four hydrogen atoms from the X ring), respectively.
  • a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed is collectively referred to as a “hydrocarbon ring”. May be written.
  • the saturated hydrocarbon ring is preferably a saturated hydrocarbon ring having 4 to 8 carbon atoms (4, 5, 6, 7, or 8), and more preferably exemplified by a cyclopentane ring and a cyclohexane ring.
  • the unsaturated hydrocarbon ring is preferably an unsaturated hydrocarbon ring having 4 to 8 carbon atoms (4, 5, 6, 7, or 8), more preferably a benzene ring or the like.
  • the saturated hydrocarbon ring and / or unsaturated hydrocarbon ring is 2, 3, Alternatively, a ring having 4 condensed rings is preferable, and a ring having 2 or 3 condensed rings is more preferable.
  • decahydronaphthalene ring More specifically, for example, decahydronaphthalene ring, adamantane ring, naphthalene ring, phenanthrene ring, anthracene ring, pyrene ring, triphenylene ring, tetralin ring, 1,2,3,4,5,6,7,8- Examples include an octahydronaphthalene ring and a norbornene ring.
  • the hydrogen atom bonded to the carbon atom constituting the hydrocarbon ring constituting the X ring and not bound to the silicon atom has 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6) an alkyl group, an alkoxy group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), or a halogen atom.
  • alkyl group having 1 to 6 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
  • Preferred examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group and isobutoxy group.
  • the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a fluorine atom, a chlorine atom, or a bromine atom, and more preferably a fluorine atom or a bromine atom.
  • the ring having a structure in which two saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are linked may be represented by the following formula (5).
  • the structure represented by these is preferable.
  • the Xa ring and the Xb ring are the same or different and represent a saturated hydrocarbon ring or an unsaturated hydrocarbon ring. That is, both the Xa ring and the Xb ring are saturated hydrocarbon rings, or both are unsaturated hydrocarbon rings, or one is a saturated hydrocarbon ring and the other is an unsaturated hydrocarbon ring. Among these, it is preferable that both the Xa ring and the Xb ring are saturated hydrocarbon rings or both are unsaturated hydrocarbon rings.
  • the Xa ring and the Xb ring are preferably both benzene rings, both cyclohexane rings, or one is a benzene ring and the other is a cyclohexane ring, and more preferably both are benzene rings.
  • Y represents a bond, an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—). ), -SO-, or -SO 2- .
  • alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, and an n-hexylene group.
  • alkyl group having 1 to 4 carbon atoms as a substituent examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
  • Preferred examples of the alkylene group having 1 to 6 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms include —CH (CH 3 ) —, —C (CH 3 ) 2 —, —CH 2 CH (CH 3 ) CH. Examples thereof include 2- , -CH 2 C (CH 3 ) 2 CH 2- and the like.
  • Y is preferably a bond, an oxygen atom, a methylene group, a dimethylmethylene group (—C (CH 3 ) 2 —), —S—, —SO 2 —, and more preferably a bond, a dimethylmethylene group, An oxygen atom, —SO 2 —.
  • the divalent, trivalent, or tetravalent group that is, X 2 , X 3 , or X 4
  • X 2 , X 3 , or X 4 is specifically represented by, for example, any one of the following formulae:
  • Y is as defined above
  • a group represented by any of the following formulas is more preferable.
  • the alkyl group having 1 to 18 carbon atoms represented by R 1 is a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Isobutyl, tert-butyl, n-pentyl, neopentyl, tert-pentyl, n-hexyl, n-heptyl, 2,2,4-trimethylpentyl, n-octyl, isooctyl, n -Nonyl group, n-decyl group, n-dodecyl group and the like.
  • An alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is further preferable, and a methyl group is particularly preferable.
  • Examples of the cycloalkyl group represented by R 1 include a 3- to 8-membered cycloalkyl group, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group.
  • Examples of the aryl group represented by R 1 include a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group. Of these, a phenyl group is preferred.
  • Examples of the aralkyl group represented by R 1 include an alkyl group having 1 to 4 carbon atoms substituted with an aryl group (particularly a phenyl group).
  • an aryl group particularly a phenyl group.
  • a benzyl group, an ⁇ -phenethyl group, a ⁇ -phenethyl group, a ⁇ -Methylphenethyl group and the like can be mentioned.
  • C 1-18 alkyl group, cycloalkyl group, aryl group or aralkyl group represented by R 1 are selected from the group consisting of oxygen atoms and nitrogen atoms, as described above. It may be substituted with at least one atom. When some carbon atoms are substituted, the number of carbon atoms to be substituted is, for example, 1 to 3, 1 or 2, or 1. The carbon atom may be substituted with an oxygen atom or a nitrogen atom, and is preferably substituted with an oxygen atom. When the number of carbon atoms to be substituted is 2 or more, all may be substituted with the same atom (oxygen atom or nitrogen atom), or a part may be substituted with a different atom.
  • R 1 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
  • an organic compound in which the total number of hydrogen atoms directly bonded to silicon atoms existing in the molecule such as dimethylphenylsilane and triphenylsilane is one; methylphenylsilane, diphenylsilane, Total number of hydrogen atoms directly bonded to silicon atoms present in the molecule such as 1,2-bis (dimethylsilyl) benzene, 1,4-bis (dimethylsilyl) benzene, bis [(p-dimethylsilyl) phenyl] ether
  • An organic compound in which the total number of hydrogen atoms directly bonded to silicon atoms present in the molecule such as normal butyl silane and cyclopentyl silane is three.
  • component A examples include bis (trimethylsiloxy) methylsilane, bis (trimethylsiloxy) ethylsilane, 3H, 5H-octamethyltetrasiloxane, 1H, 7H-octamethyltetrasiloxane, chloroethylsilane, 1, 3-diphenyltetrakis (dimethylsiloxy) disilane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetraethylcyclotetrasiloxane, pentamethylcyclopentasiloxane, organically modified silicone having hydrosilyl group Etc. are exemplified. Only 1 type may be sufficient as A component used for epoxy resin preparation, and 2 or more types may be sufficient as it. In other words, the A component structural unit contained in the epoxy resin may be only one type or two or more types.
  • the component A has a total of two or more hydrogen atoms directly bonded to silicon atoms present in the molecule from the viewpoint that the cured product of the resulting epoxy resin composition tends to have excellent low dielectric properties.
  • An organic compound is preferable, and an organic compound having two or more hydrosilyl groups in one molecule is particularly preferable.
  • a compound represented by the above formula (2) and the total number of hydrogen atoms is 2, a compound represented by the above formula (3) and the total number of hydrogen atoms is 3, and the above formula (4)
  • a compound in which the total number of hydrogen atoms is four, and a compound represented by the above formula (2) and having a total number of hydrogen atoms of two is preferable.
  • the component A may be an organic compound in which the total number of hydrogen atoms directly bonded to silicon atoms present in the molecule is one. In this case, it is easy to adjust the viscosity of the epoxy resin composition.
