[go: up one dir, main page]

WO2018131564A1 - Composition de résine époxy - Google Patents

Composition de résine époxy Download PDF

Info

Publication number
WO2018131564A1
WO2018131564A1 PCT/JP2018/000193 JP2018000193W WO2018131564A1 WO 2018131564 A1 WO2018131564 A1 WO 2018131564A1 JP 2018000193 W JP2018000193 W JP 2018000193W WO 2018131564 A1 WO2018131564 A1 WO 2018131564A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
formula
ring
atom
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/000193
Other languages
English (en)
Japanese (ja)
Inventor
矩章 福田
良太 針▲崎▼
山本　勝政
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Seika Chemicals Co Ltd
Original Assignee
Sumitomo Seika Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Seika Chemicals Co Ltd filed Critical Sumitomo Seika Chemicals Co Ltd
Priority to JP2018561362A priority Critical patent/JP6987791B2/ja
Publication of WO2018131564A1 publication Critical patent/WO2018131564A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08G59/68—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 catalysts used
    • 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
    • H01L23/31—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 composition, a method for producing the same, a use of the composition, and the like.
  • Epoxy resins are widely used in various applications such as adhesives, electronic materials and composite materials.
  • adhesives electronic materials and composite materials.
  • a rapidly curing epoxy resin material is required.
  • electrical characteristics is desired.
  • Patent Document 1 describes an epoxy resin composition excellent in rapid curability by combining an epoxy resin and a cationic polymerization initiator.
  • curability is improved by using a sulfonium borate salt as a cationic polymerization initiator.
  • electrical properties and water resistance are still not sufficient.
  • an object of the present invention is to provide an epoxy resin composition having not only fast curability but also excellent electrical properties and water resistance after curing, and a method for producing the same.
  • an epoxy resin composition containing a specific epoxy resin containing a silicon atom and a thermal cationic polymerization initiator has excellent rapid curability.
  • the present inventors have found that an epoxy resin composition having low dielectric properties and water resistance can be obtained after curing. Based on this knowledge, further research was conducted and the present invention was completed.
  • the ring X is 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 or connected
  • R Xa , R Xb , R Xc , and R Xd are the same or different and are a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, a halogen atom, or formula (3):
  • R 1 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.
  • the carbon atom may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom;
  • R 2 represents an alkylene group having 1 to 18 carbon atoms, and this group is at least one selected from the group consisting of oxygen atoms and nitrogen atoms, with some carbon atoms excluding carbon atoms directly bonded to silicon atoms.
  • R 3 s are the same or different and each 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 have 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, m represents an integer of 0 to 6, n represents an integer of 0 to 3.
  • R Xa , R Xb , R Xc , and R Xd is a group represented by the formula (3),
  • a hydrogen atom bonded to a carbon atom constituting a hydrocarbon ring constituting the X ring and to which R Xa , R Xb , R Xc , and R Xd are not bonded is a lower alkyl group or a lower alkoxy group , A lower alkenyl group, or a halogen atom.
  • ring X 1 and ring X 2 are the same or different and each represents a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, and Y is a bond, substituted with an alkyl group having 1 to 4 carbon atoms. Or a ring represented by an alkylene group having 1 to 6 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), —SO—, or —SO 2 —).
  • the saturated hydrocarbon ring is a saturated hydrocarbon ring having 4 to 8 carbon atoms;
  • the unsaturated hydrocarbon ring is an unsaturated hydrocarbon ring having 4 to 8 carbon atoms; Item 3.
  • X ii represents 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, to two hydrogen atoms
  • 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- )).
  • R 1 s are the same or different and each 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 have 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 2 is the same or different and represents an alkylene group having 1 to 18 carbon atoms, and this group is selected from the group consisting of oxygen atoms and nitrogen atoms, with some carbon atoms excluding carbon atoms directly bonded to silicon atoms.
  • R 3 s are the same or different and each 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 have 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, m represents an integer of 0 to 6, n represents an integer of 0 to 3. ) And an epoxy resin represented by the formula (1-iiia):
  • X iii is 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, to 3 hydrogen atoms
  • Item 2 The epoxy resin composition according to item 1, comprising at least one epoxy resin selected from the group consisting of epoxy resins represented by: and a thermal cationic polymerization initiator.
  • Item 5 The epoxy resin composition according to any one of Items 1 to 4, wherein the thermal cationic polymerization initiator is at least one selected from the group consisting of a sulfonium salt, a boron compound, and a mixture of a boron compound and a Lewis base.
  • Item 6. Item 6.
  • Item 7. Item 7. A cured product of the epoxy resin composition according to any one of Items 1 to 6.
  • Item 8. A semiconductor encapsulant, a liquid encapsulant, a potting material, a sealing material, an interlayer insulating film, an adhesive layer, wherein the epoxy resin composition according to any one of Items 1 to 6 or the cured product according to Item 7 is used, Coverlay film, electromagnetic shielding film, printed circuit board material or composite material.
  • Items 1 to 6 which is used for a semiconductor encapsulant, a liquid encapsulant, a potting material, a seal material, an interlayer insulating film, an adhesive layer, a cover lay film, an electromagnetic shielding film, a printed circuit board material, or a composite material
  • Item 8 The epoxy resin composition according to Item 8, or the cured product according to Item 7.
  • Any one of Items 1 to 6 for producing a semiconductor encapsulant, a liquid encapsulant, a potting material, a sealing material, an interlayer insulating film, an adhesive layer, a cover lay film, an electromagnetic wave shielding film, a printed circuit board material, or a composite material Use of the epoxy resin composition according to Item 8 or the cured product according to Item 7.
  • the epoxy resin composition of the present invention contains a specific epoxy resin and a thermal cationic polymerization initiator, it has excellent fast curability, and the cured product has electrical properties (low dielectric properties) and heat resistance. is doing. Moreover, it is excellent also in water resistance. Therefore, the epoxy resin composition of the present invention includes, for example, a semiconductor sealing body, a liquid sealing material, a potting material, a sealing material, an interlayer insulating film, an adhesive layer, a cover lay film, an electromagnetic wave shielding film, a printed board material, and a composite material. It can be suitably used for a wide range of uses.
  • the epoxy resin composition included in the present invention has the formula (1):
