US20190119434A1 - Epoxy resin composition, process for producing same, and uses of said composition - Google Patents
Epoxy resin composition, process for producing same, and uses of said composition Download PDFInfo
- Publication number
- US20190119434A1 US20190119434A1 US15/743,189 US201615743189A US2019119434A1 US 20190119434 A1 US20190119434 A1 US 20190119434A1 US 201615743189 A US201615743189 A US 201615743189A US 2019119434 A1 US2019119434 A1 US 2019119434A1
- Authority
- US
- United States
- Prior art keywords
- group
- epoxy resin
- anhydride
- resin composition
- 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.)
- Abandoned
Links
- 0 C1CCC2OC2C1.C1CCC2OC2C1.CC.CC.[1*][Si]([1*])([2*]C)C[Si]([1*])([1*])[2*]C Chemical compound C1CCC2OC2C1.C1CCC2OC2C1.CC.CC.[1*][Si]([1*])([2*]C)C[Si]([1*])([1*])[2*]C 0.000 description 9
- XSIQDSKILFNNPM-UHFFFAOYSA-N C1=CC=C([Y]C2=CC=CC=C2)C=C1.CC(C)C.CC(C)C Chemical compound C1=CC=C([Y]C2=CC=CC=C2)C=C1.CC(C)C.CC(C)C XSIQDSKILFNNPM-UHFFFAOYSA-N 0.000 description 3
- KJGRZWCUHXPMJX-UHFFFAOYSA-N CC(C)C1=CC=C([Y]C2=CC=C(C(C)C)C=C2)C=C1 Chemical compound CC(C)C1=CC=C([Y]C2=CC=C(C(C)C)C=C2)C=C1 KJGRZWCUHXPMJX-UHFFFAOYSA-N 0.000 description 2
- KFZRLMPLQBLWMG-UHFFFAOYSA-N C1C2OC1CCC2 Chemical compound C1C2OC1CCC2 KFZRLMPLQBLWMG-UHFFFAOYSA-N 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N C1CC2OC2CC1 Chemical compound C1CC2OC2CC1 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- PWWKUEVFHWDYPS-UHFFFAOYSA-N C1CCC2OC2C1.CC.CC Chemical compound C1CCC2OC2C1.CC.CC PWWKUEVFHWDYPS-UHFFFAOYSA-N 0.000 description 1
- ZTSVWFYHLXFYGF-UHFFFAOYSA-N CC.CC1CCC2OC2C1 Chemical compound CC.CC1CCC2OC2C1 ZTSVWFYHLXFYGF-UHFFFAOYSA-N 0.000 description 1
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
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
-
- 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
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4238—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof heterocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
-
- 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
- C08G59/686—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 containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1018—Macromolecular compounds having one or more carbon-to-silicon linkages
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
-
- 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
- C08G2190/00—Compositions for sealing or packing joints
Definitions
- the present invention relates to an epoxy resin composition, a process for producing the same, and use of the composition.
- Epoxy resins which are a type of thermosetting resin, are used in various fields, such as electric and electronic materials, coating compositions, adhesives, and composite materials, because cured products thereof have excellent heat resistance, electrical insulating properties, and like characteristics. Particularly in the field of electric and electronic materials, epoxy resins are used in semiconductor sealing materials, printed circuit board materials, etc.
- the frequency of transmission signals has recently increased along with an increase in the performance of electronic devices and a reduction in the weight and size thereof.
- materials used in printed circuit boards and semiconductor sealing materials are strongly required to have a lower dielectric constant in the high frequency region.
- Epoxy resins satisfy performance requirements for electrical insulating properties and heat resistance; however, highly polar hydroxyl groups are generated due to the reaction between epoxy group and active hydrogen, thereby increasing relative dielectric constant. Thus, satisfactory dielectric characteristics (low dielectric constant, etc.) are not obtained.
- PTL 6 reports a photocurable composition comprising a silicon-containing epoxy resin. Further, PTL 7 reports that a cured product is obtained using a silicon-containing epoxy resin and a curing agent.
- the content ratio of epoxy resin is reduced by using the epoxy resin in combination with other components, such as a phenol novolak resin, thereby improving the dielectric characteristics (achieving low dielectric constant and low dielectric loss tangent) of cured products of these compositions.
- other components such as a phenol novolak resin
- an object of the present invention is to provide an epoxy resin composition that can produce a cured product maintaining good dielectric characteristics (low dielectric constant and low dielectric loss tangent), and having high adhesion strength to metal; and to also provide a process for producing the same.
- Another object of the present invention is to provide a cured product obtained by curing the epoxy resin composition, and use thereof (e.g., as a semiconductor sealing material, a printed circuit board material, a composite material, etc.).
- an epoxy resin composition comprising a specific epoxy resin, an acid anhydride-based curing agent, and a curing accelerator, the epoxy resin containing a silicon atom having an alicyclic epoxy group.
- the present invention has been completed upon further studies based on this finding.
- the present invention includes an epoxy resin composition comprising a specific epoxy resin, an acid anhydride-based curing agent, and a curing accelerator, as well as a process for producing the same, and use thereof described below.
- Item 1 An epoxy resin composition comprising an epoxy resin, an acid anhydride-based curing agent, and a curing accelerator, the epoxy resin being represented by the formula (1):
- X is a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring, or a divalent group represented by the formula (2):
- Y is a bond, a C 1-6 alkylene group, an oxygen atom (—O—), or a group represented by the formula: —S(O) m — wherein m is 0, 1, or 2;
- Item 2 The epoxy resin composition according to claim 1 , wherein the curing accelerator is a nitrogen-containing curing accelerator.
- Item 3 The epoxy resin composition according to Item 2, wherein the nitrogen-containing curing accelerator is a tertiary amine compound or an imidazole compound.
- Item 4 The epoxy resin composition according to Item 2 or 3, wherein the nitrogen-containing curing accelerator is an imidazole compound.
- Item 5 The epoxy resin composition according to Item 2 or 3, wherein the nitrogen-containing curing accelerator is a tertiary amine compound.
- Item 6 A process for producing the epoxy resin composition according to Item 1, the process comprising mixing an epoxy resin represented by the formula (1), an acid anhydride-based curing agent, and a curing accelerator.
- Item 7 A cured product of the epoxy resin composition according to any one of Items 1 to 5.
- Item 8 A semiconductor sealing material, a liquid sealing material, a potting material, a sealing material, a printed circuit board material, or a composite material, each of which uses the epoxy resin composition according to any one of Items 1 to 5 or a cured product thereof (the cured product of the epoxy resin composition according to Item 7).
- Item 9 The epoxy resin composition according to any one of Items 1 to 5 for use in a semiconductor sealing material, a liquid sealing material, a potting material, a sealing material, a printed circuit board material, or a composite material.
- Item 10 Use of the epoxy resin composition according to any one of Items 1 to 5 for producing a semiconductor sealing material, a liquid sealing material, a potting material, a sealing material, a printed circuit board material, or a composite material.
- the epoxy resin composition of the present invention can produce a cured product maintaining good dielectric characteristics (low dielectric constant and low dielectric loss tangent) and having high adhesion strength to metal. Therefore, the epoxy resin composition of the present invention can be suitably used for applications, such as semiconductor sealing material, liquid sealing materials, potting materials, sealing materials, printed circuit board materials, and composite materials.
- the phrase ‘“containing” or “comprising” a component’ means that the component is contained, and that any other components may also be contained.
- this phrase includes the concept of “consisting of,” which means that only the component is contained, as well as the concept of “consisting essentially of,” which means that the component is essentially contained.
- the epoxy resin composition of the present invention characteristically comprises an epoxy resin represented by the formula (1), an acid anhydride-based curing agent, and a curing accelerator.
- the epoxy resin used in the present invention has a structure represented by the formula (1).
- R 1 is the same or different, and is a C 1-18 alkyl group, a C 2-9 alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group, wherein one or more carbon atoms of these groups may be replaced by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom.
- the one or more carbon atoms is preferably a carbon atom that is not directly bonded to the silicon atom.
- the one or more carbon atoms that may be replaced may be one or plural (e.g., 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom. In terms of ease of synthesis, etc., it is preferable that R 1 bonded to the same silicon atom be the same, and it is more preferable that all R 1 be the same.
- the C 1-18 alkyl group represented by R 1 is, for example, a linear or branched alkyl group. Examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, a 2,2,4-trimethylpentyl group, an n-octyl group, an isooctyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, and the like.
- Preferable is a C 1-10 alkyl group, more preferable is a C 1-6 alkyl group, even more preferable is a C 1-3
- the C 2-9 alkenyl group represented by R 1 is, for example, a linear or branched alkenyl group.
- Examples include a vinyl group, an allyl croup, a 2-propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and the like.
- Preferable is a C 2-4 alkenyl group.
- the cycloalkyl group represented by R 1 is, for example, a 3- to 8-membered-ring cycloalkyl group. Examples include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a methylcyclohexyl group, and the like.
- the aryl group represented by R 1 is, for example, a monocyclic or bicyclic aryl group. Examples include a phenyl group, a tolyl group, a xylyl group, an ethyl phenyl group, a naphthyl group, and the like. Preferable among them is a phenyl group.
- the aralkyl group represented by R 1 is, for example, a C 1-4 alkyl group substituted with an aryl group (particularly a phenyl group).