  • the component A contains an organic compound in which the total number of hydrogen atoms directly bonded to silicon atoms present in the molecule is 1, the content is low dielectric properties with a cured product of the resulting epoxy resin composition being excellent From the viewpoint of easily having the content, it is preferably 30% by mass or less based on the total mass of the component A. That is, when an organic compound in which the total number of hydrogen atoms directly bonded to silicon atoms present in the molecule is 1 as the component A, the total number of hydrogen atoms directly bonded to silicon atoms present in the molecule is one.
  • the total number of hydrogen atoms directly bonded to silicon atoms present in the molecule is 1 in the total amount of component A
  • the amount is preferably 20 mol% or less.
  • the component B is a compound having a carbon-carbon unsaturated bond and having no epoxy group.
  • the carbon-carbon unsaturated bond can react with the hydrosilyl group of the component A (hydrosilylation reaction).
  • the B component undergoes a hydrosilylation reaction with the A component, and the carbon-carbon unsaturated bond is converted into a C—C bond or a C ⁇ C bond to become a B component constituent unit.
  • the carbon-carbon unsaturated bond is a C ⁇ C bond, it can be converted to a C—C bond or a C ⁇ C bond.
  • the carbon-carbon unsaturated bond is a C ⁇ C bond, a C—C bond is obtained.
  • the carbon-carbon unsaturated bond examples include a carbon-carbon unsaturated double bond (C ⁇ C bond) and a carbon-carbon unsaturated triple bond (C ⁇ C bond).
  • the carbon-carbon unsaturated bond is a carbon-carbon unsaturated double bond from the viewpoint that the cured product of the resulting epoxy resin composition has excellent low dielectric properties and is easily available.
  • the component B preferably has a group: —CH ⁇ CH 2 , —CH ⁇ CH (CH 3 ), —C ⁇ CH, or —C ⁇ C—CH 3 .
  • R 2 represents an alkylene group having 1 to 8 carbon atoms, and this group may have a part of carbon atoms substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom.
  • R 3 represents * —COO— or * —OCO— (wherein “*” represents the side bonded to R 2 or L.)
  • R 4 represents an alkylene group having 1 to 4 carbon atoms, In this group, a part of carbon atoms may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom
  • R 5 represents a methyl group or a hydrogen atom
  • L represents a k valence. Each independently represents 0 or 1.
  • n represents each independently 0 or 1.
  • k represents an integer of 1 to 6.
  • R 2 is the plurality of may be each the same group, Oh There are, .R 3 which may be a part or all different groups when there are a plurality, it is possible to make each the same group, or may be different based on part or all.
  • R 4 when a plurality of R 4 are present, each may be the same group, or some or all may be different groups.
  • Examples of the alkylene group having 1 to 8 carbon atoms (1, 2, 3, 4, 5, 6, 7, or 8) represented by R 2 include a methylene group, an ethylene group, an n-propylene group, and n-butylene. Groups and the like.
  • Examples of the alkylene group having 1 to 4 (1, 2, 3, or 4) carbon atoms represented by R 4 include a methylene group, an ethylene group, an n-propylene group, and an n-butylene group.
  • Examples of the k-valent organic group represented by L include linear or branched alkanes, saturated hydrocarbon rings, unsaturated hydrocarbon rings, nitrogen-containing groups in which some carbon atoms may be substituted with oxygen atoms. Heterocycle, ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed, or ring having a structure in which two saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are connected And groups obtained by removing k hydrogen atoms from each.
  • the valence k of the organic group L is preferably 2 to 6 (2, 3, 4, 5, or 6), more preferably 2 to 3.
  • L represents 0 or 1 independently. When k is 2 or more, l is also 2 or more, but all l can have the same value or different values. Preferably all l take the same value.
  • Each m independently represents 0 or 1. When k is 2 or more, m is also 2 or more, but all m can take the same value or different values. Preferably, all m have the same value.
  • n independently represents 0 or 1. When k is 2 or more, n is also 2 or more, but all n can take the same value or different values. Preferably all l take the same value.
  • the hydrogen atom bonded to the alkane constituting the organic group L or the carbon atom constituting the ring is a linear or branched alkyl group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6). May be substituted with a linear or branched alkoxy group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), a hydroxyl group, or a halogen atom.
  • the number of hydrogen atoms that may be substituted may be, for example, 1 to 3, 1 or 2, or 1. In the case where the number of hydrogen atoms to be substituted is 2 or more, two hydrogen atoms bonded to the same carbon atom may be substituted, but one hydrogen atom to be substituted is one per carbon atom. It is preferable that
  • the linear or branched alkane constituting the organic group L is preferably a linear or branched alkane having 1 to 30 carbon atoms.
  • the carbon number is more preferably 2 to 20, and further preferably 3 to 10.
  • alkane butane, 2,2-dimethylpropane, 2,2-dimethylbutane and the like are particularly preferable.
  • saturated hydrocarbon ring constituting the organic group L for example, a saturated hydrocarbon ring having 4 to 8 carbon atoms (4, 5, 6, 7, or 8) is preferable, and more specifically, a cyclopentane ring or cyclohexane. Rings and the like are particularly preferred.
  • unsaturated hydrocarbon ring which comprises the said organic group L an aromatic hydrocarbon ring and a non-aromatic unsaturated hydrocarbon ring are mentioned.
  • aromatic hydrocarbon ring for example, a benzene ring is preferable.
  • non-aromatic unsaturated hydrocarbon ring for example, an unsaturated hydrocarbon ring having 4 to 8 carbon atoms (4, 5, 6, 7, or 8) is preferable, and more specifically, a cyclohexene ring or the like is particularly preferable. preferable.
  • Preferred examples of the nitrogen-containing heterocycle constituting the organic group L include a triazine ring and a carbazole ring.
  • Preferred examples of the triazine ring include 1,2,3-triazine, 1,2,4-triazine, and 1,3,5-triazine, and among these, 1,3,5-triazine is more preferable.
  • the ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings constituting the organic group L are condensed includes 2 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings, Three or four condensed rings are preferred, and two or three condensed rings are more preferred.
  • decahydronaphthalene ring More specifically, for example, decahydronaphthalene ring, adamantane ring, naphthalene ring, phenanthrene ring, anthracene ring, pyrene ring, triphenylene ring, tricyclodecane ring, tetralin ring, 1,2,3,4,5,6 , 7,8-octahydronaphthalene ring, norbornene ring and the like.
  • the ring having a structure in which two saturated hydrocarbon rings and / or unsaturated hydrocarbon rings constituting the organic group L are connected is preferably a ring represented by the following formula (9).
  • L a ring and L b rings are the same or different and are each a saturated hydrocarbon ring or an unsaturated hydrocarbon ring. That is, the L a ring and the L b ring are both saturated hydrocarbon rings, or both are unsaturated hydrocarbon rings, or one is a saturated hydrocarbon ring and the other is an unsaturated hydrocarbon ring. Among these, it is preferable that both the La ring and the L b ring are saturated hydrocarbon rings, or both are unsaturated hydrocarbon rings.
  • L a ring and L b rings are both benzene rings, it is preferred that both cyclohexane rings, or one of which is the other is a cyclohexane ring, benzene ring, and more preferably both are a benzene ring.