  • R Xa , R Xb , R Xc , and R Xd are the same or different and are a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, a halogen atom, or the formula (3):
  • lower alkyl group, the lower alkoxy group, and the lower alkenyl group may be collectively referred to as “lower carbon substituent”.
  • lower carbon substituents among the lower carbon substituents, a lower alkyl group or a lower alkoxy group is more preferable.
  • R Xa , R Xb , R Xc , and R Xd are a group of the formula (3).
  • R Xa , R Xb , R Xc , and R Xd are three hydrogen atoms or halogen atoms or lower carbon substituents and one is a group of formula (3), or two are hydrogen atoms or halogen atoms or Two of the lower carbon substituents are groups of formula (3), one is a hydrogen atom or halogen atom or lower carbon substituent and three are groups of formula (3), or all are of formula (3) It is a group.
  • R Xa , R Xb , R Xc , and R Xd are a hydrogen atom, a halogen atom, or a lower carbon substituent
  • R Xd is a formula (Ii) R Xa and R Xb are a hydrogen atom, a halogen atom or a lower carbon substituent, and R Xc and R Xd are a group of formula (3), or (iii) R Xa Is a hydrogen atom or a halogen atom or a lower carbon substituent, and R Xb , R Xc , and R Xd are groups of the formula (3), or (iv) all of R Xa , R Xb , R Xc , and R Xd Can be a group of formula (3).
  • R Xa , R Xb , R Xc , and R Xd are a group of formula (3).
  • R Xa , R Xb , R Xc , and R Xd may be the same or different. Therefore, (i) R Xa , R Xb, and R Xc are a hydrogen atom, a halogen atom, or a lower carbon substituent. And R Xd is a group of the formula (3), R Xa , R Xb and R Xc may be the same or different, and (ii) R Xa and R Xb are a hydrogen atom, a halogen atom or a lower carbon substituent.
  • R Xc and R Xd are a group of the formula (3)
  • R Xa and R Xb may be the same or different
  • R Xc and R Xd may be the same or different
  • R Xa is a hydrogen atom
  • R Xb , R Xc , and R Xd are a group of formula (3) with a halogen atom or lower carbon substituent
  • R Xb , R Xc , and R Xd may be the same or different
  • the groups of the formula (3) are preferably the same.
  • R Xa , R Xb , R Xc , and R Xd are halogen atoms or lower carbon substituents
  • these halogen atoms or lower carbon substituents may be the same or different.
  • it is more preferable that 2 or 3 of R Xa , R Xb , R Xc , and R Xd are the same lower carbon substituent.
  • the lower carbon substituent refers to a lower alkyl group, a lower alkoxy group, or a lower alkenyl group.
  • “lower” means 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6).
  • a lower alkyl group or a lower alkoxy group is preferred.
  • Specific examples of the lower alkyl group 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 lower alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an 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 X ring represents 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 or connected.
  • the saturated hydrocarbon ring for example, a saturated hydrocarbon ring having 4 to 8 carbon atoms (4, 5, 6, 7, or 8) is preferable, and a cyclopentane ring, a cyclohexane ring and the like are particularly preferable.
  • the unsaturated hydrocarbon ring for example, an unsaturated hydrocarbon ring having 4 to 8 carbon atoms (4, 5, 6, 7, or 8) is preferable, and a benzene ring or the like is particularly preferable.
  • the saturated hydrocarbon ring and / or unsaturated hydrocarbon rings 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.
  • 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 called.
  • the ring represented by is preferable.
  • the X 1 ring and the X 2 ring are the same or different and represent a saturated hydrocarbon ring or an unsaturated hydrocarbon ring. That is, the X 1 ring and the X 2 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. It is preferable that both the X 1 ring and the X 2 ring are saturated hydrocarbon rings or both are unsaturated hydrocarbon rings.
  • the X 1 ring and the X 2 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 -is shown.
  • the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene 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, —S—, —SO 2 —, and more preferably a bond, a dimethylmethylene group, an oxygen atom, —SO 2 —.
  • the ring represented by formula (2) is substituted with R Xa , R Xb , R Xc , and R Xd .
  • the ring X in the formula (1) is a ring represented by the formula (2), wherein three of R Xa to R Xd are a hydrogen atom, a halogen atom or a lower carbon substituent, and one is a group of the formula (3). In some cases, either X 1 ring or X 2 ring may be substituted with a group of formula (3).
  • substituted (X 1 ring halogen atom or a lower carbon substituent Number: X 2 ring substitution number) is (1: 0), (0: 1), (2: 0), (1: 1), (0: 2), (3: 0), (2: 1) ), (1: 2), or (0: 3).
  • R Xa to R Xd are a hydrogen atom, a halogen atom or a lower carbon substituent and two are groups of the formula (3)
  • either the X 1 ring or the X 2 ring is a group of the formula (3) in may be substituted, X 1 ring and X 2 rings may be substituted by one by one group of the formula (3), X 1 ring and X 2 ring group of the formula (3) one by one It is preferably substituted with.
  • the ring represented by the formula (2) is substituted with 0, 1, or 2 halogen atoms or lower carbon substituents, and the halogen atom or lower carbon substituent (X 1 ring substitution number: X 2
  • the number of ring substitutions can be (1: 0), (0: 1), (2: 0), (1: 1), or (0: 2).
  • R Xa to R Xd is a hydrogen atom, a halogen atom or a lower carbon substituent, and three are groups of the formula (3)
  • either the X 1 ring or the X 2 ring is a group of the formula (3) May be substituted with two X 1 rings
  • one X 2 ring may be substituted with one group of formula (3), one X 1 ring and two X 2 rings with formula (3)
  • two X 1 rings are substituted with one X 2 group or one X 1 ring and two X 2 rings are represented by formula (3).
  • the ring represented by the formula (2) is substituted with 0 or 1 halogen atom or a lower carbon substituent, and the halogen atom or lower carbon substituent (the number of substitution of X 1 ring: substitution of X 2 ring) The number) can be (1: 0) or (0: 1).
  • R Xa to R Xd are groups of the formula (3)
  • either the X 1 ring or the X 2 ring may be substituted with four groups of the formula (3), and the X 1 ring is 3
  • One X 2 ring may be substituted with one group of formula (3)
  • one X 1 ring may be substituted with three X 2 rings with three groups of formula (3)
  • X 1 ring There may be substituted with two X 2 rings two formulas (3) group, it is preferred that X 1 ring are two X 2 ring is substituted by two groups of formula (3).
  • ring X is the same as above.
  • a group represented by the following formula is particularly preferable. That is,
  • R 1 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 (preferably an oxygen atom) selected from the group consisting of an oxygen atom and a nitrogen atom.
  • the partial carbon atoms are preferably carbon atoms that are not directly bonded to a silicon atom.
  • the part of carbon atoms that may be substituted is 1 or plural (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom.
  • R 1 bonded to the same silicon atom in view like the simplicity of the synthesis is preferably the same.
  • it is more preferable that all R 1 existing in the formula (1) is the same.
  • the alkyl group having 1 to 18 carbon atoms represented by R 1 is a linear or branched alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl.
  • n-butyl group n-pentyl group, neopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, 2,2,4-trimethylpentyl group, n-octyl group, isooctyl group, n- Nonyl group, n-decyl group, n-dodecyl group and the like can be mentioned.