- Examples include a benzyl group, an ⁇ -phenethyl group, a ⁇ -phenethyl group, a ⁇ -methylphenethyl group, and the like.
- R 1 is preferably a C 1-3 alkyl group, and more preferably a methyl group.
- R 3 is the same or different, and is a C 1-18 alkyl group, a C 2-9 alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group, wherein one or more carbon atoms of these groups may be replaced by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom.
- the one or more carbon atoms that may be replaced may be one or plural (e.g., 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom.
- the one or more carbon atoms is preferably a carbon atom that is not directly bonded to the oxirane ring.
- Examples of the C 1-18 alkyl group, a C 2-9 alkenyl group, cycloalkyl group, aryl group, and aralkyl group represented by R 3 include the same corresponding substituents represented by R 1 described above.
- R 3 is preferably a C 1-3 alkyl group, and more preferably a methyl group.
- n is the same or different, and is an integer of 0 to 3 (0, 1, 2, or 3). n is preferably 0 or 1, and more preferably 0. n represents the number of R 3 bonded to one alicyclic epoxy group contained in the formula (1).
- the formula (1) includes two alicyclic epoxy groups bonded to R 2 and represented by:
- R 3 bonded to one of the alicyclic epoxy groups is regarded as R 3a
- R 3 bonded to the other alicyclic epoxy group is regarded as R 3b
- the formula (1) is the following formula (1′):
- each of R 3a may be the same or different, each of R 3b may also be the same or different, and 3a and R 3b may be the same or different.
- n of (R 3a ) n and n of (R 3b ) n may also be the same or different.
- the formula (1) also includes the embodiment of the formula (1′).
- the alicyclic epoxy group is preferably:
- n 1 or 0.
- the alicyclic epoxy group is particularly preferably:
- n 0.
- R 2 is the same or different, and is a C 1-18 alkylene group, or a linear or branched alkylene group.
- Examples include a methylene group, a methylmethylene group, an ethylmethylene group, a dimethylmethylene group, a diethylmethylene group, a dimethylene group (—CH 2 CH 2 —), a trimethylene group (—CH 2 CH 2 CH 2 —), a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a tridecamethylene group, and the like.
- Preferable is a C 2-10 alkylene group, more preferable is a C 2-4 alkylene group, even more preferable is a C 2 or C 3 alkylene group, (particularly a dimethylene group or a trimethylene group), and particularly preferable is a C 2 alkylene group (particularly a dimethylene group).
- one or more carbon atoms other than the carbon atom directly bonded to the silicon atom may be replaced by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom.
- the one or more carbon atoms is preferably a carbon atom that is not directly bonded to the oxirane ring.
- R 2 and R 3 be bonded to different carbon atoms in the alicyclic epoxy group.
- the “hydrocarbon ring” of the divalent group represented by X obtained by removing two hydrogen atoms from a hydrocarbon ring is a monocyclic or polycyclic (particularly bicyclic or tricyclic) aliphatic hydrocarbon ring, or a monocyclic or polycyclic aromatic hydrocarbon ring.
- Examples include a cyclopentane ring, a cyclohexane ring, a tetralin ring, a decahydronaphthalene ring, a 1,2,3,4,5,6,7,8-octahydronaphthalene ring, a norbornene ring, an adamantane ring, a benzene ring, a toluene ring, a xylene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a pyrene ring, a triphenylene ring, and the like.
- a cyclohexane ring and a benzene ring Preferable are a cyclohexane ring and a benzene ring.
- the divalent group represented by X is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group; and more preferably a 1,4-phenylene group.
- the C 1-6 alkylene group represented by Y is, for example, a chain or branched alkylene group.
- examples include a methylene group, a methylmethylene group, an ethylmethylene group, a dimethylmethylene group, a diethylmethylene group, a dimethylene group (—CH2CH 2 —), a trimethylene group (—CH 2 CH 2 CH 2 —), and the like.
- m is 0, 1, or 2; and preferably 0 or 2.
- Y is preferably a bond, an oxygen atom, a methylene group, a dimethylmethylene group, —S—, or —SO 2 —; and more preferably a bond, a dimethylmethylene group, an oxygen atom, or —SO 2 —.
- Y is preferably a bond, a dimethylmethylene group, an oxygen atom, or —SO 2 —.
- R 1 are C 1-3 , alkyl groups (particularly methyl groups), both n are 0, both R 2 are dimethylene groups, and X is a 1,4-phenylene group.
- the epoxy resin represented by the formula (1) (including the epoxy resins represented by the formulas (1′) and (1a)) can be produced by a known method, for example, based on or according to the disclosures of PTL 6 and PTL 7.
- the epoxy resin can be produced by the following reaction formula.
- R 2A is a C 1-18 alkylidene group or a C 2-18 alkenyl group, and other symbols are as defined above.
- the C 1-18 alkylidene group represented by R 2A is, for example, a linear or branched alkylidene group.
- Examples include a methylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a sec-butylidene group, a pentylidene group, an isopentylidene group, an octylidene group, an isooctylidene group, and the like.
- Preferable is a C 1-10 alkylidene group, more preferable is a C 1-4 alkylidene group, even more preferable is a C 1-3 alkylidene group, and particularly preferable is a methylidene group or an ethylidene group.
- the C 2-18 alkenyl group represented by R 2A is, for example, a linear or branched alkenyl group.
- 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, a cyclohexenyl group, and the like.
- Preferable is a C 2-10 alkenyl group, more preferable is a C 2-4 alkenyl group, even more preferable is a C 2 or C 3 alkenyl group, and particularly preferable is a vinyl group or an allyl group.
- the epoxy resin can be produced by hydrosilylation of the compound represented by the formula (3) and the compound represented by the formula (4). Hydrosilylation can be generally performed in the presence of a catalyst in the presence or absence of a solvent.
- the catalyst used in hydrosilylation may be a known catalyst.
- platinum-based catalysts such as platinum carbon, chloroplatinic acid, olefin complexes of platinum, alkenylsiloxane complexes of platinum, and carbonyl complexes of platinum
- rhodium-based catalysts such as tris(triphenylphosphine)rhodium
- iridium-based catalysts such as bis(cyclooctadienyl)dichloroiridium.
- These catalysts may be in the form of solvates (e.g., hydrates, alcoholates, etc.). Further, the catalyst may be used in the form of a solution obtained by dissolving the catalyst in an alcohol (e.g., ethanol) when used.
- the amount of the catalyst used may be an effective amount as the catalyst, and is not particularly limited.
- the amount of the catalyst used is generally 0.00001 to 20 parts by mass, and preferably 0.0005 to 5 parts by mass, based on the total amount of 100 parts by mass of the compound represented the formula (3) and the compound represented by the formula (4).
- solvents 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; and the like. These may be used singly or in combination of two or more.
- the amount of the compound represented by the formula (4) is generally 0.5 to 2 mol, preferably 0.6 to 1.5 mol, and more preferably 0.8 to 1.2 mol, per mol of the Si—H group in the compound represented by the formula (3).
- the reaction temperature is 20° C. to 150° C., and preferably 50° C. to 120° C.
- the reaction time is about 1 hour to 24 hours.
- the epoxy resin composition of the present invention may contain an epoxy resin other than the epoxy resin represented by the formula (1) within a range in which the effects of the present invention can be exhibited.
- examples include bisphenol A epoxy resins, bisphenol F epoxy resins, phenol novolak epoxy resins, cresol novolak epoxy resins, cycloaliphatic epoxy resins, brominated epoxy resins, nitrogen-containing ring epoxy resins such as triglycidyl isocyanurate- and hydantoin-type epoxy resins, hydrogenated bisphenol A epoxy resins, aliphatic epoxy resins, glycidyl ether epoxy resins, bisphenol S epoxy resins, biphenyl epoxy resins, dicyclo epoxy resins, naphthalene epoxy resins, and the like. These epoxy resins may be used singly or in combination of two or more.
- the acid anhydride-based curing agent used in the present invention may be a known acid anhydride-based curing agent.
- Examples include cyclic aliphatic acid anhydrides, aromatic acid anhydrides, aliphatic acid anhydrides, and the like. Specific examples include hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 1-methylnorbornane-2,3-dicarboxylic anhydride, 5-methylnorbornane-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, 1-methylnadic anhydride, 5-methylnadic anhydride, nadic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and the like.
- cyclic aliphatic acid anhydrides such as hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride.
- These curing agents may be used singly or in combination of two or more.
- the amount of acid anhydride-based curing agent used is not particularly limited; however, the amount of the active group (acid anhydride group) in the curing agent reactive with the epoxy group is preferably 0.5 to 1.5 equivalents, and more preferably 0.7 to 1.2 equivalents, per equivalent of the epoxy group in the epoxy resin composition.
- the epoxy resin composition of the present invention may contain a curing agent other than the acid anhydride-based curing agent within a range in which the effects of the present invention can be exhibited.
- a curing agent other than the acid anhydride-based curing agent within a range in which the effects of the present invention can be exhibited.
- examples include aliphatic polyamines, such as triethylenetetramine; polyaminoamide; polymercaptans; aromatic polyamines, such as diaminodiphenylmethane; phenol novolak resin; dicyandiamide; and the like.
- the acid anhydride-based curing agent used in the epoxy resin composition of the present invention has a long pot life and low toxicity; however, the curing reaction may proceed relatively slowly, and curing may require a high temperature and a long period of time. Accordingly, it is preferable to use a curing accelerator in combination.