  • Q is a bond, an alkylene group having 1 to 6 carbon atoms that may be substituted with an alkyl group having 1 to 4 carbon atoms, an oxygen atom (—O—), a sulfur atom (— S—), —SO—, or —SO 2 —.
  • alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, and an n-hexylene group.
  • alkyl group having 1 to 4 carbon atoms as a substituent examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
  • Preferred examples of the alkylene group having 1 to 6 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms include —CH (CH 3 ) —, —C (CH 3 ) 2 —, —CH 2 CH (CH 3 ) CH. Examples thereof include 2- , -CH 2 C (CH 3 ) 2 CH 2- and the like.
  • Q is preferably a bond, an oxygen atom, a methylene group, a dimethylmethylene group (—C (CH 3 ) 2 —), —S—, —SO 2 —, more preferably a bond, a dimethylmethylene group, An oxygen atom, —SO 2 —.
  • B component for example, one carbon in one molecule such as vinylbenzene, vinylnaphthalene (1-vinylnaphthalene, 2-vinylnaphthalene), vinylcyclohexane, vinyl stearate, allylbenzene, allylmethyl carbonate, allylphenyl ether, etc.
  • An organic compound having a carbon unsaturated double bond divinylbenzene (o-, m-, or p-divinylbenzene), divinyl adipate, diallyl phthalate, 5-vinyl-2-norbornene, vinylcyclohexene (preferably 4 -Vinyl-1-cyclohexene), polyethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, organic compounds having two carbon-carbon unsaturated double bonds in one molecule, such as 2,2'-diallylbisphenol A; Isocyanuric acid tri Organic compounds having three or more carbon-carbon unsaturated double bonds in one molecule, such as ril, triallyl 1,3,5-benzenetricarboxylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc.
  • component B examples include allylmethoxymethylsilane, 1,4-bis (dimethylvinylsilyl) benzene, divinylmethylphenylsilane, diallyldiphenylsilane, dicyclopentadiene, ethylidene norbornene, and 9,9-bis.
  • examples include [4- (2-acryloyloxyethoxy) phenyl] fluorene, trimethylolpropane diallyl ether, divinyl sulfone, organically modified silicone having a carbon-carbon unsaturated double bond, polyethylene glycol diacrylate, and the like. Only 1 type may be sufficient as B component used for epoxy resin preparation, and 2 or more types may be sufficient as it. In other words, the B component structural unit contained in the epoxy resin may be only one type or two or more types.
  • the component B is an organic compound having two or more carbon-carbon unsaturated double bonds in the molecule from the viewpoint that the cured product of the resulting epoxy resin composition tends to have excellent low dielectric properties.
  • An organic compound having 2 or 3 carbon-carbon unsaturated double bonds in the molecule is more preferable.
  • a compound in which k is 2 or 3 in the above formula (8) is preferable.
  • the component B includes divinylbenzene represented by the following formula (10), divinyl adipate represented by the following formula (11), diallyl phthalate represented by the following formula (12), and represented by the following formula (13).
  • divinyl-2-norbornene and triallyl isocyanurate represented by the following formula (14) are preferred.
  • the component B is also preferably an organic compound having one carbon-carbon unsaturated double bond in the molecule. In this case, it is easy to adjust the viscosity of the epoxy resin composition.
  • the B component may contain an organic compound having one carbon-carbon unsaturated double bond in the molecule.
  • content of the said organic compound shall be 30 mass% or less with respect to the total mass of B component from a viewpoint that a hardened
  • the component B includes an organic compound having one carbon-carbon unsaturated double bond in the molecule, the organic compound having two or more carbon-carbon unsaturated double bonds in the molecule (for example, the above formula (8 ) And a compound in which k represents an integer of 2 to 6).
  • the amount of the organic compound having one carbon-carbon unsaturated double bond in the molecule is preferably 20 mol% or less.
  • the compound having a carbon-carbon unsaturated bond and an epoxy group as the component C may be any organic compound having a carbon-carbon unsaturated bond and an epoxy group and hydrosilylating with a hydrosilyl (Si—H) group.
  • the C component becomes a structural unit formed by a hydrosilylation reaction with the hydrosilyl (Si—H) group of the A component, and the carbon-carbon unsaturated bond is converted into a C ⁇ C bond or a C—C bond.
  • the carbon-carbon saturated bond is a C ⁇ C bond
  • it is a structural unit formed by conversion to a C—C bond or C ⁇ C bond.
  • the carbon-carbon unsaturated bond is a C ⁇ C bond
  • the carbon-carbon unsaturated bond examples include a carbon-carbon unsaturated double bond and a carbon-carbon unsaturated triple bond.
  • the carbon-carbon unsaturated bond is preferably a carbon-carbon unsaturated double bond from the viewpoint that the cured product easily has excellent low dielectric properties and the raw material is easily available.
  • Examples of the compound having a carbon-carbon unsaturated bond (double bond) and an epoxy group, which are component C, include compounds represented by the following formula (15).
  • R 6A is an alkenyl group or alkynyl group having 2 to 18 carbon atoms, and this group is at least one selected from the group consisting of an oxygen atom and a nitrogen atom.
  • R 7 represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and these groups are partially
  • the carbon atom may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom, o represents an integer of 0 to 6, and p represents an integer of 0 to 3.
  • 2 to 18 carbon atoms represented by R 6A 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or
  • the alkenyl group of 18 is a linear or branched alkenyl group, and is preferably linear. Specific examples include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a norbornenyl group, and a cyclohexenyl group.
  • alkenyl group having 2 to 10 carbon atoms is preferred, an alkenyl group having 2 to 8 carbon atoms is more preferred, an alkenyl group having 2 to 6 carbon atoms is more preferred, and a vinyl group, allyl group or It is a butenyl group.
  • the alkenyl group is preferably an ⁇ -alkenyl group (that is, an alkenyl group in which the terminal carbon atom and the adjacent carbon atom form a double bond).
  • 2 to 18 carbon atoms represented by R 6A (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or
  • the alkynyl group of 18 is a linear or branched alkynyl group, and is preferably linear.
  • an ethynyl group, a propargyl group, etc. are mentioned, for example.
  • An alkynyl group having 2 to 10 carbon atoms is preferable, an alkynyl group having 2 to 8 carbon atoms is more preferable, an alkynyl group having 2 to 6 carbon atoms is more preferable, and an ethynyl group, a propargyl group, and the like are particularly preferable.
  • the alkynyl group is preferably an ⁇ -alkynyl group (that is, an alkynyl group in which the terminal carbon atom and the adjacent carbon atom form a triple bond).
  • some carbon atoms may be substituted with at least one atom (preferably an oxygen atom) selected from the group consisting of an oxygen atom and a nitrogen atom.
  • the some carbon atoms are preferably carbon atoms not directly bonded to the epoxy ring.
  • the part of carbon atoms that may be substituted may be 1 or a plurality of (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom.