  • 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.
  • the alkenyl group having 2 to 9 carbon atoms represented by R 1 is a linear or branched alkenyl group such as vinyl group, allyl group, 2-propenyl group, butenyl group, pentenyl group, 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.
  • 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. Preferably, it is a phenyl group.
  • Examples of the aralkyl group represented by R 1 include an alkyl group having 1 to 4 carbon atoms substituted with an aryl group (especially a phenyl group).
  • an aryl group especially a phenyl group.
  • benzyl group, ⁇ -phenethyl group, ⁇ -phenethyl group, ⁇ - Examples thereof include a methylphenethyl group.
  • R 1 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
  • R 2 represents an alkylene group having 1 to 18 carbon atoms.
  • the alkylene group is a linear or branched alkylene group, preferably a linear alkylene group.
  • 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 18 carbon atoms preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and further preferably an alkylene group having 2 to 6 carbon atoms. And particularly preferably an alkylene group having 2 to 5 carbon atoms.
  • 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 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 that may be substituted is 1 or plural (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom.
  • Examples of the group include, when the side bonded to the silicon atom of R 2 is (*), for example, (*)-alkylene having 2 to 9 carbon atoms-O-alkylene having 1 to 8 carbon atoms, preferably (*)-C2-C4 alkylene-O-C1-C3 alkylene-, more preferably (*)-C2-C4 alkylene-O-C1-C2 alkylene-, especially Preferably, (*)-C3 alkylene-O-methylene- is used.
  • m represents an integer of 0 to 6 (that is, 0, 1, 2, 3, 4, 5, or 6).
  • N represents an integer of 0 to 3 (that is, 0, 1, 2, or 3).
  • group of formula (4) a group to which R 2 of formula (3) is bonded (side not bonded to a silicon atom) is represented by formula (4) (hereinafter, sometimes referred to as “group of formula (4)”). It becomes as follows.
  • n is an integer of 0 to 3, and thus represents any of the following groups.
  • R 2 and R 3 are bonded to a 3- to 8-membered ring or an epoxy ring.
  • n represents the number of R 3 bonded to a 3- to 8-membered ring or an epoxy ring.
  • R 3 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.
  • R 3 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.
  • R 1 , R 2 , R 3 , m, and n are the same as described above, and all of R 1 are the same, and R 3 is present in a plural number.
  • groups that are all identical are mentioned.
  • the group is present in the epoxy resin represented by the formula (1) in 1, 2, 3 or 4, and each group may be the same or different, and is preferably the same.
  • R 3 is the same as above, and m is 0, 1, 2, 3 or 4, and n is 0, 1 or 2. Among them, more preferred are the following groups (all of which R 3 is as defined above).
  • the group of the formula (4) is 1, 2, 3 or 4 in the epoxy resin represented by the formula (1), but each group may be the same or different and is preferably the same.
  • a hydrogen atom bonded to a carbon atom constituting a hydrocarbon ring constituting the X ring and to which R Xa , R Xb , R Xc , and R Xd are not bonded is a lower carbon substituent or It may be substituted with a halogen atom (preferably a lower carbon substituent). That is, when the X ring is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed, these rings are constituted.
  • a hydrogen atom bonded to a carbon atom to which R Xa , R Xb , R Xc , and R Xd are not bonded is substituted with a lower carbon substituent or a halogen atom (preferably a lower carbon substituent)
  • a halogen atom preferably a lower carbon substituent
  • the X ring is a ring having a structure in which two saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are connected, these connected saturated hydrocarbon rings and / or unsaturated hydrocarbon rings and R Xa a carbon atom constituting the hydrocarbon ring, R Xb, R Xc, and hydrogen atoms bonded to the carbon atom to which R Xd is not bound is a lower carbon substituent or a halogen atom (preferably lower carbon location It may be substituted by a group).
  • the case where the X ring is a ring represented by the formula (2) will be described more specifically.
  • the carbon atoms constituting the X 1 ring and the X 2 ring, and R Xa , R Xb , R Xc , And a hydrogen atom bonded to a carbon atom to which R Xd is not bonded may be substituted with a lower carbon substituent or a halogen atom (preferably a lower carbon substituent).
  • R Xa-d non-bonded a carbon atom that constitutes a hydrocarbon ring constituting the X ring and to which R Xa , R Xb , R Xc , and R Xd are not bonded.
  • R Xa-d non-bonded Sometimes called a "carbon atom.”
  • R Xa-d non-bonded hydrogen atoms bonded to carbon atoms may be substituted lower carbon substituent group or a halogen atom, it is preferable to only one single R Xa-d unbound carbon atoms bonds. That is, when the hydrogen atom attached to R Xa-d unbound carbon atoms is substituted, one hydrogen atom have a lower carbon substituent or a halogen of the hydrogen atoms bonded to R Xa-d unbound carbon atoms It is preferably substituted with an atom. Further, the number of substitutions (that is, the total of the lower carbon substituent and the halogen atom) is preferably smaller than the number of R Xa-d non-bonded carbon atoms.
  • the number of the substitution is preferably 1 to 6 (1, 2, 3, 4, 5, or 6), more preferably 1 to 4, and still more preferably 1 to 2.
  • the hydrogen atom to be substituted is preferably a hydrogen atom bonded to a carbon atom to which Y is not bonded.
  • R Xa , R Xb , R Xc , and R Xd is a lower carbon substituent and at least one lower carbon substituent is bonded to an R Xa-d unbonded carbon atom
  • the carbon substituents are the same. That is, if there is a lower carbon substituent in R Xa , R Xb , R Xc , and R Xd and there is a lower carbon substituent bonded to an R Xa-d unbonded carbon atom, all lower carbon substitutions It is preferred that the groups are the same.
  • R Xa , R Xb , R Xc , and R Xd when at least one of R Xa , R Xb , R Xc , and R Xd is a halogen atom, and at least one halogen atom is bonded to the R Xa-d non-bonded carbon atom. It is preferred that all halogen atoms are the same. That is, when a halogen atom is present in R Xa , R Xb , R Xc , and R Xd and a halogen atom bonded to an R Xa-d unbonded carbon atom is present, all halogen atoms are the same. Is preferred.
  • R Xa , R Xb , R Xc , and R Xd are the same as defined above, and R Xg1 and R Xg2 are the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group.
  • An epoxy resin represented by a group or a lower alkenyl group is preferred.
  • R Xa , R Xb , R Xc , R Xd , R Xg1 and R Xg2 are bonded to different carbon atoms on the benzene ring, respectively.
  • the epoxy resins represented by the formula (1-X1) those in which R Xg1 and R Xg2 are hydrogen atoms are preferable.
  • R Xa , R Xb , R Xc , and R Xd are the same as above, and R Xg1 and R Xg2 are the same as above). it can.
  • R Xa and R Xb are hydrogen atoms
  • R Xc and R Xd are groups of the formula (3)
  • R Xg1 and R Xg2 are hydrogen atoms.
  • R Xa and R Xc are hydrogen atoms
  • R Xb and R Xd are groups of the formula (3)
  • R Xg1 and R Xg2 are more preferably hydrogen atoms.
  • R Xa is a hydrogen atom
  • R Xb , R Xc and R Xd are groups of the formula (3)
  • R Xg1 and R Xg2 are hydrogen. More preferably, it is an atom.
  • Y is the same as defined above;
  • R Xa , R Xb , R Xc , and R Xd are the same as defined above;