- curing accelerators include tertiary amine compounds, such as benzyldimethylamine, cyclohexyldimethylamine, pyridine, triethanolamine, 2-(dimethylaminomethyl)phenol, dimethylpiperazine, 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DEN), 1,4-diazabicyclo[2.2.2]octane (DABCO), and 2,4,6-tris(dimethylaminomethyl)phenol; imidazole compounds, such as 2-methylimidazole, 2-ethylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethyl
- a curing accelerator containing a nitrogen atom is preferably used.
- a nitrogen-containing curing accelerator is used, an epoxy resin composition having better metal adhesion can be obtained.
- a tertiary amine compound or an imidazole compound as a curing accelerator, thereby obtaining an epoxy resin composition having good heat resistance and metal adhesion.
- the amount of the nitrogen-containing curing accelerator is not particularly limited; however, the amount of the nitrogen-containing curing accelerator is preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the epoxy resin in the epoxy resin composition, because an epoxy resin composition that can produce a cured product having good heat resistance and metal adhesion is obtained.
- the specific epoxy resins, acid anhydride-based curing agents, and curing accelerators mentioned above can be used in any combination. Although it is not particularly limited, it is preferable to use the epoxy resin represented by the formula (1) (including the epoxy resins represented by the formulas (1′) and (1a)) in combination with a cyclic aliphatic acid anhydride as an acid anhydride-based curing agent, and a tertiary amine compound or an imidazole compound as a curing accelerator (a nitrogen-containing curing accelerator).
- the epoxy resin represented by the formula (1) in combination with at least one acid anhydride-based curing agent selected from the group consisting of hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride, and at least one curing accelerator selected from the group consisting of 2-ethyl-4-methylimidazole, 2,4,6-tris(dimethylaminomethyl)phenol, 1,4-diazabicyclo[2.2.2]octane, and 1,8-diazabicyclo[5.4.0]undec-7-ene.
- at least one acid anhydride-based curing agent selected from the group consisting of hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride
- at least one curing accelerator selected from the group consisting of 2-ethyl-4-methylimidazole, 2,4,6-tris(dimethylamino
- the epoxy resin composition of the present invention may optionally contain additives within a range that does not impair the objects and effects of the present invention.
- additives include inorganic fillers, fibrous reinforcing agents, antioxidants, inorganic fluorescent substances, lubricants, ultraviolet absorbers, heat light stabilizers, dispersants, antistatic agents, polymerization inhibitors, antifoaming agents, solvents, anti-aging agents, radical inhibitors, adhesion-improving agents, flame retardants, surfactants, storage stability-improving agents, ozone aging inhibitors, thickeners, plasticizers, radiation-blocking agents, nucleating agents, coupling agents, conductivity-imparting agents, phosphorus-based peroxide-decomposing agents, pigments, metal deactivators, physical property-controlling agents, and the like.
- the epoxy resin composition of the present invention can be produced by mixing the epoxy resin represented by the formula (1), an acid anhydride-based curing agent, and a curing accelerator, and further optionally other components.
- the mixing method is not particularly limited, as long as it allows uniform mixing.
- a cured product can be obtained by curing the epoxy resin composition of the present invention.
- the curing method is not particularly limited; for example, the composition can be cured by heating.
- the epoxy resin composition can be dissolved in a solvent (e.g., toluene, acetone, etc.) to prepare a varnish, and then the varnish can be applied to a substrate (e.g., copper foil, aluminum foil, a polyimide film, etc.), followed by heating, thereby obtaining a film-like cured product.
- the curing temperature is generally room temperature to 200° C.
- the curing time varies depending on the composition liquid, and can be generally widely set from 30 minutes to 1 week.
- a cured product obtained by curing the epoxy resin composition of the present invention has good dielectric characteristics (low dielectric constant and low dielectric loss tangent) and high adhesion strength to metal, such as copper and aluminum; therefore, for example, the cured product can be suitably used for applications, such as semiconductor sealing materials, liquid sealing materials, potting materials, sealing materials, printed circuit board materials, and composite materials.
- the present invention includes a semiconductor sealing material, a liquid sealing material, a potting material, a sealing material, a printed circuit board material, and a composite material, each of which uses the epoxy resin composition or a cured product thereof.
- 1,2-Epoxy-4-vinylcyclohexane 25 g
- 0.25 g of 2 wt % ethanol solution of hexachloroplatinic acid hexahydrate 250 g
- toluene 250 g
- toluene 250 g
- 20 g of 1,4-bis(dimethylsilyl)benzene was slowly added dropwise, and the mixture was then stirred at 90° C. for 4 hours.
- 42 g of slightly yellow liquid epoxy resin A:
- the epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each applied to an aluminum plate (JIS A1050P) (size: 2 ⁇ 25 ⁇ 100 mm) so that the adhesive part had a rectangular shape (12.5 ⁇ 25 mm). Then, another aluminum plate was bonded thereto, and cured by heating at 100° C. for 1 hour, 120° C. for 2 hours, and 150° C. for 2 hours. Thus, tensile shear adhesion test pieces were obtained.
- the obtained adhesion test pieces were each subjected to a tensile shear adhesion test using a tensile tester (AGS-X, produced by Shimadzu Corp.) with a clamp distance of 100 mm at a test rate of 5 mm/min, and the tensile shear adhesion strength was calculated from the measured maximum breaking strength and the adhesion area. Table 1 shows the results.
- the epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each applied to an aluminum plate (JIS A1050P) (size: 2 ⁇ 25 ⁇ 100 mm) so that the adhesive part had a rectangular shape (12.5 ⁇ 25 mm). Then, another aluminum plate was bonded thereto, and cured by heating at 100° C. for 1 hour, 120° C. for 2 hours, and 150° C. for 2 hours. Thus, tensile shear adhesion test pieces were obtained.
- the obtained adhesion test pieces were allowed to stand in an atmosphere at 85° C. with 85% RH for 168 hours. Subsequently, the test pieces were each subjected to a tensile shear adhesion test using a tensile tester (AGS-X, produced by Shimadzu Corp.) with a clamp distance of 100 mm at a test rate of 5 mm/min, and the tensile shear adhesion strength was calculated from the measured maximum breaking strength and the adhesion area.
- AGS-X tensile tester
- the maintenance rate (%) of tensile shear adhesion strength to aluminum after the high-temperature high-humidity test was calculated by dividing the tensile shear adhesion strength to aluminum after the high-temperature high-humidity test by the tensile shear adhesion strength to aluminum before the high-temperature high-humidity test. Table 1 shows the results.
- the epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each applied to an oxygen-free copper plate (JIS C1020P) (size: 2 ⁇ 25 ⁇ 100 mm) so that the adhesive part had a rectangular shape (12.5 ⁇ 25 mm). Then, another oxygen-free copper plate was bonded thereto, and cured by heating at 100° C. for 1 hour, 120° C. for 2 hours, and 150° C. for 2 hours. Thus, tensile shear adhesion test pieces were obtained.
- JIS C1020P oxygen-free copper plate
- the obtained adhesion test pieces were each subjected to a tensile shear adhesion test using a tensile tester (AGS-X, produced by Shimadzu Corp.) with a clamp distance of 100 mm at a test rate of 5 mm/min, and the tensile shear adhesion strength was calculated from the measured maximum breaking strength and the adhesion area. Table 1 shows the results.
- the epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each applied to an oxygen-free copper plate (JIS C1020P) (size: 2 ⁇ 25 ⁇ 100 mm) so that the adhesive part had a rectangular shape (12.5 ⁇ 25 mm). Then, another oxygen-free copper plate was bonded thereto, and cured by heating at 100° C. for 1 hour, 120° C. for 2 hours, and 150° C. for 2 hours. Thus, tensile shear adhesion test pieces were obtained.
- JIS C1020P oxygen-free copper plate
- the obtained adhesion test pieces were allowed to stand in an atmosphere at 85° C. with 85% RH for 168 hours. Subsequently, the test pieces were each subjected to a tensile shear adhesion test using a tensile tester (AGS-X, produced by Shimadzu Corp.) with a clamp distance of 100 mm at a test rate of 5 mm/min, and the tensile shear adhesion strength was calculated from the measured maximum breaking strength and the adhesion area.
- AGS-X tensile tester
- the maintenance rate (5) of tensile shear adhesion strength to copper after the high-temperature high-humidity test was calculated by dividing the tensile shear adhesion strength to copper after the high-temperature high-humidity test by the tensile shear adhesion strength to copper before the high-temperature high-humidity test. Table 1 shows the results.
- the epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each poured into a resin mold (thickness: 2 mm), and cured by heating at 100° C. for 1 hour, 120° C. for 2 hours, and 150° C. for 2 hours. Thus, test pieces for dielectric measurement were obtained.
- test pieces were each calibrated with PTFE using a dielectric constant measuring device (Impedance Analyzer, produced by Agilent), and then the relative dielectric constant (1 GHz) and the dielectric loss tangent (1 GHz) were measured. Table 1 shows the results.
- the epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each poured into a resin mold, and cured by heating at 100° C. for 1 hour, 120° C. for 2 hours, and 150° C. for 2 hours. Thus, test pieces for glass transition temperature measurement were obtained.
- the glass transition temperature of the obtained test pieces was measured using a thermomechanical analyzer (SSC5200, produced by SII Nanotechnology Inc.) in compressed mode at a load of 50 mN at 5° C./min. Table 1 shows the results.