  • an alkenyl group having 2 to 18 carbon atoms in which some carbon atoms are substituted with at least one atom (preferably an oxygen atom) selected from the group consisting of an oxygen atom and a nitrogen atom.
  • the group may include, for example, 2 to 9 alkenyl-O-carbon having 1 to 8 alkylene, preferably 2 to 4 alkenyl-O, 1 to 3 alkylene, more preferably carbon.
  • Examples thereof include 2 to 4 alkenyl-O-alkylene having 1 to 2 carbon atoms, particularly preferably 3 alkenyl-O—CH 2 —.
  • it is an alkynyl group having 2 to 18 carbon atoms, and some of the carbon atoms may be substituted with at least one atom (preferably an oxygen atom) selected from the group consisting of an oxygen atom and a nitrogen atom.
  • Examples of the group include, for example, 2 to 9 alkynyl-O-carbon having 1 to 8 alkylene, preferably 2 to 4 alkynyl-O, 1 to 3 alkylene, more preferably 2 to 4 carbon.
  • Alkynyl-O—C 1-2 alkylene, particularly preferably alkynyl O—CH 2 — is used. More specifically, for example, CH ⁇ C—O—CH 2 —, CH ⁇ C—CH 2 —O—CH 2 —, CH ⁇ C—CH 2 —O— (CH 2 ) 2 —, CH ⁇ C — (CH 2 ) 3 —O— (CH 2 ) 4 — and the like can be mentioned, and among these, CH ⁇ C—CH 2 —O—CH 2 — is preferable.
  • R 7 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
  • Part of the carbon atoms may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom.
  • the partial carbon atom is preferably a carbon atom that is not directly bonded to a 3- to 8-membered ring or an epoxy ring.
  • the part of carbon atoms which may be substituted may be 1 or a plurality of (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom.
  • Alkyl group R 7 having 1 to 18 carbon atoms represented by, a cycloalkyl group, each aryl group and aralkyl group, the same as the corresponding groups represented by R 1 can be mentioned.
  • the alkenyl group having 2 to 9 carbon atoms represented by R 7 is a linear or branched alkenyl group such as a vinyl group, an allyl group, a 2-propenyl group, a butenyl group, a pentenyl group, a hexenyl group, A heptenyl group, an octenyl group, a nonenyl group, etc. are mentioned.
  • An alkenyl group having 2 to 4 carbon atoms is preferred.
  • R 7 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.
  • Preferred o is 0 to 4 (0, 1, 2, 3, or 4), more preferably 0 or 4.
  • Preferred p is 0 or 1, more preferably 0.
  • the compound represented by the formula (15) is a compound represented by the following formula (15 ′).
  • the component C includes a compound in which o is 0 (that is, a compound represented by the formula (15 ′))
  • the component B is an organic group according to the formula (8) from the viewpoint that the reaction proceeds easily.
  • L is a linear or branched alkane, aromatic hydrocarbon ring, non-aromatic unsaturated hydrocarbon ring, nitrogen-containing heterocycle, saturated carbonization, in which some carbon atoms may be substituted with oxygen atoms
  • It is preferably composed of a ring in which 2 to 6 hydrogen rings and / or unsaturated hydrocarbon rings are condensed, or a ring in which two saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are connected. More preferably, it is composed of a hydrogen ring, a non-aromatic unsaturated hydrocarbon ring, a nitrogen-containing heterocycle, or a ring in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed.
  • the component B is an organic group L according to the formula (8) in which some carbon atoms are oxygen atoms. It is composed of a linear or branched alkane, an aromatic hydrocarbon ring, a nitrogen-containing heterocycle, or a ring in which two saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are connected. It is preferable that it is composed of an aromatic hydrocarbon ring or a nitrogen-containing heterocyclic ring.
  • component C examples include, for example, 1,3-butadiene monoepoxide represented by the following formula (16), 1,2-epoxy-5-hexene represented by the following formula (17), and represented by the following formula (18).
  • component C examples include glycidyl methacrylate, 1-allyl-3,5-diglycidyl isocyanurate, 4-hydroxybutyl acrylate glycidyl ether, and the like.
  • C component may be only 1 type and may contain 2 or more types.
  • the epoxy resin (hydrosilylated epoxy resin) of the present invention can be obtained, for example, by subjecting the A component, the B component and the C component to a hydrosilylation reaction. More precisely, the hydrosilylated epoxy resin has a structure derived from each of the A component, the B component, and the C component as a skeleton (that is, has an A component constitutional unit, a B component constitutional unit, and a C component constitutional unit). It is an epoxy resin.
  • the component A constituent unit and the component B constituent unit are alternately bonded one or more times (for example, 1 to 20 times on average), and each terminal portion of the alternate bond has a component C constituent unit.
  • Is an epoxy resin having a structure in which More specifically, for example, the component A is a divalent compound (for example, a compound represented by the formula (2)), and the component B is a divalent compound (for example, a compound in which k 2 in the formula (8)).
  • the component C is a compound represented by the formula (15)
  • the epoxy resin represented by the formula (23) can be produced by the following reaction formula.
  • R 6 represents an alkylene group having 2 to 18 carbon atoms or an alkenylene group having 2 to 18 carbon atoms, in which some carbon atoms except for a carbon atom directly bonded to a silicon atom are oxygen atoms
  • L 2 may be substituted with at least one atom selected from the group consisting of an atom and a nitrogen atom, L 2 is a linear or branched alkane in which some carbon atoms may be substituted with oxygen atoms
  • a divalent group obtained by removing two hydrogen atoms from a ring, q is an average value and represents a positive number greater than 0 and not greater than 20.
  • R 6 represents an alkylene group having 2 to 18 carbon atoms or an alkenylene group having 2 to 18 carbon atoms.
  • the alkylene group is a linear or branched alkylene group, preferably a linear alkylene group.
  • dimethylene —CH 2 CH 2 —
  • trimethylene —CH 2 CH 2 CH 2 —
  • tetramethylene penta
  • Examples include a methylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, and a tridecamethylene group.
  • An alkylene group having 2 to 10 carbon atoms is preferable, an alkylene group having 2 to 8 carbon atoms is more preferable, an alkylene group having 2 to 6 carbon atoms is further preferable, and an alkylene group having 2 to 5 carbon atoms is particularly preferable.
  • the alkenylene group is a linear or branched alkenylene group, preferably a linear alkenylene group.
  • alkenylene group having 2 to 10 carbon atoms is preferred, more preferred is an alkenylene group having 2 to 8 carbon atoms, still more preferred is an alkenylene group having 2 to 6 carbon atoms, and particularly preferred is an alkenylene group having 2 to 5 carbon atoms. Alkenylene group.
  • the alkylene group having 2 to 18 carbon atoms or the alkenylene group having 2 to 18 carbon atoms as R 6 has at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. It may be preferably substituted with an oxygen atom).
  • the partial carbon atom is preferably a carbon atom that is not directly bonded to any of a silicon atom and a 3- to 8-membered ring or an epoxy ring.
  • the part of carbon atoms which may be substituted may be 1 or a plurality of (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom.