  • R X11 , R X12 , R X13 , and R X21 , R X22 and R X23 may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group.
  • R Xa , R Xc , R X11 , R X12 , and R X13 are more preferably bonded to different carbon atoms
  • R Xb , R Xd , R X21 , More preferably, R X22 and R X23 are bonded to different carbon atoms.
  • R Xa , R Xb , R Xc , R Xd , R X11 , R X12 , R X13 , R X21 , R X22 , and R X23 are not bonded to the carbon atom to which Y is bonded.
  • Y is the same as defined above;
  • R Xa , R Xb , R Xc , and R Xd are the same as defined above;
  • R X11 , R X12 , and R X13 and R X21 , R X22 and R X23 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group), or an epoxy resin represented by the formula (1-X2b):
  • Y is the same as defined above;
  • R Xa , R Xb , R Xc , and R Xd are the same as defined above;
  • R X11 , R X12 , R X13 , and R X21 , R X22 and R X23 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group), or an epoxy resin represented by the formula (1-X2c):
  • Y is the same as defined above;
  • R Xa , R Xb , R Xc , and R Xd are the same as defined above;
  • R X11 , R X12 , and R X13 and R X21 , R X22 and R X23 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group.
  • R Xa , R Xb , R Xc , and R Xd are groups of the formula (3), and R X11 and R X21 are lower carbon substituents. Yes , it is preferable that R X12 , R X13 , R X22 , and R X23 are hydrogen atoms.
  • Y is an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms (particularly —C (CH 3 ) 2 —), and R Xa , R Xb , R Xc , And R Xd is a group of the formula (3), R X11 and R X21 are lower alkoxy groups, and R X12 , R X13 , R X22 , and R X23 are particularly preferably hydrogen atoms.
  • R Xa , R Xb , R Xc and R Xd are all the same, and the lower carbon substituents of R X11 and R X21 are the same.
  • R Xa and R Xb are hydrogen atoms
  • R Xc and R Xd are groups of the formula (3)
  • R X11 , R X12 , R X13 , R X21 , R X22 , and R X23 are preferably a hydrogen atom.
  • R Xc and R Xd are the same.
  • R Xa is a hydrogen atom
  • R Xb , R Xc and R Xd are groups of the formula (3)
  • R X11 , R X12 , R X13 , R X21 , R X22 , and R X23 are preferably a hydrogen atom.
  • R Xb , R Xc and R Xd are the same.
  • R Xa-d -bonded hydrogen atom has not been substituted in the non-bonded carbon atom, and, R Xa, R Xb, of R Xc, and R Xd, R Xa and R Xb is a hydrogen atom and R Xc and R Xd are groups of the formula (3), or (iii) the hydrogen atom bonded to the R Xa-d non-bonded carbon atom is not substituted, and R Xa , R Among Xb , R Xc , and R Xd , R Xa is a hydrogen atom and R Xb , R Xc , and R Xd are groups of the formula (3), or (iva) R Xa-d is bonded to a non-bonded carbon atom.
  • the bonded hydrogen atoms are not substituted and all of R Xa , R Xb , R Xc , and R Xd can be groups of formula (3).
  • X ii represents a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring, or a formula (2 g -ia):
  • R 1 , R 2 , R 3 , m, and n are the same as described above.
  • the epoxy resin represented by these is preferably included. Note that R 1 , R 2 , R 3 , m, and n may all be the same or different, and are preferably the same.
  • X ii preferably cyclohexane-1,4-diyl group, a 1,4-phenylene group, more preferably a 1,4-phenylene group.
  • a group in which Y is a bond, a dimethylmethylene group, an oxygen atom, or —SO 2 — is particularly preferable.
  • X ii among them preferably a cyclohexane-1,4-diyl group, a 1,4-phenylene group, the formula (2 g -iia ') can be mentioned, more preferably a 1,4-phenylene group.
  • m is the same 0, 1, 2, 3, or 4 (particularly preferably, m is the same 0 or 4) and n is the same 0 (ie, R 3 is a ring
  • X ii is a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring), and R 1 is the same and has 1 to 3 carbon atoms.
  • a group of 2 to 6 carbon atoms in which R 2 is the same and one carbon atom which is not directly bonded to any of a silicon atom and a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom
  • An epoxy resin represented by showing each group can be more preferably used in the present invention.
  • X iii is a trivalent group obtained by removing three hydrogen atoms from a hydrocarbon ring, or a compound represented by the formula (2 g -iii):
  • R 1 , R 2 , R 3 , m, and n are the same as above.
  • the epoxy resin represented by these is preferably included. Note that R 1 , R 2 , R 3 , m, and n may all be the same or different, and are preferably the same.
  • the trivalent group represented by X iii is preferably the following group:
  • the formula (2 g -iiia) is preferable.
  • a group in which Y is a bond, a dimethylmethylene group, an oxygen atom, or —SO 2 — is particularly preferable.
  • m is the same 0, 1, 2, 3, or 4 (particularly preferably, m is the same 0 or 4), and n is the same 0 (ie, R 3 represents a ring X iii is a trivalent group obtained by removing three hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring), and R 1 is the same and has 1 to 3 carbon atoms.
  • a group of 2 to 6 carbon atoms in which R 2 is the same and one carbon atom which is not directly bonded to any of a silicon atom and a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom
  • An epoxy resin represented by showing each group can be more preferably used in the present invention.
  • X iv represents a tetravalent group represented by the above (1 ′) and a hydrogen atom bonded to an R Xa-d non-bonded carbon atom in the X ring is not substituted, R 1 , R 2 , R 3 , m, and n are the same as described above.
  • the epoxy resin represented by these is included. Note that R 1 , R 2 , R 3 , m, and n may all be the same or different, and are preferably the same.
  • the tetravalent group represented by X iv is preferably the following group:
  • the tetravalent group represented by X iv is preferably a tetravalent group represented by the formula (2 g ), wherein a hydrogen atom bonded to an R Xa-d non-bonded carbon atom is not substituted.
  • a hydrogen atom bonded to an R Xa-d non-bonded carbon atom is not substituted.
  • a group in which Y is a bond, a dimethylmethylene group, an oxygen atom, or —SO 2 — is particularly preferable.
  • m is the same 0, 1, 2, 3, or 4 (particularly preferably, m is the same 0 or 4) and n is the same 0 (ie, R 3 is a ring X iv is a tetravalent group obtained by removing four hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring), and R 1 is the same and has 1 to 3 carbon atoms.
  • a group of 2 to 6 carbon atoms in which R 2 is the same and one carbon atom which is not directly bonded to any of a silicon atom and a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom
  • An epoxy resin represented by showing each group can be more preferably used in the present invention.
  • epoxy resins represented by the formula (1) More preferable examples include, for example, the formula (1-IIa):
  • X ii is a 1,4-phenylene group or a group represented by the formula (2 g- ia ′) (preferably a 1,4-phenylene group).
  • R 1 is the same or different (preferably the same) and is an alkyl group having 1 to 3 carbon atoms (particularly a methyl group), and
  • R 2 is the same or different (preferably the same) an alkylene having 2 to 6 carbon atoms Group (*) — (CH 2 ) 2 —O—CH 2 —, (*) — (CH 2 ) 3 —O—CH 2 —, (*) — (CH 2 ) 3 —O— (CH 2 )
  • a compound which is 2- or (*)-(CH 2 ) 5 -O- (CH 2 ) 4- is preferred. The above same, (*) indicates the side bonded to the silicon atoms of R 2.
  • epoxy resins represented by the above formula (1-IIa) More preferred are those represented by the formula (1-IIa1):
  • R 1 and X ii are the same as above).
  • the epoxy resin represented by these can be illustrated. Note that R 1 may be the same or different, and is preferably the same.
  • R 1 is the same or different (preferably the same) and is an alkyl group having 1 to 3 carbon atoms (particularly a methyl group), and X ii is 1, More preferred is a 4-phenylene group or a group represented by the formula (2 g -ia ′).