- the epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each poured into a resin mold, and cured by heating at 100° C. for 1 hour, 120° C. for 2 hours, and 150° C. for 2 hours. After the glass transition temperature of the cured test pieces was measured, the test pieces after measurement were observed, and the presence of cracks was evaluated based on their appearance.
- Example 2 Example 3
- Example 4 Example 1
- Example 2 Epoxy resin A 100 100 100 100 100 100 0 0 Epoxy resin B 0 0 0 0 100 100 100 Acid anhydride-based curing agent 76 76 76 88 88 Curing accelerator A 1 0 0 0 1 0 Curing accelerator B 0 1 0 0 0 0 Curing accelerator C 0 0 1 0 0 0 Curing accelerator D 0 0 0 1 0 1
- the epoxy resin compositions obtained in Examples 1 to 4 have high adhesion strength to metal. In particular, even after the high-temperature high-humidity test, they can maintain high adhesion strength and have adhesion reliability. Furthermore, they have good dielectric characteristics and heat resistance.
- the epoxy resin compositions obtained in Comparative Examples 1 and 2 have a certain degree of initial adhesion strength to metal; however, their adhesion was rapidly reduced after the high-temperature high-humidity test. In addition, it was confirmed that their dielectric characteristics and heat resistance were inferior to those of the epoxy resin compositions obtained in Examples 1 to 4.
Abstract
The present invention also includes a process for producing the same, a cured product of the epoxy resin composition, and use thereof.
Description
- The present invention relates to an epoxy resin composition, a process for producing the same, and use of the composition.
- Epoxy resins, which are a type of thermosetting resin, are used in various fields, such as electric and electronic materials, coating compositions, adhesives, and composite materials, because cured products thereof have excellent heat resistance, electrical insulating properties, and like characteristics. Particularly in the field of electric and electronic materials, epoxy resins are used in semiconductor sealing materials, printed circuit board materials, etc.
- The frequency of transmission signals has recently increased along with an increase in the performance of electronic devices and a reduction in the weight and size thereof. In accordance with the increased frequency, materials used in printed circuit boards and semiconductor sealing materials are strongly required to have a lower dielectric constant in the high frequency region.
- Epoxy resins satisfy performance requirements for electrical insulating properties and heat resistance; however, highly polar hydroxyl groups are generated due to the reaction between epoxy group and active hydrogen, thereby increasing relative dielectric constant. Thus, satisfactory dielectric characteristics (low dielectric constant, etc.) are not obtained.
- Accordingly, for the purpose of improving the dielectric characteristics (achieving low dielectric constant and low dielectric loss tangent) of epoxy resins, resin compositions comprising an epoxy resin in combination with a phenol novolak resin or the like are reported (PTL 1 to PTL 5, etc.).
- Moreover, in copper wiring used in substrate materials, the development of low-roughness copper foil and copper plating corresponding to the increased frequency of transmission signals has been advanced. However, if the surface roughness of copper wiring is low, the anchor effect of copper and epoxy resin is reduced, thereby making it difficult to ensure adhesion strength. For this reason, there is a demand for epoxy resins having sufficient adhesion to copper wiring that has low surface roughness and a small anchor effect.
- PTL 6 reports a photocurable composition comprising a silicon-containing epoxy resin. Further, PTL 7 reports that a cured product is obtained using a silicon-containing epoxy resin and a curing agent.
- PTL 1: JP1995-157540A
- PTL 2: JP2005-187800A
- PTL 3: JP2009-227992A
- PTL 4: JPH06-192393A
- PTL 5: JPH08-325355A
- PTL 6: JP2012-001668A
- PTL 7: GB123960
- In the compositions of PTL 1 to PTL 5, the content ratio of epoxy resin is reduced by using the epoxy resin in combination with other components, such as a phenol novolak resin, thereby improving the dielectric characteristics (achieving low dielectric constant and low dielectric loss tangent) of cured products of these compositions. However, there was a problem such that sufficient adhesion strength to metal, such as copper and aluminum, was not achieved.
- Accordingly, an object of the present invention is to provide an epoxy resin composition that can produce a cured product maintaining good dielectric characteristics (low dielectric constant and low dielectric loss tangent), and having high adhesion strength to metal; and to also provide a process for producing the same.
- Another object of the present invention is to provide a cured product obtained by curing the epoxy resin composition, and use thereof (e.g., as a semiconductor sealing material, a printed circuit board material, a composite material, etc.).
- As a result of extensive research to solve the above problem, the present inventor found that the above problem can be solved by an epoxy resin composition comprising a specific epoxy resin, an acid anhydride-based curing agent, and a curing accelerator, the epoxy resin containing a silicon atom having an alicyclic epoxy group. The present invention has been completed upon further studies based on this finding.
- The present invention includes an epoxy resin composition comprising a specific epoxy resin, an acid anhydride-based curing agent, and a curing accelerator, as well as a process for producing the same, and use thereof described below.
- Item 1. An epoxy resin composition comprising an epoxy resin, an acid anhydride-based curing agent, and a curing accelerator, the epoxy resin being represented by the formula (1):
- wherein X is a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring, or a divalent group represented by the formula (2):
- wherein Y is a bond, a C1-6 alkylene group, an oxygen atom (—O—), or a group represented by the formula: —S(O)m— wherein m is 0, 1, or 2;
-
- R1 is the same or different, and is a C1-18 alkyl group, a C2-9 alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group, wherein one or more carbon atoms of these groups may be replaced by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom;
- R2 is the same or different, and is a C1-18 alkylene group, wherein one or more carbon atoms of this group other than a carbon atom directly bonded to a silicon atom may be replaced by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom;
- R3 is the same or different, and is a C1-18 alkyl group, a C2-9 alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group, wherein one or more carbon atoms of these groups may be replaced by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; and
- n is the same or different, and is an integer of 0 to 3.
- Item 2. The epoxy resin composition according to claim 1, wherein the curing accelerator is a nitrogen-containing curing accelerator.
- Item 3. The epoxy resin composition according to Item 2, wherein the nitrogen-containing curing accelerator is a tertiary amine compound or an imidazole compound.
- Item 4. The epoxy resin composition according to Item 2 or 3, wherein the nitrogen-containing curing accelerator is an imidazole compound.
- Item 5. The epoxy resin composition according to Item 2 or 3, wherein the nitrogen-containing curing accelerator is a tertiary amine compound.
- Item 6. A process for producing the epoxy resin composition according to Item 1, the process comprising mixing an epoxy resin represented by the formula (1), an acid anhydride-based curing agent, and a curing accelerator.
- Item 7. A cured product of the epoxy resin composition according to any one of Items 1 to 5.
- Item 8. A semiconductor sealing material, a liquid sealing material, a potting material, a sealing material, a printed circuit board material, or a composite material, each of which uses the epoxy resin composition according to any one of Items 1 to 5 or a cured product thereof (the cured product of the epoxy resin composition according to Item 7).
- Item 9. The epoxy resin composition according to any one of Items 1 to 5 for use in a semiconductor sealing material, a liquid sealing material, a potting material, a sealing material, a printed circuit board material, or a composite material.
- Item 10. Use of the epoxy resin composition according to any one of Items 1 to 5 for producing a semiconductor sealing material, a liquid sealing material, a potting material, a sealing material, a printed circuit board material, or a composite material.
- The epoxy resin composition of the present invention can produce a cured product maintaining good dielectric characteristics (low dielectric constant and low dielectric loss tangent) and having high adhesion strength to metal. Therefore, the epoxy resin composition of the present invention can be suitably used for applications, such as semiconductor sealing material, liquid sealing materials, potting materials, sealing materials, printed circuit board materials, and composite materials.
- In the present specification, the phrase ‘“containing” or “comprising” a component’ means that the component is contained, and that any other components may also be contained. In addition, this phrase includes the concept of “consisting of,” which means that only the component is contained, as well as the concept of “consisting essentially of,” which means that the component is essentially contained.
- The present invention is described in detail below.
- The epoxy resin composition of the present invention characteristically comprises an epoxy resin represented by the formula (1), an acid anhydride-based curing agent, and a curing accelerator.
- The epoxy resin used in the present invention has a structure represented by the formula (1). In the formula (1), R1 is the same or different, and is a C1-18 alkyl group, a C2-9 alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group, wherein one or more carbon atoms of these groups may be replaced by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. The one or more carbon atoms is preferably a carbon atom that is not directly bonded to the silicon atom. The one or more carbon atoms that may be replaced may be one or plural (e.g., 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom. In terms of ease of synthesis, etc., it is preferable that R1 bonded to the same silicon atom be the same, and it is more preferable that all R1 be the same.
- The C1-18 alkyl group represented by R1 is, for example, a linear or branched alkyl group. Examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, a 2,2,4-trimethylpentyl group, an n-octyl group, an isooctyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, and the like. Preferable is a C1-10 alkyl group, more preferable is a C1-6 alkyl group, even more preferable is a C1-3 alkyl group, and particularly preferable is a methyl group.
- The C2-9 alkenyl group represented by R1 is, for example, a linear or branched alkenyl group. Examples include a vinyl group, an allyl croup, a 2-propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and the like. Preferable is a C2-4 alkenyl group.
- The cycloalkyl group represented by R1 is, for example, a 3- to 8-membered-ring cycloalkyl group. Examples include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a methylcyclohexyl group, and the like.