  • the group includes, for example, (*)-alkylene having 2 to 9 carbon atoms-O-carbon having 1 to 8 carbon atoms when (*) is the side bonded to the silicon atom of R 6 .
  • Alkylene- preferably (*)-alkylene having 2 to 4 carbon atoms-O-alkylene having 1 to 3 carbon atoms, more preferably (*)-alkylene having 2 to 4 carbon atoms-O-1-2 carbon atoms.
  • (*)-alkenylene having 2 to 9 carbon atoms-O-alkylene having 1 to 8 carbon atoms preferably (*)-alkenylene having 2 to 4 carbon atoms-O-alkylene having 1 to 3 carbon atoms- More preferable is (*)-alkenylene having 2 to 4 carbon atoms-O-alkylene having 1 to 2 carbon atoms, and particularly preferably (*)-alkenylene having 3 carbon atoms-O-methylene-.
  • the amount of component A, component B and component C used is, for example, a carbon-carbon unsaturated bond (however, an aromatic ring per component B) per mole of hydrosilyl (Si—H) group in component A. (Excluding the carbon-carbon unsaturated bond) can be 0.05 to 0.95 mol, preferably 0.1 to 0.9 mol, more preferably 0.2 to 0.8 mol.
  • the component C contains 0.05 to 0.001 carbon-carbon unsaturated bond (excluding carbon-carbon unsaturated bonds in the aromatic ring) per mole of hydrosilyl (Si—H) group in the component A.
  • the amount can be 95 mol, preferably 0.1 to 0.9 mol, more preferably 0.2 to 0.8 mol.
  • the number of hydrogen atoms bonded to a silicon atom is counted as the number of hydrosilyl (Si—H) groups.
  • the number of hydrosilyl (Si—H) groups is counted as two.
  • q represents a positive number greater than 0 and 20 or less as an average value, as described above, preferably a positive number of 0.1 to 15 as an average value, and more preferably a positive number as an average value of 0.2 to 10. Show.
  • the hydrosilylation reaction can be carried out by a known method.
  • the hydrosilylation reaction can be carried out in the presence of a catalyst, in the presence or absence of a solvent.
  • the A component, the B component, and the C component may be reacted simultaneously. Further, after reacting the A component and the B component, the reactant and the C component may be reacted. After reacting the A component and the C component, the reactant and the B component are reacted. May be. From the viewpoint of easy manufacturing and easy reaction control, it is preferable to react the A component and the B component and then react the reaction product with the C component.
  • Catalysts include platinum carbon, chloroplatinic acid, platinum olefin complexes, platinum alkenylsiloxane complexes, platinum carbonyl complexes and other platinum catalysts; tris (triphenylphosphine) rhodium and other rhodium catalysts; bis (cycloocta Examples thereof include iridium catalysts such as (dienyl) dichloroiridium.
  • the catalyst may be in the form of a solvate (eg, hydrate, alcohol solvate, etc.), or in the form of a solution dissolved in an alcohol such as ethanol.
  • the amount of catalyst used may be an effective amount as a catalyst, that is, an amount capable of exhibiting the function of the catalyst.
  • the catalyst is used in an amount of 0.00001 to 20 parts by weight, preferably 0.0005 to 5 parts by weight, per 100 parts by weight of component A.
  • the hydrosilylation reaction does not need to use a solvent, but by using a solvent, the hydrosilylation reaction can be performed under milder conditions.
  • the solvent include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane and octane; ether solvents such as tetrahydrofuran and dioxane; alcohol solvents such as ethanol and isopropanol. . These solvents may be used alone or in combination of two or more.
  • the temperature of the hydrosilylation reaction is, for example, 0 ° C. to 150 ° C., preferably 10 ° C. to 120 ° C.
  • the reaction time of the hydrosilylation reaction is, for example, 5 minutes to 24 hours.
  • the A component reacts with the B component and the C component to produce a hydrosilylated epoxy resin.
  • the weight average molecular weight of the hydrosilylated epoxy resin is preferably from 500 to 100,000, more preferably from 1,000 to 50,000, and even more preferably from 1,000 to 30,000.
  • the weight average molecular weight of the hydrosilylated epoxy resin is 500 or more, a low dielectric property more excellent when it is made into a cured product is easily exhibited.
  • the weight average molecular weight of the hydrosilylated epoxy resin is 500 or more, it is possible to suppress deterioration of solder heat resistance (heat resistant blistering property) due to the low molecular weight epoxy resin.
  • a weight average molecular weight of the hydrosilylated epoxy resin is 100,000 or less, the solubility of the hydrosilylated epoxy resin in a solvent and the low dielectric properties when cured are hardly impaired.
  • a weight average molecular weight here says the weight average molecular weight measured in polystyrene conversion by GPC measurement.
  • Epoxy resin composition An epoxy resin composition containing these can be prepared in combination with the hydrosilylated epoxy resin of the present invention and other components.
  • examples of other components include epoxy resins other than hydrosilylated epoxy resins, curing catalysts, curing agents, additives, and the like.
  • the present invention also includes the epoxy resin composition.
  • the epoxy resin composition may include the hydrosilylated epoxy resin of the present invention and an epoxy resin other than the hydrosilylated epoxy resin.
  • the hydrosilylated epoxy resin may be referred to as “first epoxy resin”
  • the epoxy resin other than the hydrosilylated epoxy resin may be referred to as “second epoxy resin”.
  • Examples of the second epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, triglycidyl isocyanurate, Examples thereof include hydrogenated bisphenol A type epoxy resins, aliphatic epoxy resins, glycidyl ether type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, dicyclo type epoxy resins, and naphthalene type epoxy resins.
  • the second epoxy resin may be only one type, or two or more types may be combined.
  • the blending ratio of both is, for example, the first epoxy resin and the second epoxy as long as the effects of the present invention are not impaired.
  • the content ratio of the second epoxy resin can be 99% by mass or less with respect to the total mass of the resin.
  • the content ratio of the second epoxy resin is preferably 80 to 1% by mass, more preferably 50 to 1% by mass, and further preferably 30 to 1% by mass.
  • the epoxy resin composition may contain the epoxy resin of the present invention and a curing catalyst and / or a curing agent as other components.
  • the curing reaction rate for obtaining a cured product of the epoxy resin composition can be increased, and the strength of the resulting cured product can be increased.
  • the curing catalyst examples include imidazole compounds, phosphorus compounds, and cationic curing catalysts from the viewpoint of improving the electrical characteristics of the cured product of the epoxy resin composition.
  • Specific examples of the curing catalyst include imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole; dicyandiamide and derivatives thereof; 1,8-diazabicyclo (5 , 4,0) -undecene-7,1,5-diazabicyclo (4,3,0) -nonene-5, 2,4,6-tris (dimethylaminomethyl) phenol, tertiary amines such as dimethylaminopyridine
  • Phosphorus compounds such as triphenylphosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetra-p-tolylborate, t
  • the amount of the curing catalyst is, for example, 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total epoxy resin. More preferably, it is 5 to 3 parts by mass.
  • the total epoxy resin refers to the first epoxy resin and the second epoxy resin, and the same applies to the following.