  • epoxy resins represented by the formula (1) more preferable examples include, for example, the formula (1-IIb):
  • R 1 , R 2 , R 3 , X ii , and n are the same as above.
  • the epoxy resin represented by these can also be mentioned. Note that R 1 , R 2 , R 3 , and n may all be the same or different, and are preferably the same.
  • X ii is a 1,4-phenylene group or a group represented by the formula (2 g -ia ′) (preferably a 1,4-phenylene group), and R 1 is the same or different.
  • R 1 is the same or different.
  • R 1 is an alkyl group having 1 to 3 carbon atoms (particularly a methyl group)
  • n is both 0 (that is, the ring is not substituted with R 3 )
  • R 2 is the same or different ( More preferably, it is the same and is an alkylene group having 2 to 6 carbon atoms (preferably a dimethylene group: — (CH 2 ) 2 —).
  • epoxy resins represented by the formula (1) more preferable examples include, for example, the formula (1-IIIa):
  • R 1 , R 2 , R 3 , X iii and n are the same as above
  • the epoxy resin represented by these can also be mentioned. Note that R 1 , R 2 , R 3 , and n may all be the same or different, and are preferably the same.
  • R 1 is the same or different (preferably the same) and is an alkyl group having 1 to 3 carbon atoms (particularly a methyl group), and both n are 0 (That is, the ring is not substituted with R 3 ), and R 2 is the same or different (preferably the same) and is an alkylene group having 2 to 6 carbon atoms (preferably a dimethylene group: — (CH 2 ) 2 —) Is more preferable.
  • the epoxy resin represented by the formula (1) can be used alone or in combination of two or more.
  • the epoxy resin represented by the formula (1) can be produced based on or according to a known method, for example, based on or according to the description of Patent Document 2 (UK Patent No. 1123960). Also, for example, an epoxy resin represented by the formula (1-ia) can be produced by a reaction represented by the following reaction formula.
  • R 2A is an alkenyl group having 2 to 18 carbon atoms, and in this group, some carbon atoms are substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom.
  • R 1 , R 2 , R 3 , and X ii are the same as above.
  • the alkenyl group having 2 to 18 carbon atoms represented by R 2A is a linear or branched alkenyl group, and is preferably a straight chain. 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.
  • alkenyl groups having 2 to 18 carbon atoms 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 is 1 or a plurality of (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom.
  • Examples of the group include 2 to 9 alkenyl-O-carbon having 1 to 8 carbon atoms, preferably 2 to 4 alkenyl-O carbon atoms having 1 to 3 carbon atoms, more preferably 2 to 3 carbon atoms.
  • Examples thereof include 4 alkenyl-O-alkylene having 1 to 2 carbon atoms, particularly preferably 3 alkenyl-O—CH 2 —.
  • the epoxy resin represented by the formula (1-ia) can be produced by subjecting the compound represented by the formula (5-ia) and the compound represented by the formula (6) to a hydrosilylation reaction.
  • the hydrosilylation reaction can usually be carried out in the presence of a catalyst, in the presence or absence of a solvent. Further, in place of the compound represented by the formula (5-ia), the formula (5-iii):
  • X i represents a monovalent group obtained by removing one hydrogen atom from a hydrocarbon ring
  • R 1 is the same as above.
  • X i to X iv are each a monovalent group obtained by removing one hydrogen atom from the X ring, and 2 obtained by removing two hydrogen atoms from the X ring.
  • the catalyst used in the hydrosilylation reaction may be a known catalyst such as platinum catalyst such as platinum carbon, chloroplatinic acid, platinum olefin complex, platinum alkenylsiloxane complex, platinum carbonyl complex, etc .; Fin) rhodium and other rhodium catalysts; and iridium catalysts such as bis (cyclooctadienyl) dichloroiridium.
  • platinum catalyst such as platinum carbon, chloroplatinic acid, platinum olefin complex, platinum alkenylsiloxane complex, platinum carbonyl complex, etc .
  • Fin rhodium and other rhodium catalysts
  • iridium catalysts such as bis (cyclooctadienyl) dichloroiridium.
  • the above catalyst may be in the form of a solvate (for example, hydrate, alcohol solvate, etc.). In use, the catalyst may be dissolved in an alcohol (for example, ethanol) and used in the form of
  • the amount of the catalyst used may be an effective amount as a catalyst.
  • the hydrosilylation reaction proceeds without using a solvent, but the reaction can be performed under mild conditions by using a solvent.
  • 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 may be used alone or in combination of two or more.
  • the amount of the compound represented by the formula (6) is, for example, Si— in the compound represented by the formula (5-ia), (5-ia), (5-iii), or (5-iva).
  • the amount is usually 0.5 to 2 mol, preferably 0.6 to 1.5 mol, more preferably 0.8 to 1.2 mol, relative to 1 mol of the H group.
  • the reaction temperature is usually 0 ° C. to 150 ° C., preferably 10 ° C. to 120 ° C., and the reaction time is usually about 1 hour to 24 hours.
  • the epoxy resin represented by the formula (1) can be obtained by using a known isolation method such as distilling off the solvent from the reaction solution.
  • the thermal cationic polymerization initiator generates an acid species capable of cationic polymerization of a cationically polymerizable compound by heat.
  • thermal cationic polymerization initiator used in the present invention known ones that are used as thermal cationic polymerization initiators for epoxy resins can be appropriately selected and used.
  • thermal cationic polymerization initiator can be used individually or in combination of 2 or more types.
  • boron compound a Lewis acid disclosed in WO2012 / 060449 can be preferably used.
  • a cationic curing catalyst comprising a Lewis acid (boron compound) and a Lewis base disclosed in WO2012 / 060449 can be used.
  • the Lewis base for example, an amine compound, a phosphine compound, a sulfide compound, and the like can be used, and among them, an amine compound can be preferably used.
  • a mixture of a boron compound and an amine compound a mixture composed of a Lewis acid disclosed in WO2012 / 060449 and an amine compound described below can also be used.
  • the contents described in the specification and / or drawings of WO2012 / 060449 are incorporated herein by reference.
  • thermal cationic polymerization initiators Commercially available products can be used for the thermal cationic polymerization initiator.
  • Commercially available products of thermal cationic polymerization initiators include CP-66 and CP-77 manufactured by ADEKA, CI-2855 and CI-2639 manufactured by Nippon Soda Co., Ltd., Sun Aid SI-60, SI-60L and SI manufactured by Sanshin Chemical Industry Co., Ltd.
  • Preferred examples include -80, SI-80L, SI-100, SI-100L, and aromatic fluorine-based acid generators TPB, TEPBD and FX-TP-BC-PC series manufactured by Nippon Shokubai Co., Ltd.
  • a sulfonium salt from the viewpoint of water resistance and low dielectric properties of the cured epoxy resin composition obtained, it is particularly preferable to use a sulfonium salt, a boron compound, or a mixture of a boron compound and a Lewis base, a sulfonium salt, Alternatively, it is more preferable to use a mixture of a boron compound and an amine compound.
  • R 4 represents a hydrogen atom, halogen, or an alkyl group having 1 to 12 carbon atoms
  • R 5a and R 5b are the same or different and each represents an alkyl group having 1 to 12 carbon atoms, a benzyl group, or halogenobenzyl.