- The aryl group represented by R1 is, for example, a monocyclic or bicyclic aryl group. Examples include a phenyl group, a tolyl group, a xylyl group, an ethyl phenyl group, a naphthyl group, and the like. Preferable among them is a phenyl group.
- The aralkyl group represented by R1 is, for example, a C1-4 alkyl group substituted with an aryl group (particularly a phenyl group). Examples include a benzyl group, an α-phenethyl group, a β-phenethyl group, a β-methylphenethyl group, and the like.
- R1 is preferably a C1-3 alkyl group, and more preferably a methyl group.
- In the formula (1), R3 is the same or different, and is a C1-18 alkyl group, a C2-9 alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group, wherein one or more carbon atoms of these groups may be replaced by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. The one or more carbon atoms that may be replaced may be one or plural (e.g., 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom. When R3 is directly bonded to the oxirane ring, the one or more carbon atoms is preferably a carbon atom that is not directly bonded to the oxirane ring.
- Examples of the C1-18 alkyl group, a C2-9 alkenyl group, cycloalkyl group, aryl group, and aralkyl group represented by R3 include the same corresponding substituents represented by R1 described above.
- R3 is preferably a C1-3 alkyl group, and more preferably a methyl group.
- In the formula (1), n is the same or different, and is an integer of 0 to 3 (0, 1, 2, or 3). n is preferably 0 or 1, and more preferably 0. n represents the number of R3 bonded to one alicyclic epoxy group contained in the formula (1).
- The formula (1) includes two alicyclic epoxy groups bonded to R2 and represented by:
- When R3 bonded to one of the alicyclic epoxy groups is regarded as R3a, whereas R3 bonded to the other alicyclic epoxy group is regarded as R3b, that is, when the formula (1) is the following formula (1′):
- wherein R1, R2, X, and n are as defined in the formula (1), each of R3a may be the same or different, each of R3b may also be the same or different, and 3a and R3b may be the same or different. In this case, n of (R3a)n and n of (R3b)n may also be the same or different. The formula (1) also includes the embodiment of the formula (1′).
- The alicyclic epoxy group is preferably:
- In this group, it is particularly preferable that n be 1 or 0. The alicyclic epoxy group is particularly preferably:
- It is even more preferable that n be 0.
- In the formula (1), R2 is the same or different, and is a C1-18 alkylene group, or a linear or branched alkylene group. Examples include a methylene group, a methylmethylene group, an ethylmethylene group, a dimethylmethylene group, a diethylmethylene group, a dimethylene group (—CH2CH2—), a trimethylene group (—CH2CH2CH2—), a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a tridecamethylene group, and the like. Preferable is a C2-10 alkylene group, more preferable is a C2-4 alkylene group, even more preferable is a C2 or C3 alkylene group, (particularly a dimethylene group or a trimethylene group), and particularly preferable is a C2 alkylene group (particularly a dimethylene group).
- In the C1-18 alkylene group, one or more carbon atoms other than the carbon atom directly bonded to the silicon atom may be replaced by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. When R2 is directly bonded to the oxirane ring, the one or more carbon atoms is preferably a carbon atom that is not directly bonded to the oxirane ring.
- It is preferable that R2 and R3 be bonded to different carbon atoms in the alicyclic epoxy group.
- In the formula (1), the “hydrocarbon ring” of the divalent group represented by X obtained by removing two hydrogen atoms from a hydrocarbon ring is a monocyclic or polycyclic (particularly bicyclic or tricyclic) aliphatic hydrocarbon ring, or a monocyclic or polycyclic aromatic hydrocarbon ring. Examples include a cyclopentane ring, a cyclohexane ring, a tetralin ring, a decahydronaphthalene ring, a 1,2,3,4,5,6,7,8-octahydronaphthalene ring, a norbornene ring, an adamantane ring, a benzene ring, a toluene ring, a xylene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a pyrene ring, a triphenylene ring, and the like. Preferable are a cyclohexane ring and a benzene ring. The divalent group represented by X is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group; and more preferably a 1,4-phenylene group.
- In the formula (2), the C1-6 alkylene group represented by Y is, for example, a chain or branched alkylene group. Examples include a methylene group, a methylmethylene group, an ethylmethylene group, a dimethylmethylene group, a diethylmethylene group, a dimethylene group (—CH2CH2—), a trimethylene group (—CH2CH2CH2—), and the like.
- In the formula (2), m is 0, 1, or 2; and preferably 0 or 2.
- Y is preferably a bond, an oxygen atom, a methylene group, a dimethylmethylene group, —S—, or —SO2—; and more preferably a bond, a dimethylmethylene group, an oxygen atom, or —SO2—.
- Preferable among the divalent groups represented by the formula (2) is a group represented by the formula (2a):
- wherein Y is as defined above.
- In the formula (2a), Y is preferably a bond, a dimethylmethylene group, an oxygen atom, or —SO2—.
- Preferable among the epoxy resins represented by the formula (1) is a compound represented by the formula (1a):
- wherein each symbol is as defined above.
- It is preferable that in the formula (1a), all R1 are C1-3 , alkyl groups (particularly methyl groups), both n are 0, both R2 are dimethylene groups, and X is a 1,4-phenylene group.
- The epoxy resin represented by the formula (1) (including the epoxy resins represented by the formulas (1′) and (1a)) can be produced by a known method, for example, based on or according to the disclosures of PTL 6 and PTL 7. As a specific example, the epoxy resin can be produced by the following reaction formula.
- wherein R2A is a C1-18 alkylidene group or a C2-18 alkenyl group, and other symbols are as defined above.
- The C1-18 alkylidene group represented by R2A is, for example, a linear or branched alkylidene group. Examples include a methylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a sec-butylidene group, a pentylidene group, an isopentylidene group, an octylidene group, an isooctylidene group, and the like. Preferable is a C1-10 alkylidene group, more preferable is a C1-4 alkylidene group, even more preferable is a C1-3 alkylidene group, and particularly preferable is a methylidene group or an ethylidene group.
- The C2-18 alkenyl group represented by R2A is, for example, a linear or branched alkenyl group. 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, a cyclohexenyl group, and the like. Preferable is a C2-10 alkenyl group, more preferable is a C2-4 alkenyl group, even more preferable is a C2 or C3 alkenyl group, and particularly preferable is a vinyl group or an allyl group.
- The epoxy resin can be produced by hydrosilylation of the compound represented by the formula (3) and the compound represented by the formula (4). Hydrosilylation can be generally performed in the presence of a catalyst in the presence or absence of a solvent.
- The catalyst used in hydrosilylation may be a known catalyst. Examples include platinum-based catalysts, such as platinum carbon, chloroplatinic acid, olefin complexes of platinum, alkenylsiloxane complexes of platinum, and carbonyl complexes of platinum; rhodium-based catalysts, such as tris(triphenylphosphine)rhodium; and iridium-based catalysts, such as bis(cyclooctadienyl)dichloroiridium. These catalysts may be in the form of solvates (e.g., hydrates, alcoholates, etc.). Further, the catalyst may be used in the form of a solution obtained by dissolving the catalyst in an alcohol (e.g., ethanol) when used.
- The amount of the catalyst used may be an effective amount as the catalyst, and is not particularly limited. The amount of the catalyst used is generally 0.00001 to 20 parts by mass, and preferably 0.0005 to 5 parts by mass, based on the total amount of 100 parts by mass of the compound represented the formula (3) and the compound represented by the formula (4).
- Although hydrosilylation proceeds without use of a solvent, the reaction can be carried out under milder conditions by using a solvent. Examples of solvents 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; and the like. These may be used singly or in combination of two or more.
- The amount of the compound represented by the formula (4) is generally 0.5 to 2 mol, preferably 0.6 to 1.5 mol, and more preferably 0.8 to 1.2 mol, per mol of the Si—H group in the compound represented by the formula (3).
- The reaction temperature is 20° C. to 150° C., and preferably 50° C. to 120° C. The reaction time is about 1 hour to 24 hours.
- After completion of the reaction, for example, the solvent is distilled off from the reaction mixture, thereby obtaining an epoxy resin represented by the formula (1).
- The epoxy resin composition of the present invention may contain an epoxy resin other than the epoxy resin represented by the formula (1) within a range in which the effects of the present invention can be exhibited. Examples include bisphenol A epoxy resins, bisphenol F epoxy resins, phenol novolak epoxy resins, cresol novolak epoxy resins, cycloaliphatic epoxy resins, brominated epoxy resins, nitrogen-containing ring epoxy resins such as triglycidyl isocyanurate- and hydantoin-type epoxy resins, hydrogenated bisphenol A epoxy resins, aliphatic epoxy resins, glycidyl ether epoxy resins, bisphenol S epoxy resins, biphenyl epoxy resins, dicyclo epoxy resins, naphthalene epoxy resins, and the like. These epoxy resins may be used singly or in combination of two or more.
- The acid anhydride-based curing agent used in the present invention may be a known acid anhydride-based curing agent. Examples include cyclic aliphatic acid anhydrides, aromatic acid anhydrides, aliphatic acid anhydrides, and the like. Specific examples include hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 1-methylnorbornane-2,3-dicarboxylic anhydride, 5-methylnorbornane-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, 1-methylnadic anhydride, 5-methylnadic anhydride, nadic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and the like. Preferable are cyclic aliphatic acid anhydrides, such as hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride. These curing agents may be used singly or in combination of two or more.