  • the curing agent is preferably one that can react with an epoxy resin to obtain a cured product of the epoxy resin composition.
  • an amine curing agent an amide curing agent, an acid anhydride curing agent, a phenol curing agent, an active ester curing agent, a cyanate ester curing agent, a mercaptan curing agent, an isocyanate curing agent, etc.
  • a curing agent an amine curing agent, an amide curing agent, an acid anhydride curing agent, a phenol curing agent, an active ester curing agent, a cyanate ester curing agent, a mercaptan curing agent, an isocyanate curing agent, etc. Can be mentioned.
  • amine curing agents include chain aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; isophoronediamine, mensendiamine, bis (4-aminocyclohexyl) methane, and bis (aminomethyl).
  • Alicyclic amines such as cyclohexane and diaminodicyclohexylmethane; aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diethyltoluenediamine and diaminodiethyldiphenylmethane; benzyldimethylamine, triethylenediamine, piperidine, 2- (dimethylaminomethyl) phenol Secondary and tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene-7, etc. It is below.
  • amide-based curing agent examples include dicyandiamide and derivatives thereof, polyamide resin (polyaminoamide and the like), and the like.
  • the acid anhydride-based curing agent examples include aliphatic acid anhydrides such as maleic anhydride and dodecenyl succinic anhydride; aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride; methyl anhydride Examples thereof include alicyclic acid anhydrides such as nadic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride.
  • phenolic curing agent examples include phenol novolak resin, cresol novolak resin, biphenyl type novolak resin, triphenylmethane type phenol resin, naphthol novolak resin, phenol biphenylene resin, phenol aralkyl resin, biphenyl aralkyl type phenol resin, modified polyphenylene ether.
  • phenol novolak resin cresol novolak resin
  • biphenyl type novolak resin triphenylmethane type phenol resin
  • naphthol novolak resin phenol biphenylene resin
  • phenol aralkyl resin phenol aralkyl resin
  • biphenyl aralkyl type phenol resin modified polyphenylene ether.
  • modified polyphenylene ether examples include resins and compounds having a benzoxazine ring.
  • the active ester curing agent is, for example, a compound having at least one ester group that reacts with an epoxy resin in one molecule, and specifically includes phenol ester, thiophenol ester, N-hydroxyamine ester, and heterocyclic ring. Examples include hydroxy compound esters.
  • cyanate ester-based curing agent examples include novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, and bisphenol type cyanate resin such as tetramethylbisphenol F type cyanate resin.
  • Examples of mercaptan curing agents include trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate). , Tetraethylene glycol bis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate) ), Trimethylolethane tris (3-mercaptobutyrate), polysulfide polymer and the like.
  • isocyanate curing agent examples include hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, lysine diisocyanate, isophorone diisocyanate, and norbornane diisocyanate.
  • the curing agent may be used alone or in combination of two or more.
  • the curing agent it is preferable to include any one or more of an acid anhydride curing agent, a phenol curing agent, an active ester curing agent and an amine curing agent. Is easy to improve.
  • the amount of the curing agent contained in the epoxy resin composition of the present invention is, for example, from 0.1 to 5 reactive functional groups in the curing agent with respect to 1 equivalent of epoxy group in the epoxy resin composition of the present invention. Equivalent to 0.3 to 3 equivalents, more preferably 0.5 to 2 equivalents.
  • the epoxy resin composition of the present invention may contain other additives.
  • the additive include a thermoplastic resin and a filler.
  • thermoplastic resin examples include polyolefin resins, acrylic resins, phenoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyurethane resins, polyarylate resins, polyphenylene ether resins, polyacetal resins, and resins in which these are acid-modified. It is done. From the viewpoint of compatibility with the epoxy resin composition according to the present invention and heat resistance, polyolefin resins, acrylic resins, phenoxy resins, polyarylate resins, polyphenylene ether resins, and resins in which these are acid-modified are preferred.
  • Examples of the filler include silica (more specifically, crystalline silica, fused silica, spherical fused silica, etc.), titanium oxide, zirconium oxide, zinc oxide, tin oxide, silicon nitride, silicon carbide, boron nitride, calcium carbonate, Examples include inorganic compounds such as calcium silicate, potassium titanate, aluminum nitride, indium oxide, alumina, antimony oxide, cerium oxide, magnesium oxide, iron oxide, and tin-doped indium oxide (ITO). Moreover, metals, such as gold
  • filler examples include minerals such as montmorillonite, talc, mica, boehmite, kaolin, smectite, zonolite, verculite, and sericite.
  • Other fillers include carbon compounds such as carbon black, acetylene black, ketjen black and carbon nanotubes; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; various glasses such as glass beads, glass flakes and glass balloons Can be mentioned.
  • the filler may be a powder or may be dispersed in a resin.
  • the filler is singly or plural in consideration of the properties such as fluidity, heat resistance, low thermal expansion, mechanical properties, hardness, scratch resistance and adhesion required for the epoxy resin composition or its cured product.
  • a combination of species can be used.
  • additives include, for example, antioxidants, inorganic phosphors, lubricants, ultraviolet absorbers, heat-light stabilizers, antistatic agents, polymerization inhibitors, antifoaming agents, solvents, anti-aging agents, radical inhibitors, adhesives Property improver, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocker, nucleating agent, coupling agent, conductivity imparting agent, phosphorus peroxide Decomposition agents, pigments, metal deactivators, physical property modifiers, and the like may be included in the epoxy resin composition.
  • the epoxy resin composition of the present invention can be produced, for example, by a method including a step of mixing a hydrosilylated epoxy resin (first epoxy resin) with a curing catalyst and / or a curing agent.
  • a hydrosilylated epoxy resin first epoxy resin
  • other additives such as a second epoxy resin and a filler can be blended as necessary.
  • the hydrosilylated epoxy resin and the curing catalyst and / or curing agent can be mixed while warming.
  • the method of mixing the hydrosilylated epoxy resin with the curing catalyst and / or the curing agent can be performed using, for example, a commercially available mixer.
  • a cured product can be obtained by curing the epoxy resin composition of the present invention.
  • a cured product of the epoxy resin composition can be obtained by heating the epoxy resin composition.
  • the curing temperature is, for example, room temperature (for example, 20 ° C.) to 250 ° C.
  • the curing time can be appropriately adjusted according to the components, concentration and blending ratio of the epoxy resin composition, and can be set, for example, from 10 minutes to 1 week.
  • the cured product may be obtained by dividing the heating into several stages, such as heating at a predetermined temperature and then further increasing the temperature and heating for a predetermined time.
  • the cured product thus obtained has excellent electrical characteristics, for example, excellent low dielectric constant and low dielectric loss tangent. Furthermore, the said hardened
  • the cured product of the epoxy resin composition of the present invention includes only an epoxy resin and a curing catalyst and / or a curing agent (that is, epoxy resin + curing catalyst, epoxy resin + curing agent, or epoxy resin + curing catalyst + curing agent).
  • the relative dielectric constant (1 GHz) of the cured product is preferably about 2.5 to 3.0, more preferably about 2.5 to 2.8.