  • R 6 represents a hydrogen atom, halogen, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, or —O—R 7
  • R 7 represents a methyl group, an acetyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a benzoyl group, A phenoxycarbonyl group, a chloroacetyl group, a dichloroacetyl group, a trichloro
  • Z ⁇ represents tetrakispentafluorophenyl borate.
  • the sulfonium salt represented by these is preferable.
  • the alkyl group having 1 to 12 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) is more preferably an alkyl group having 1 to 8 carbon atoms.
  • An alkyl group having 1 to 6 carbon atoms is more preferable. Further, it may be a linear or branched alkyl group.
  • R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 5a represents an alkyl group having 1 to 4 carbon atoms, benzyl group, halogenobenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl.
  • R 5b represents an alkyl group having 1 to 4 carbon atoms, a benzyl group, or a naphthylmethyl group
  • R 6 represents a hydrogen atom, a hydroxyl group, or —O—R 7
  • R 7 represents a methyl group or acetyl group It is more preferable to show a group.
  • Examples of commercially available sulfonium salts represented by the formula include San-Aid SI-60, SI-60L, SI-80, SI-80L, SI-100, SI-100L and the like manufactured by Sanshin Chemical Industry Co., Ltd. Illustrated.
  • boron compound including a boron compound in a mixture of a boron compound and a Lewis base
  • R is the same or different and represents a hydrocarbon group which may have a substituent.
  • H is an integer of 1 to 5, and is the same or different and is a fluorine atom bonded to an aromatic ring.
  • the hydrocarbon group here is preferably a hydrocarbon group having 1 to 20 carbon atoms.
  • the hydrocarbon group having 1 to 20 carbon atoms is not limited as long as it has 1 to 20 carbon atoms as a whole, but is preferably an alkyl group, an aryl group, or an alkenyl group.
  • the alkyl group, aryl group, and alkenyl group may be an unsubstituted group or a group in which one or more hydrogen atoms are substituted with another organic group or a halogen atom.
  • organic groups in this case include an alkyl group (when the hydrocarbon group represented by R is an alkyl group, the substituted hydrocarbon group corresponds to an unsubstituted alkyl group as a whole), An aryl group, an alkenyl group, an alkoxy group, a hydroxyl group, etc. are mentioned.
  • H in the above formula is 1, 2, 3, 4, or 5, and is the same or different and represents the number of fluorine atoms bonded to the aromatic ring.
  • the bonding position of the fluorine atom in the aromatic ring is not particularly limited. h is preferably 2 to 5, more preferably 3 to 5, and most preferably 5.
  • the Lewis acid is one in which at least one aromatic ring to which a fluorine atom is bonded is bonded to a boron atom.
  • j is more preferably 2 or more, and further preferably 3, that is, a form in which three aromatic rings to which fluorine atoms are bonded are bonded to boron atoms.
  • specific boron compounds include, for example, tris (pentafluorophenyl) borane (TPB), bis (pentafluorophenyl) phenylborane, pentafluorophenyl-diphenylborane, and tris (4-fluorophenyl) borane.
  • TPB tris (pentafluorophenyl) borane
  • bis (pentafluorophenyl) phenylborane bis (pentafluorophenyl) phenylborane
  • pentafluorophenyl-diphenylborane pentafluorophenyl-diphenylborane
  • 4-fluorophenyl) borane tris (4-fluorophenyl) borane.
  • a mixture of a boron compound and a Lewis base a mixture of a boron compound and an amine compound is preferable, and as the mixture, for example, a mixture of tris (pentafluorophenyl) borane and an amine compound such as piperidine is preferable.
  • a boron compound and amine compound mixture described in WO2012 / 036164 can be preferably used. The contents described in the specification and / or drawings of WO2012 / 036164 are incorporated herein by reference.
  • the above-described boron compound can be preferably used, and tris (pentafluorophenyl) borane is particularly preferable.
  • the compound described in each following item described in WO2012 / 036164 other than piperidine etc. is illustrated preferably.
  • Carbon numbers 1 to 6 indicate carbon numbers 1, 2, 3, 4, 5 or 6, and carbon numbers 1 to 20 indicate carbon numbers 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20; 3 to 10 carbon atoms represents 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms; 6 to 14 carbon atoms indicate 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms.
  • R 1N to R 5N are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms]
  • Item 2n The amine compound according to Item 1n, wherein the amine compound has a piperidine structure represented by the following formula.
  • R 1N to R 5N are as defined above;
  • X N represents an —O— group, — (C ⁇ O) — group, —NR 7N — group (R 7N represents a hydrogen atom or 1 to 6 represents an alkyl group), —O (C ⁇ O) — group, — (C ⁇ O) O— group, —NH (C ⁇ O) — group or — (C ⁇ O) NH— group]
  • Item 3n The amine compound according to Item 1n, wherein the amine compound is represented by the following formula.
  • R 1N to R 5N are as defined above;
  • X N and Z N are the same or different and are —O— group, — (C ⁇ O) — group, —NR 7N — group (R 7N represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), Represents —O (C ⁇ O) — group, — (C ⁇ O) O— group, —NH (C ⁇ O) — group or — (C ⁇ O) NH— group;
  • Y N represents an optionally substituted alkylene group having 1 to 20 carbon atoms;
  • R 6N represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the above-mentioned piperidine structure;
  • the substituent that the alkylene group having 1 to 20 carbon atoms may have a halogen atom, a hydroxyl group, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon
  • aryl groups having 6 to 14 carbon atoms One or more selected from the group consisting of aryl groups having 6 to 14 carbon atoms;
  • the substituent that the aryl group having 6 to 14 carbon atoms may have is one or more selected from the group consisting of a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms Show] Item 4n.
  • the amine compound according to Item 1n, wherein the amine compound is represented by the following formula.
  • R 8N to R 11N represents the above-mentioned piperidine structure, and the rest represents an alkyl group having 1 to 20 carbon atoms
  • Item 5n The amine compound according to Item 1n, wherein the amine compound is a polymer.
  • Item 6n The amine compound according to Item 1n, wherein the amine compound is represented by the following formula.
  • R 1N to R 5N are as defined above
  • examples of preferred specific amine compounds are shown below by structural formulas.
  • the following compound is mentioned as a preferable example of the amine compound of said item 3n.
  • particularly preferable amine compounds include the amine compounds described in Table 1 below.
  • the mixture of the boron compound and the amine compound a commercially available product can be used.
  • FX-TP-BC-PC series manufactured by Nippon Shokubai Co., Ltd. can be used.
  • thermal cationic polymerization initiators examples include diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, tris (pentafluorophenyl) borane (TPB), and bis (pentafluorophenyl).
  • the blending ratio of the thermal cationic polymerization initiator used in the present invention is not particularly limited as long as the effects of the present invention can be exhibited.
  • the amount is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin, the lower limit is more preferably 0.05 parts by weight or more, further preferably 0.1 parts by weight or more, and 0.5 parts by weight or more Even more preferred is 1 part by weight or more.