- The amount of acid anhydride-based curing agent used is not particularly limited; however, the amount of the active group (acid anhydride group) in the curing agent reactive with the epoxy group is preferably 0.5 to 1.5 equivalents, and more preferably 0.7 to 1.2 equivalents, per equivalent of the epoxy group in the epoxy resin composition.
- The epoxy resin composition of the present invention may contain a curing agent other than the acid anhydride-based curing agent within a range in which the effects of the present invention can be exhibited. Examples include aliphatic polyamines, such as triethylenetetramine; polyaminoamide; polymercaptans; aromatic polyamines, such as diaminodiphenylmethane; phenol novolak resin; dicyandiamide; and the like.
- The acid anhydride-based curing agent used in the epoxy resin composition of the present invention has a long pot life and low toxicity; however, the curing reaction may proceed relatively slowly, and curing may require a high temperature and a long period of time. Accordingly, it is preferable to use a curing accelerator in combination.
- Examples of curing accelerators include tertiary amine compounds, such as benzyldimethylamine, cyclohexyldimethylamine, pyridine, triethanolamine, 2-(dimethylaminomethyl)phenol, dimethylpiperazine, 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DEN), 1,4-diazabicyclo[2.2.2]octane (DABCO), and 2,4,6-tris(dimethylaminomethyl)phenol; imidazole compounds, such as 2-methylimidazole, 2-ethylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole, 1-(2-cyanoethyl)-2-n-undecylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di(hydroxymethyl)imidazole, 1-(2-cyanoethyl)-2-phenyl-4,5-di((2′-cyanoethoxy)methyl)imidazole, 1-(2-cyanoethyl)-2-n-undecyl imidazolium trimellitate, 1-(2-cyanoethyl)-2-phenyl imidazolium trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methyl imidazolium trimellitate, 2,4-diamino-6-(2′-methylimidazolyl-(1′))ethyl-s-triazine, 2,4-diamino-6-(2′-n-undecylimidazolyl)ethyl-s-triazine, 2,4-diamino-6-(2′-ethyl-4′-methylimidazolyl-(1′))ethyl-s-triazine, isocyanuric acid adducts of 2-methylimidazole, isocyanuric acid adducts of 2-phenylimidazole, and isocyanuric acid adducts of 2,4-diamino-6-(2′-methylimidazolyl-(1′))ethyl-s-triazine; phosphine compounds, such as triphenylphosphine; phosphonium salts, such as tetraphenyl phosphonium tetraphenyl borate; metal compounds, such as tin octylate; and the like. These may be used singly or in combination of two or more.
- Among these, a curing accelerator containing a nitrogen atom is preferably used. When a nitrogen-containing curing accelerator is used, an epoxy resin composition having better metal adhesion can be obtained.
- It is more preferable to use a tertiary amine compound or an imidazole compound as a curing accelerator, thereby obtaining an epoxy resin composition having good heat resistance and metal adhesion.
- The amount of the nitrogen-containing curing accelerator is not particularly limited; however, the amount of the nitrogen-containing curing accelerator is preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the epoxy resin in the epoxy resin composition, because an epoxy resin composition that can produce a cured product having good heat resistance and metal adhesion is obtained.
- The specific epoxy resins, acid anhydride-based curing agents, and curing accelerators mentioned above can be used in any combination. Although it is not particularly limited, it is preferable to use the epoxy resin represented by the formula (1) (including the epoxy resins represented by the formulas (1′) and (1a)) in combination with a cyclic aliphatic acid anhydride as an acid anhydride-based curing agent, and a tertiary amine compound or an imidazole compound as a curing accelerator (a nitrogen-containing curing accelerator). Further, it is more preferable to use the epoxy resin represented by the formula (1) in combination with at least one acid anhydride-based curing agent selected from the group consisting of hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride, and at least one curing accelerator selected from the group consisting of 2-ethyl-4-methylimidazole, 2,4,6-tris(dimethylaminomethyl)phenol, 1,4-diazabicyclo[2.2.2]octane, and 1,8-diazabicyclo[5.4.0]undec-7-ene.
- The epoxy resin composition of the present invention may optionally contain additives within a range that does not impair the objects and effects of the present invention. Examples of additives include inorganic fillers, fibrous reinforcing agents, antioxidants, inorganic fluorescent substances, lubricants, ultraviolet absorbers, heat light stabilizers, dispersants, antistatic agents, polymerization inhibitors, antifoaming agents, solvents, anti-aging agents, radical inhibitors, adhesion-improving agents, flame retardants, surfactants, storage stability-improving agents, ozone aging inhibitors, thickeners, plasticizers, radiation-blocking agents, nucleating agents, coupling agents, conductivity-imparting agents, phosphorus-based peroxide-decomposing agents, pigments, metal deactivators, physical property-controlling agents, and the like.
- The epoxy resin composition of the present invention can be produced by mixing the epoxy resin represented by the formula (1), an acid anhydride-based curing agent, and a curing accelerator, and further optionally other components. The mixing method is not particularly limited, as long as it allows uniform mixing.
- A cured product can be obtained by curing the epoxy resin composition of the present invention. The curing method is not particularly limited; for example, the composition can be cured by heating. Moreover, the epoxy resin composition can be dissolved in a solvent (e.g., toluene, acetone, etc.) to prepare a varnish, and then the varnish can be applied to a substrate (e.g., copper foil, aluminum foil, a polyimide film, etc.), followed by heating, thereby obtaining a film-like cured product. The curing temperature is generally room temperature to 200° C. The curing time varies depending on the composition liquid, and can be generally widely set from 30 minutes to 1 week.
- A cured product obtained by curing the epoxy resin composition of the present invention has good dielectric characteristics (low dielectric constant and low dielectric loss tangent) and high adhesion strength to metal, such as copper and aluminum; therefore, for example, the cured product can be suitably used for applications, such as semiconductor sealing materials, liquid sealing materials, potting materials, sealing materials, printed circuit board materials, and composite materials. Furthermore, the present invention includes a semiconductor sealing material, a liquid sealing material, a potting material, a sealing material, a printed circuit board material, and a composite material, each of which uses the epoxy resin composition or a cured product thereof.
- The present invention is described in more detail below with reference to Examples; however, the present invention is not limited to only these Examples.
- 1,2-Epoxy-4-vinylcyclohexane (25 g), 0.25 g of 2 wt % ethanol solution of hexachloroplatinic acid hexahydrate, and 250 g of toluene were placed in a 500-mL four-necked flask equipped with a stirrer, a thermometer, and a condenser in a nitrogen atmosphere. After the temperature was raised to 70° C., 20 g of 1,4-bis(dimethylsilyl)benzene was slowly added dropwise, and the mixture was then stirred at 90° C. for 4 hours. After the toluene was concentrated, 42 g of slightly yellow liquid (epoxy resin A:
- 1,4-di[2-(3,4-epoxycyclohexylethyl)dimethylsilyl]benzene) was obtained.
- Components in amounts (mass ratio) shown in Table 1 were uniformly mixed, and the mixture was then sufficiently degassed, thereby preparing epoxy resin compositions.
- The components in Table 1 are as follows.
- Epoxy resin B: Bis-A epoxy resin (JER Grade 828, produced by Mitsubishi Chemical Corporation)
- Acid anhydride-based curing agent: 4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride=70/30 (RIKACID MH-700, produced by New Japan Chemical Co., Ltd.)
- Curing accelerator A: 2-ethyl-4-methylimidazole (2E4MZ, produced by Mitsubishi Chemical Corporation)
- Curing accelerator B: 2,4,6-tris(dimethylaminomethyl)phenol (DMP, produced by Tokyo Chemical Industry Co., Ltd.)
- Curing accelerator C: 1,4-diazabicyclo[2.2.2]octane (DABCO, produced by Tokyo Chemical Industry Co., Ltd.)
- Curing accelerator D: 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, produced by Tokyo Chemical Industry Co., Ltd.)
- The epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each applied to an aluminum plate (JIS A1050P) (size: 2×25×100 mm) so that the adhesive part had a rectangular shape (12.5×25 mm). Then, another aluminum plate was bonded thereto, and cured by heating at 100° C. for 1 hour, 120° C. for 2 hours, and 150° C. for 2 hours. Thus, tensile shear adhesion test pieces were obtained.
- The obtained adhesion test pieces were each subjected to a tensile shear adhesion test using a tensile tester (AGS-X, produced by Shimadzu Corp.) with a clamp distance of 100 mm at a test rate of 5 mm/min, and the tensile shear adhesion strength was calculated from the measured maximum breaking strength and the adhesion area. Table 1 shows the results.
- The epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each applied to an aluminum plate (JIS A1050P) (size: 2×25×100 mm) so that the adhesive part had a rectangular shape (12.5×25 mm). Then, another aluminum plate was bonded thereto, and cured by heating at 100° C. for 1 hour, 120° C. for 2 hours, and 150° C. for 2 hours. Thus, tensile shear adhesion test pieces were obtained.
- The obtained adhesion test pieces were allowed to stand in an atmosphere at 85° C. with 85% RH for 168 hours. Subsequently, the test pieces were each subjected to a tensile shear adhesion test using a tensile tester (AGS-X, produced by Shimadzu Corp.) with a clamp distance of 100 mm at a test rate of 5 mm/min, and the tensile shear adhesion strength was calculated from the measured maximum breaking strength and the adhesion area.