  • the cured product of the epoxy resin composition of the present invention preferably has a dielectric loss tangent (1 GHz) of about 0.001 to 0.009, about 0.002 to 0.008, or 0.002 to 0.007. More preferably, it is about. Those satisfying both of these conditions are more preferable.
  • the epoxy resin of the present invention preferably has a cured product satisfying the above-mentioned relative dielectric constant (1 GHz) and / or dielectric loss tangent (1 GHz).
  • the relative dielectric constant (1 GHz) and the dielectric loss tangent (1 GHz) are measured by a parallel plate capacitor method. The measurement by the parallel plate capacitor method can be performed using, for example, a known dielectric constant measuring apparatus.
  • the epoxy resin composition of the present invention can be suitably used for a wide range of applications such as semiconductor sealing materials, liquid sealing materials, potting materials, sealing materials, printed circuit board materials, and composite materials.
  • the epoxy resin composition of the present invention can be suitably used in order to enhance electrical properties and metal adhesion.
  • the cured product of the epoxy resin composition of the present invention can be applied as a component (constituent member) such as a semiconductor sealing material, a liquid sealing material, a potting material, a sealing material, a printed board material, and a composite material.
  • a component such as a semiconductor sealing material, a liquid sealing material, a potting material, a sealing material, a printed board material, and a composite material.
  • a component is the following A-1 or A-2
  • the B component is the following B-1, B-2, B-3 or B-4
  • the C component is the following C- 1 or C-2 was prepared.
  • A-1 1,4-bis (dimethylsilyl) benzene (manufactured by Gelest)
  • A-2 Bis [(p-dimethylsilyl) phenyl] ether (Gelest)
  • B-1 Divinylbenzene (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
  • B-2 Diallyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • B-3 Triallyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • B-4 5-vinyl-2-norbornene (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • C-1 4-Vinyl-1,2-epoxycyclohexane (manufactured by Tokyo Chemical
  • An epoxy resin was prepared as follows. As shown in Table 1, A-1 was used as the A component, B-2 was used as the B component, and C-1 was used as the C component. The components A and B were dissolved in 20 mL of toluene in the amounts shown in Table 1, and a 100 mL four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel was added. Next, 20 mg of platinum catalyst (manufactured by N.E. Chemcat, Pt-VTS-IPA solution) was added at 25 ° C., and the mixture was stirred at 40 ° C. for 2 hours.
  • platinum catalyst manufactured by N.E. Chemcat, Pt-VTS-IPA solution
  • the thus obtained epoxy resin 1 was dissolved in tetrahydrofuran, and the weight average molecular weight in terms of polystyrene was measured by GPC.
  • the results are shown in Table 1.
  • the A component, B component, and C component of the types and amounts shown in Table 1 were reacted in the same manner as in Production Example 1.
  • the components of the reaction solution were analyzed by high performance liquid chromatography (HPLC), and the completion of the reaction was confirmed by confirming the disappearance of the component A. Thereafter, toluene was removed by distillation, and the reaction solution was concentrated to obtain epoxy resins 2 to 10 (Table 1).
  • the obtained epoxy resins 2 to 10 were all slightly yellow transparent liquids. Moreover, it carried out similarly to manufacture example 1, and measured the weight average molecular weight of each epoxy resin. The results are shown in Table 1.
  • Example 1 The ratio (mass ratio) of the epoxy resin 1 obtained in Production Example 1 and the cationic curing catalyst (manufactured by Sanshin Chemical Industry Co., Ltd., Sun-Aid SI-100L; sometimes referred to as curing catalyst A) are shown in Table 2. The mixture was weighed into a cup and stirred uniformly while heating to 30 ° C. to prepare an epoxy resin composition.
  • the cationic curing catalyst manufactured by Sanshin Chemical Industry Co., Ltd., Sun-Aid SI-100L; sometimes referred to as curing catalyst A
  • Example 2 An epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy resin 1 was changed to the epoxy resin 3 obtained in Production Example 3 and the ratio (mass ratio) shown in Table 2 was changed.
  • Example 3 An epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy resin 1 was changed to the epoxy resin 5 obtained in Production Example 5 and the ratio (mass ratio) shown in Table 2 was changed.
  • Example 4 Epoxy resin 1 obtained in Production Example 1, curing catalyst 2-ethyl-4-methylimidazole (manufactured by Mitsubishi Chemical Corporation, EMI24; sometimes referred to as curing catalyst B), and acid anhydride curing agent (New Nippon Rika) MH-700; sometimes referred to as curing agent A) was weighed into a cup at the ratio (mass ratio) shown in Table 2 and stirred uniformly while heating to 30 ° C. A resin composition was prepared.
  • Example 5 An epoxy resin composition was prepared in the same manner as in Example 4 except that the epoxy resin 1 was changed to the epoxy resin 2 obtained in Production Example 2 and the ratio (mass ratio) shown in Table 2 was changed.
  • Example 6 An epoxy resin composition was prepared in the same manner as in Example 4 except that the epoxy resin 1 was changed to the epoxy resin 3 obtained in Production Example 3 and the ratio (mass ratio) shown in Table 2 was changed.
  • Example 7 An epoxy resin composition was prepared in the same manner as in Example 4 except that the epoxy resin 1 was changed to the epoxy resin 4 obtained in Production Example 4 and the ratio (mass ratio) shown in Table 2 was changed.
  • Example 8 An epoxy resin composition was prepared in the same manner as in Example 4 except that the epoxy resin 1 was changed to the epoxy resin 5 obtained in Production Example 5 and the ratio (mass ratio) shown in Table 2 was changed.
  • Example 9 An epoxy resin composition was prepared in the same manner as in Example 4 except that the epoxy resin 1 was changed to the epoxy resin 6 obtained in Production Example 6 and the ratio (mass ratio) shown in Table 2 was changed.
  • Example 10 An epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy resin 1 was changed to the epoxy resin 7 obtained in Production Example 7 and the ratio (mass ratio) shown in Table 2 was changed.
  • Example 11 An epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy resin 1 was changed to the epoxy resin 8 obtained in Production Example 8 and the ratio (mass ratio) shown in Table 2 was changed.
  • Example 12 An epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy resin 1 was changed to the epoxy resin 9 obtained in Production Example 9 and the ratio (mass ratio) shown in Table 2 was changed.
  • Example 13 An epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy resin 1 was changed to the epoxy resin 10 obtained in Production Example 10 and the ratio (mass ratio) shown in Table 2 was changed.
  • Epoxy resin 5 obtained in Production Example 5 triphenylphosphine as a curing catalyst (manufactured by Tokyo Chemical Industry Co., Ltd .; sometimes referred to as curing catalyst C), and phenol resin-based curing agent ([phenol novolak resin (DIC) TD-2131)]; sometimes referred to as curing agent B) at a ratio (mass ratio) shown in Table 2 and weighed into a cup, and stirred uniformly while heating to 30 ° C.
  • An epoxy resin composition was prepared.