  • 30 mass parts or less are more preferable, as for an upper limit, 10 mass parts or less are more preferable, and 5 mass parts or less are more preferable.
  • the epoxy resin composition of the present invention may contain an epoxy resin other than the epoxy resin represented by the formula (1) as long as the curing of the present invention is not impaired.
  • the 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, hydrogenated Examples thereof include 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. These epoxy resins may be used alone or in combination of two or more.
  • the blending ratio of the epoxy resin represented by formula (1) and the epoxy resin other than the epoxy resin represented by formula (1) is The mass ratio is, for example, 100: 0 to 20:80, preferably 100: 0 to 30:70, and more preferably 100: 0 to 40:60.
  • the epoxy resin composition of the present invention may contain a filler, a curing agent, a curing catalyst, a thermoplastic resin, an additive, and the like as necessary within a range that does not impair the object and effect of the present invention.
  • the filler examples 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.
  • 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).
  • money, silver, copper, aluminum, nickel, iron, zinc, stainless steel, are mentioned.
  • 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 used as it is, or a filler dispersed in a resin may be used. As the filler, considering the fluidity, heat resistance, low thermal expansion, mechanical properties, hardness, scratch resistance and adhesiveness required for the composition and the cured product, alone or in combination of two or more kinds. Can be used.
  • curing agent examples include an amine curing agent, an amide curing agent, an acid anhydride curing agent, a phenol curing agent, a mercaptan curing agent, an isocyanate curing agent, an active ester curing agent, and a cyanate ester curing. Agents and the like.
  • curing agent may be used independently, and can be used properly according to the characteristic to request
  • amine curing agents include chain aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; isophoronediamine, benzenediamine, bis (4-aminocyclohexyl) methane, and bis (aminomethyl) cyclohexane.
  • Alicyclic amines such as diaminodicyclohexylmethane; aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diethyltoluenediamine, diaminodiethyldiphenylmethane; benzyldimethylamine, triethylenediamine, piperidine, 2- (dimethylaminomethyl) phenol, 2 , 4,6-Tris (dimethylaminomethyl) phenol, DBU (1,8-diazabicyclo (5,4,0) -undecene-7), DBN (1, - diazabicyclo (4,3,0) - nonene-5), and a secondary and tertiary amines, such as.
  • amide-based curing agents examples include dicyandiamide and its derivatives, polyamide resins (polyaminoamide, etc.), and the like.
  • acid anhydride curing agents 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 nadic anhydride And alicyclic acid anhydrides such as acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride.
  • phenolic curing agents include phenol novolak resins, cresol novolak resins, biphenyl type novolak resins, triphenylmethane type phenol resins, naphthol novolak resins, phenol biphenylene resins, phenol aralkyl resins, biphenyl aralkyl type phenol resins, and modified polyphenylene ether resins. And compounds having a benzoxazine ring.
  • 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) , Trimethylol ethane 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 active ester curing agent examples include compounds having at least one ester group that reacts with an epoxy resin in one molecule, such as phenol ester, thiophenol ester, N-hydroxyamine ester, and heterocyclic hydroxy compound ester. Can be mentioned.
  • curing catalyst examples include imidazole compounds, dicyandiamides, tertiary amines, phosphorus compounds, Lewis acid compounds, and the like.
  • a curing catalyst may be used independently and can be used properly according to the characteristic to require, and may use 2 or more types together.
  • thermoplastic resin examples include polyolefin resin, acrylic resin, phenoxy resin, polyamide resin, polyester resin, polycarbonate resin, polyurethane resin, polyarylate resin, polyphenylene ether resin, polyacetal resin, and those obtained by acid modification. Is mentioned. 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 those obtained by acid modification are preferred, among these More preferred are polyolefin resins and acid-modified polyolefin resins.
  • a thermoplastic resin can be used individually or in combination of 2 or more types.
  • the additive examples include an antioxidant, an inorganic phosphor, a lubricant, an ultraviolet absorber, a heat and light stabilizer, an antistatic agent, a polymerization inhibitor, an antifoaming agent, a solvent, an antiaging agent, a radical inhibitor, and an adhesive.
  • Examples include decomposing agents, pigments, metal deactivators, and physical property modifiers.
  • the epoxy resin composition of the present invention can be produced by mixing the epoxy resin represented by the formula (1), a thermal cationic polymerization initiator, and, if necessary, other components.
  • the mixing method is not particularly limited as long as it can be uniformly mixed.
  • a solvent for example, toluene, xylene, methyl ethyl ketone, acetone, cyclohexanone, methylcyclohexane, cyclohexane, etc.
  • a cured product (that is, a cured product of the epoxy resin composition) can be obtained by curing the epoxy resin composition of the present invention.
  • the curing method is not particularly limited, and can be carried out, for example, by heat curing the composition.
  • the curing temperature is usually from room temperature to 250 ° C., and the curing time varies depending on the composition, and can usually be set widely from 30 minutes to 1 week.
  • Each component in Table 2 and Table 3 is as follows. In addition, the numerical value of each component of Table 2 and Table 3 shows a mass part.
  • Epoxy resin F Bis-A type epoxy resin (grade 828) manufactured by Mitsubishi Chemical Corporation (epoxy equivalent 189 g / eq)
  • Epoxy resin G Alicyclic epoxy resin manufactured by Daicel (Celoxide 2021P; generic name is 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate) (epoxy equivalent 137 g / eq) -Cationic polymerization initiator A: San-Aid SI-60L manufactured by Sanshin Chemical Industry Co., Ltd.
  • Cationic polymerization initiator B FX-TP-BC-PC-AD-57103 manufactured by Nippon Shokubai Co., Ltd.
  • Test example 1 (1) Fast Curing Epoxy resin compositions obtained in Examples and Comparative Examples were heated in an oven at 140 ° C. and cured within 30 seconds, ⁇ cured within 2 minutes, and 2 What did not harden within minutes was set as x. The results are shown in Tables 2 and 3.
  • the obtained test piece was measured for dielectric constant (1 GHz) and dielectric loss tangent (1 GHz) at 25 ° C. using a dielectric constant measuring device (impedance analyzer, manufactured by Agilent).
  • the dielectric constant measuring apparatus was calibrated using PTFE. The results are shown in Tables 2 and 3.
  • the storage modulus of the test piece was measured using a dynamic viscoelasticity measuring device (RSG-G2, manufactured by TA Instruments) at a tensile mode and a temperature increase rate of 10 ° C./min.
  • the change rate of the elastic modulus before and after water absorption was calculated from the following formula. (Storage elastic modulus at 30 ° C. after water absorption test / Storage elastic modulus at 30 ° C. before water absorption) ⁇ 100 The results are shown in Tables 2 and 3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