- The maintenance rate (%) of tensile shear adhesion strength to aluminum after the high-temperature high-humidity test was calculated by dividing the tensile shear adhesion strength to aluminum after the high-temperature high-humidity test by the tensile shear adhesion strength to aluminum before the high-temperature high-humidity test. Table 1 shows the results.
- The epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each applied to an oxygen-free copper plate (JIS C1020P) (size: 2×25×100 mm) so that the adhesive part had a rectangular shape (12.5×25 mm). Then, another oxygen-free copper plate was bonded thereto, and cured by heating at 100° C. for 1 hour, 120° C. for 2 hours, and 150° C. for 2 hours. Thus, tensile shear adhesion test pieces were obtained.
- The obtained adhesion test pieces were each subjected to a tensile shear adhesion test using a tensile tester (AGS-X, produced by Shimadzu Corp.) with a clamp distance of 100 mm at a test rate of 5 mm/min, and the tensile shear adhesion strength was calculated from the measured maximum breaking strength and the adhesion area. Table 1 shows the results.
- The epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each applied to an oxygen-free copper plate (JIS C1020P) (size: 2×25×100 mm) so that the adhesive part had a rectangular shape (12.5×25 mm). Then, another oxygen-free copper plate was bonded thereto, and cured by heating at 100° C. for 1 hour, 120° C. for 2 hours, and 150° C. for 2 hours. Thus, tensile shear adhesion test pieces were obtained.
- The obtained adhesion test pieces were allowed to stand in an atmosphere at 85° C. with 85% RH for 168 hours. Subsequently, the test pieces were each subjected to a tensile shear adhesion test using a tensile tester (AGS-X, produced by Shimadzu Corp.) with a clamp distance of 100 mm at a test rate of 5 mm/min, and the tensile shear adhesion strength was calculated from the measured maximum breaking strength and the adhesion area.
- The maintenance rate (5) of tensile shear adhesion strength to copper after the high-temperature high-humidity test was calculated by dividing the tensile shear adhesion strength to copper after the high-temperature high-humidity test by the tensile shear adhesion strength to copper before the high-temperature high-humidity test. Table 1 shows the results.
- The epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each poured into a resin mold (thickness: 2 mm), and cured by heating at 100° C. for 1 hour, 120° C. for 2 hours, and 150° C. for 2 hours. Thus, test pieces for dielectric measurement were obtained.
- The obtained test pieces were each calibrated with PTFE using a dielectric constant measuring device (Impedance Analyzer, produced by Agilent), and then the relative dielectric constant (1 GHz) and the dielectric loss tangent (1 GHz) were measured. Table 1 shows the results.
- The epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each poured into a resin mold, and cured by heating at 100° C. for 1 hour, 120° C. for 2 hours, and 150° C. for 2 hours. Thus, test pieces for glass transition temperature measurement were obtained.
- The glass transition temperature of the obtained test pieces was measured using a thermomechanical analyzer (SSC5200, produced by SII Nanotechnology Inc.) in compressed mode at a load of 50 mN at 5° C./min. Table 1 shows the results.
- The epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each poured into a resin mold, and cured by heating at 100° C. for 1 hour, 120° C. for 2 hours, and 150° C. for 2 hours. After the glass transition temperature of the cured test pieces was measured, the test pieces after measurement were observed, and the presence of cracks was evaluated based on their appearance.
-
TABLE 1 Comparative Comparative Example 1 Example 2 Example 3 Example 4 Example 1 Example 2 Epoxy resin A 100 100 100 100 0 0 Epoxy resin B 0 0 0 0 100 100 Acid anhydride-based curing agent 76 76 76 76 88 88 Curing accelerator A 1 0 0 0 1 0 Curing accelerator B 0 1 0 0 0 0 Curing accelerator C 0 0 1 0 0 0 Curing accelerator D 0 0 0 1 0 1 Tensile shear adhesion strength 5.0 4.8 4.0 4.5 4.4 4.2 (MPa) to aluminum Maintenance rate (%) of tensile shear 96 92 92 93 27 25 adhesion strength to aluminum after high-temperature high-humidity test Tensile shear adhesion strength 8.0 7.7 6.9 7.5 4.9 7.0 (MPa) to copper Maintenance rate (%) of tensile shear 99 100 98 99 65 54 adhesion strength to copper after high-temperature high-humidity test Relative dielectric constant (1 GHz) 2.6 2.6 2.6 2.6 2.8 2.9 Dielectric loss tangent (1 GHz) 0.005 0.006 0.006 0.005 0.010 0.010 Glass transition temperature (° C.) 162 160 160 161 162 159 Cracks after heat resistance test None None None None Observed Observed - The epoxy resin compositions obtained in Examples 1 to 4 have high adhesion strength to metal. In particular, even after the high-temperature high-humidity test, they can maintain high adhesion strength and have adhesion reliability. Furthermore, they have good dielectric characteristics and heat resistance.
- In contrast, the epoxy resin compositions obtained in Comparative Examples 1 and 2 have a certain degree of initial adhesion strength to metal; however, their adhesion was rapidly reduced after the high-temperature high-humidity test. In addition, it was confirmed that their dielectric characteristics and heat resistance were inferior to those of the epoxy resin compositions obtained in Examples 1 to 4.
Claims (13)
1-10. (canceled)
11. An epoxy resin composition comprising an epoxy resin, an acid anhydride-based curing agent, and a curing accelerator, the epoxy resin being represented by the formula (1):
wherein X is a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring, or a divalent group represented by the formula (2):
wherein Y is a bond, a C1-6 alkylene group, an oxygen atom (—O—), or a group represented by the formula: —S(O)m— wherein m is 0, 1, or 2;
R1 is the same or different, and is a C1-18 alkyl group, a C2-9 alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group, wherein one or more carbon atoms of these groups may be replaced by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom;
R2 is the same or different, and is a C1-18 alkylene group, wherein one or more carbon atoms of this group other than a carbon atom directly bonded to a silicon atom may be replaced by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom;
R3 is the same or different, and is a C1-18 alkyl group, a C2-9 alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group, wherein one or more carbon atoms of these groups may be replaced by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; and
n is the same or different, and is an integer of 0 to 3.
12. The epoxy resin composition according to claim 11 , wherein the curing accelerator is a nitrogen-containing curing accelerator.
13. The epoxy resin composition according to claim 12 , wherein the nitrogen-containing curing accelerator is a tertiary amine compound or an imidazole compound.
14. The epoxy resin composition according to claim 12 , wherein the nitrogen-containing curing accelerator is an imidazole compound.
15. The epoxy resin composition according to claim 12 , wherein the nitrogen-containing curing accelerator is a tertiary amine compound.
16. The epoxy resin composition according to claim 11 , wherein the epoxy resin is represented by the formula (1a):
wherein
X is a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring, or a divalent group represented by the formula (2a):
wherein
Y is a bond, a C1-6 alkylene group, an oxygen atom (—O—), or a group represented by the formula: —S(O)m— wherein m is 0, 1, or 2;
R1 is the same or different, and is a C1-18 alkyl group, a C2-9 alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group, wherein one or more carbon atoms of these groups may be replaced by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom;
R2 is the same or different, and is a C1-18 alkylene group, wherein one or more carbon atoms of this group other than a carbon atom directly bonded to a silicon atom may be replaced by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom;
R3 is the same or different, and is a C1-18 alkyl group, a C2-9 alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group, wherein one or more carbon atoms of these groups may be replaced by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; and
n is the same or different, and is an integer of 0 to 3.
18. The epoxy resin composition according to claim 11 , wherein the acid anhydride-based curing agent is at least one member selected from the group consisting of cyclic aliphatic acid anhydrides, aromatic acid anhydrides, and aliphatic acid anhydrides.
19. The epoxy resin composition according to claim 11 , wherein the acid anhydride-based curing agent is at least one member selected from the group consisting of hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 1-methylnorbornane-2,3-dicarboxylic anhydride, 5-methylnorbornane-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, 1-methylnadic anhydride, 5-methylnadic anhydride, nadic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, and dodecenylsuccinic anhydride.
20. A process for producing the epoxy resin composition according to claim 11 , the process comprising mixing an epoxy resin represented by the formula (1), an acid anhydride-based curing agent, and a curing accelerator.