  • Epoxy resin 5 obtained in Production Example 5 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd .: sometimes referred to as curing catalyst D) and an active ester curing agent (active ester resin, DIC) EPICLON HPC-8000-65T (sometimes referred to as “Curing agent C”) was weighed into a cup at the ratio (mass ratio) shown in Table 2 and stirred while heating to 30 ° C. to uniformly mix.
  • An epoxy resin composition was prepared.
  • Example 1 (Comparative Example 1) In Example 1, the epoxy resin 1 was changed to a Bis-A type epoxy resin (JER828 manufactured by Mitsubishi Chemical Co., Ltd .; sometimes expressed as an epoxy resin 11) and changed to the ratio (mass ratio) shown in Table 3. Except for the above, an epoxy resin composition was prepared in the same manner as in Example 1.
  • a Bis-A type epoxy resin JER828 manufactured by Mitsubishi Chemical Co., Ltd .; sometimes expressed as an epoxy resin 11
  • Example 2 In Example 4, the epoxy resin composition was prepared in the same manner as in Example 4 except that the epoxy resin 1 was changed to the epoxy resin 11 and the ratio (mass ratio) shown in Table 3 was changed.
  • Example 3 (Comparative Example 3)
  • the epoxy resin 1 was changed to 1,4-bis ⁇ [2- (3,4-epoxycyclohexyl) ethyl] dimethylsilyl ⁇ benzene (may be referred to as the epoxy resin 12).
  • An epoxy resin composition was prepared in the same manner as in Example 1 except that the ratio (mass ratio) was changed.
  • the epoxy resin composition prepared in each Example and Comparative Example was applied to an aluminum plate, and a 35 ⁇ m thick electrolytic copper foil (Furukawa Electric Co., Ltd.) was laminated thereon to form a laminate.
  • the laminated body was heated at 100 ° C. for 1 hour, then at 120 ° C. for 2 hours, and then at 150 ° C. for 2 hours to form a cured product of the epoxy resin composition. After curing, a cut was made with a cutter so that the width was 1 cm, and this was used as a 90-degree peel strength test piece.
  • the obtained test piece was subjected to a 90 degree peel strength test using AGS-X (manufactured by Shimadzu Corporation) at a test speed of 50 mm / min.
  • the epoxy resin composition prepared in each example and comparative example was poured into a resin mold (thickness 1 mm) and heated at 100 ° C. for 1 hour, then at 120 ° C. for 2 hours, and then at 150 ° C. for 2 hours. A cured product of the resin composition was formed. Then, it cut out into the size of width 20mm * length 30mm * thickness 1mm, and this was made into the test piece for dielectric constant measurement.
  • the epoxy resin composition prepared in each Example and Comparative Example was applied to an electrolytic copper foil (made by Furukawa Electric Co., Ltd.) having a thickness of 35 ⁇ m, and the electrolytic copper foil was stacked thereon to form a laminate.
  • the laminated body was heated at 100 ° C. for 1 hour, then at 120 ° C. for 2 hours, and then at 150 ° C. for 2 hours to form a cured product of the epoxy resin composition. After curing, it was cut with a cutter so as to have a width of 1 cm, and this was used as a heat-resistant blister test piece.
  • FIG. 1 shows an example of a test piece with blisters.
  • Table 1 shows the blending amounts of the components used in each production example and the weight average molecular weight of the obtained epoxy resin.
  • “Mol” in parentheses in Table 1 represents the number of moles of the hydrosilyl group of the A component, the carbon-carbon unsaturated bond group of the B component, or the functional group of the unsaturated bond group of the C component.
  • Tables 2 and 3 show the results of 90 degree peel strength and electrical characteristics (relative dielectric constant and dielectric loss tangent) and solder heat resistance against copper foil. From these results, a hydrosilylated epoxy resin obtained by a hydrosilylation reaction of the A component, the B component and the C component (that is, a hydrosilylated epoxy resin having the A component, the B component and the C component as structural units), and a curing catalyst It can be seen that the epoxy resin composition containing the above can form a cured product having excellent low dielectric properties and excellent adhesion to metals.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne : une résine époxy capable de former des objets durcis qui sont excellents en termes de caractéristiques de faible constante diélectrique et d'adhésivité à des métaux ; une composition de résine époxy ; et un objet durci obtenu à partir de celle-ci, son utilisation et procédé de production. La résine époxy comprend : (A) un motif structural dérivé d'un composé organique hydrosilylé et formé par élimination d'un atome d'hydrogène du groupe hydrosilyle ; (B) un motif structural dérivé d'un composé ne contenant pas de groupe époxy mais contenant une liaison insaturée carbone-carbone et formé par conversion de la liaison insaturée carbone-carbone en liaison C=C ou liaison C-C ; et (C) un motif structural dérivé d'un composé contenant à la fois une liaison insaturée carbone-carbone et un groupe époxy et formé par conversion de la liaison insaturée carbone-carbone en liaison C=C ou liaison C-C.
PCT/JP2018/013257 2017-03-31 2018-03-29 Résine époxy, composition de résine époxy, et objet durci obtenu à partir de celle-ci, son utilisation et procédé de production WO2018181719A1 (fr)

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US11066510B2 (en) 2015-07-10 2021-07-20 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition, process for producing same, and uses of said composition
US11091627B2 (en) 2017-01-10 2021-08-17 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
US11111382B2 (en) 2017-01-10 2021-09-07 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
CN113667097A (zh) * 2021-03-26 2021-11-19 蓝赛夫(上海)电子材料有限公司 环氧树脂单体的中间体化合物及其制备方法和应用
US11292872B2 (en) 2017-01-10 2022-04-05 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
CN114458303A (zh) * 2021-06-29 2022-05-10 中国海洋石油集团有限公司 一种压裂监测用覆膜控释示踪剂颗粒及其制备方法
US11603466B2 (en) 2017-01-10 2023-03-14 Sumitomo Seika Chemicals Co.. Ltd. Epoxy resin composition
WO2024043038A1 (fr) * 2022-08-22 2024-02-29 信越化学工業株式会社 Composition durcissable par voie cationique, objet durci, et dispositif optique à semi-conduteurs

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US11066510B2 (en) 2015-07-10 2021-07-20 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition, process for producing same, and uses of said composition
US11091627B2 (en) 2017-01-10 2021-08-17 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
US11111382B2 (en) 2017-01-10 2021-09-07 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
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CN113667097A (zh) * 2021-03-26 2021-11-19 蓝赛夫(上海)电子材料有限公司 环氧树脂单体的中间体化合物及其制备方法和应用
CN113667097B (zh) * 2021-03-26 2024-01-23 蓝赛夫(上海)电子材料有限公司 环氧树脂单体的中间体化合物及其制备方法和应用
CN114458303A (zh) * 2021-06-29 2022-05-10 中国海洋石油集团有限公司 一种压裂监测用覆膜控释示踪剂颗粒及其制备方法
WO2024043038A1 (fr) * 2022-08-22 2024-02-29 信越化学工業株式会社 Composition durcissable par voie cationique, objet durci, et dispositif optique à semi-conduteurs

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