L'invention concerne une composition de résine époxy ayant non seulement des propriétés de durcissement rapide mais également d'excellentes caractéristiques électriques et une excellente résistance à l'eau après durcissement. De façon spécifique, l'invention concerne une composition de résine époxy qui contient un initiateur de polymérisation cationique thermique et une résine époxy ayant une structure spécifique.
PCT/JP2018/000193 2017-01-10 2018-01-09 Composition de résine époxy Ceased WO2018131564A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018561362A JP6987791B2 (ja) 2017-01-10 2018-01-09 エポキシ樹脂組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-002212 2017-01-10
JP2017002212 2017-01-10

Publications (1)

Publication Number Publication Date
WO2018131564A1 true WO2018131564A1 (fr) 2018-07-19

Family

ID=62840049

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/000193 Ceased WO2018131564A1 (fr) 2017-01-10 2018-01-09 Composition de résine époxy

Country Status (3)

Country Link
JP (1) JP6987791B2 (fr)
TW (1) TW201833214A (fr)
WO (1) WO2018131564A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019026822A1 (fr) * 2017-07-31 2019-02-07 住友精化株式会社 Composition de résine époxyde
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
US11292872B2 (en) 2017-01-10 2022-04-05 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
US11603466B2 (en) 2017-01-10 2023-03-14 Sumitomo Seika Chemicals Co.. Ltd. Epoxy resin composition

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3445483A (en) * 1966-03-02 1969-05-20 Dow Corning Organosilicon epoxides
JP2003519705A (ja) * 2000-01-13 2003-06-24 スリーエム エスペ アーゲー ケイ素を含むエポキシドを主成分とする重合可能な調製物
JP2004527602A (ja) * 2001-02-19 2004-09-09 スリーエム エスペ アーゲー 脂肪族および脂環式エポキシド基を含むケイ素化合物をベースとした重合性配合物
JP2008505945A (ja) * 2004-07-14 2008-02-28 スリーエム イーエスピーイー アーゲー エポキシ官能性カルボシラン化合物を含む歯科用組成物
JP2012001668A (ja) * 2010-06-18 2012-01-05 Shin-Etsu Chemical Co Ltd シルフェニレン含有光硬化性組成物、それを用いたパターン形成方法およびその方法により得られる光半導体素子
WO2013140601A1 (fr) * 2012-03-23 2013-09-26 株式会社Adeka Composition de résine durcissable contenant du silicium
WO2017010401A1 (fr) * 2015-07-10 2017-01-19 住友精化株式会社 Composition de résine époxy, son procédé de fabrication, et utilisations de ladite composition
WO2017086368A1 (fr) * 2015-11-18 2017-05-26 住友精化株式会社 Composition de résine époxy, procédé pour sa production et utilisation de la composition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3445483A (en) * 1966-03-02 1969-05-20 Dow Corning Organosilicon epoxides
JP2003519705A (ja) * 2000-01-13 2003-06-24 スリーエム エスペ アーゲー ケイ素を含むエポキシドを主成分とする重合可能な調製物
JP2004527602A (ja) * 2001-02-19 2004-09-09 スリーエム エスペ アーゲー 脂肪族および脂環式エポキシド基を含むケイ素化合物をベースとした重合性配合物
JP2008505945A (ja) * 2004-07-14 2008-02-28 スリーエム イーエスピーイー アーゲー エポキシ官能性カルボシラン化合物を含む歯科用組成物
JP2012001668A (ja) * 2010-06-18 2012-01-05 Shin-Etsu Chemical Co Ltd シルフェニレン含有光硬化性組成物、それを用いたパターン形成方法およびその方法により得られる光半導体素子
WO2013140601A1 (fr) * 2012-03-23 2013-09-26 株式会社Adeka Composition de résine durcissable contenant du silicium
WO2017010401A1 (fr) * 2015-07-10 2017-01-19 住友精化株式会社 Composition de résine époxy, son procédé de fabrication, et utilisations de ladite composition
WO2017086368A1 (fr) * 2015-11-18 2017-05-26 住友精化株式会社 Composition de résine époxy, procédé pour sa production et utilisation de la composition

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US11292872B2 (en) 2017-01-10 2022-04-05 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
US11603466B2 (en) 2017-01-10 2023-03-14 Sumitomo Seika Chemicals Co.. Ltd. Epoxy resin composition
WO2019026822A1 (fr) * 2017-07-31 2019-02-07 住友精化株式会社 Composition de résine époxyde

Also Published As

Publication number Publication date
JP6987791B2 (ja) 2022-01-05
TW201833214A (zh) 2018-09-16
JPWO2018131564A1 (ja) 2019-11-07

Similar Documents

Publication Publication Date Title
JP6556965B2 (ja) エポキシ樹脂組成物
WO2018131564A1 (fr) Composition de résine époxy
JP6530574B2 (ja) エポキシ樹脂組成物
EP3569628B1 (fr) Composition de résine époxyde
JP7146766B2 (ja) エポキシ樹脂組成物
US20190322858A1 (en) Epoxy resin composition
EP3378897A1 (fr) Composition de résine époxy, procédé pour sa production et utilisation de la composition
WO2018181719A1 (fr) Résine époxy, composition de résine époxy, et objet durci obtenu à partir de celle-ci, son utilisation et procédé de production
JP6553311B2 (ja) エポキシ樹脂組成物
CN114008104B (zh) 环氧树脂组合物
JP2024062263A (ja) エポキシ樹脂組成物

Legal Events

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

Ref document number: 18738748

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018561362

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18738748

Country of ref document: EP

Kind code of ref document: A1