21. A cured product of the epoxy resin composition according to claim 11 .
22. A semiconductor sealing material, a liquid sealing material, a potting material, a sealing material, a printed circuit board material, or a composite material, each of which uses the epoxy resin composition according to claim 11 or a cured product thereof.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015-139146 | 2015-07-10 | ||
JP2015139146 | 2015-07-10 | ||
JP2015-201380 | 2015-10-09 | ||
JP2015201380 | 2015-10-09 | ||
PCT/JP2016/070158 WO2017010401A1 (en) | 2015-07-10 | 2016-07-07 | Epoxy resin composition, process for producing same, and uses of said composition |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/070158 A-371-Of-International WO2017010401A1 (en) | 2015-07-10 | 2016-07-07 | Epoxy resin composition, process for producing same, and uses of said composition |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/882,016 Division US11066510B2 (en) | 2015-07-10 | 2020-05-22 | Epoxy resin composition, process for producing same, and uses of said composition |
Publications (1)
Publication Number | Publication Date |
---|---|
US20190119434A1 true US20190119434A1 (en) | 2019-04-25 |
Family
ID=57757015
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/743,189 Abandoned US20190119434A1 (en) | 2015-07-10 | 2016-07-07 | Epoxy resin composition, process for producing same, and uses of said composition |
US16/882,016 Active US11066510B2 (en) | 2015-07-10 | 2020-05-22 | Epoxy resin composition, process for producing same, and uses of said composition |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/882,016 Active US11066510B2 (en) | 2015-07-10 | 2020-05-22 | Epoxy resin composition, process for producing same, and uses of said composition |
Country Status (7)
Country | Link |
---|---|
US (2) | US20190119434A1 (en) |
EP (1) | EP3321302B1 (en) |
JP (1) | JP6602865B2 (en) |
KR (1) | KR102534679B1 (en) |
CN (1) | CN107849223B (en) |
TW (1) | TWI708810B (en) |
WO (1) | WO2017010401A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109554148A (en) * | 2017-09-25 | 2019-04-02 | Sika技术股份公司 | Single-component thermosetting epoxy adhesive with improved adhesiveness |
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 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017010401A1 (en) | 2015-07-10 | 2017-01-19 | 住友精化株式会社 | Epoxy resin composition, process for producing same, and uses of said composition |
WO2018131569A1 (en) * | 2017-01-10 | 2018-07-19 | 住友精化株式会社 | Epoxy resin composition |
WO2018131564A1 (en) * | 2017-01-10 | 2018-07-19 | 住友精化株式会社 | Epoxy resin composition |
JP6870657B2 (en) * | 2018-05-17 | 2021-05-12 | 信越化学工業株式会社 | Photosensitive resin composition, photosensitive dry film, and pattern forming method |
CN115124748A (en) * | 2022-07-28 | 2022-09-30 | 海南联塑科技实业有限公司 | Method for inhibiting degradation of plastic and precipitating micro plastic and application |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5639413A (en) * | 1995-03-30 | 1997-06-17 | Crivello; James Vincent | Methods and compositions related to stereolithography |
US5863970A (en) * | 1995-12-06 | 1999-01-26 | Polyset Company, Inc. | Epoxy resin composition with cycloaliphatic epoxy-functional siloxane |
US20040122186A1 (en) * | 2002-12-20 | 2004-06-24 | Herr Donald E. | Epoxy-functional hybrid copolymers |
US6779656B2 (en) * | 2000-01-13 | 2004-08-24 | 3M Espe Ag | Polymerizable preparations based on epoxides that contain silicon |
US6908953B2 (en) * | 1996-11-21 | 2005-06-21 | Espe Dental Ag | Polymerizable compositions based on epoxides |
US7235602B2 (en) * | 2001-02-19 | 2007-06-26 | 3M Espe Ag | Polymerizable preparations on the basis of silicon compounds comprising aliphatic and cycloaliphatic epoxide groups |
US7368524B2 (en) * | 2004-04-30 | 2008-05-06 | 3M Innovative Properties Company | Cationically curing two component materials containing a noble metal catalyst |
US7740482B2 (en) * | 2004-05-13 | 2010-06-22 | Bluestar Silicones France | Stable cationically crosslinkable/polymerizable dental composition with a high filler content |
US7799846B2 (en) * | 2004-07-14 | 2010-09-21 | 3M Espe Ag | Dental composition containing an epoxy functional carbosilane compound |
US7893130B2 (en) * | 2004-05-13 | 2011-02-22 | Bluestar Silicones France Sas | Photocurable dental composition |
US8715905B2 (en) * | 2010-06-18 | 2014-05-06 | Shin-Etsu Chemical Co., Ltd. | Silphenylene-containing photocurable composition, pattern formation method using same, and optical semiconductor element obtained using the method |
WO2015041325A1 (en) * | 2013-09-20 | 2015-03-26 | 信越化学工業株式会社 | Silicone-modified epoxy resin and composition and cured article thereof |
Family Cites Families (57)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US123960A (en) | 1872-02-20 | Improvement in handles for children s carriages | ||
NL130557C (en) | 1966-03-02 | |||
JPS5948942A (en) | 1982-09-14 | 1984-03-21 | Toshiba Corp | Resin seal type semiconductor device |
JPH07692B2 (en) | 1986-03-24 | 1995-01-11 | 住友化学工業株式会社 | Thermoplastic resin composition |
JP2716640B2 (en) | 1992-12-24 | 1998-02-18 | 住友ベークライト株式会社 | Low dielectric constant thermosetting resin composition |
JPH07157540A (en) | 1993-12-08 | 1995-06-20 | Sumitomo Bakelite Co Ltd | Thermosetting resin composition having low dielectric constant |
JP3608865B2 (en) | 1995-03-30 | 2005-01-12 | 三井化学株式会社 | Epoxy resin composition for laminates with high heat resistance and low dielectric constant |
JP3735896B2 (en) | 1995-08-08 | 2006-01-18 | 大日本インキ化学工業株式会社 | Epoxy resin composition and semiconductor sealing material |
JP3638404B2 (en) * | 1997-06-03 | 2005-04-13 | 信越化学工業株式会社 | Flexible printed wiring board |
US6194490B1 (en) * | 1998-02-27 | 2001-02-27 | Vantico, Inc. | Curable composition comprising epoxidized natural oils |
JP3820834B2 (en) | 2000-02-28 | 2006-09-13 | 大日本インキ化学工業株式会社 | RESIN COMPOSITION FOR CIRCUIT BOARD USED FOR SEMICONDUCTOR DEVICE HAVING LATTICE CURRENT TERMINAL |
JP4849654B2 (en) | 2000-09-12 | 2012-01-11 | 日東電工株式会社 | Adhesive composition and adhesive sheet |
JP4049611B2 (en) | 2001-04-20 | 2008-02-20 | 三菱レイヨン株式会社 | Epoxy resin composition and fiber reinforced resin composite material |
JP2003321482A (en) | 2002-04-30 | 2003-11-11 | Shin Etsu Chem Co Ltd | Silphenylene compound having oxirane ring and method for producing the same |
JP2004231728A (en) | 2003-01-29 | 2004-08-19 | Mitsubishi Gas Chem Co Inc | Epoxy resin curing agent, curable epoxy resin composition and cured product |
JP3816454B2 (en) | 2003-03-12 | 2006-08-30 | Tdk株式会社 | Epoxy resin composition and sheet obtained therefrom, prepreg-like material, sheet with metal foil, laminate, electrical insulation material, resist material |
WO2005028537A1 (en) | 2003-09-18 | 2005-03-31 | Kaneka Corporation | Photocuring resin composition containing organic polymer having epoxy group and/or oxethane group-containing silicon group at end, and method for producing same |
JP2005187800A (en) | 2003-12-01 | 2005-07-14 | Hitachi Chem Co Ltd | Resin composition, and prepreg, metal-clad laminated sheet, and printed-wiring board using the composition |
JP4347103B2 (en) | 2004-03-22 | 2009-10-21 | 信越化学工業株式会社 | Curable silicone composition |
JP4827145B2 (en) | 2004-07-14 | 2011-11-30 | スリーエム イノベイティブ プロパティズ カンパニー | Dental composition containing oxirane monomer |
JP4820629B2 (en) * | 2004-11-25 | 2011-11-24 | 株式会社トクヤマ | Curable composition |
JP4983228B2 (en) | 2005-11-29 | 2012-07-25 | 味の素株式会社 | Resin composition for insulating layer of multilayer printed wiring board |
FR2904321B1 (en) | 2006-07-25 | 2008-09-05 | Rhodia Recherches Et Technologies Sas | POLYMERIZABLE AND / OR CROSS-LINKABLE COMPOSITION UNDER CATIONIC AND / OR RADICAL IRRADIATION |
US20080071035A1 (en) | 2006-09-15 | 2008-03-20 | Delsman Erik R | Curable poly(arylene ether) composition and method |
JP2009227992A (en) | 2008-02-29 | 2009-10-08 | Sekisui Chem Co Ltd | Film and printed circuit board |
JP2010215858A (en) | 2009-03-18 | 2010-09-30 | Sekisui Chem Co Ltd | Epoxy resin composition, sheet-like molding, laminated sheet, prepreg, cured product and multilayer laminated sheet |
JP5707607B2 (en) | 2009-04-24 | 2015-04-30 | Jnc株式会社 | Organosilicon compound and thermosetting resin composition containing the same |
JP5413340B2 (en) | 2009-09-30 | 2014-02-12 | 信越化学工業株式会社 | Epoxy group-containing polymer compound, photocurable resin composition using the same, pattern forming method, and film for protecting electric / electronic parts |
TWI506082B (en) | 2009-11-26 | 2015-11-01 | Ajinomoto Kk | Epoxy resin composition |
KR20120001668A (en) | 2010-06-28 | 2012-01-04 | 에프 아이 에이치 (홍콩) 리미티드 | Molded article and method for making the same |
KR101259446B1 (en) | 2010-09-29 | 2013-05-02 | 요코하마 고무 가부시키가이샤 | Cationic polymerization initiator and thermosetting epoxy resin composition |
JP2012162585A (en) | 2011-02-03 | 2012-08-30 | Namics Corp | Resin sealng material for semiconductor |
JP5900355B2 (en) | 2011-02-18 | 2016-04-06 | Jnc株式会社 | Curable resin composition and color conversion material using the same |
KR101858638B1 (en) * | 2012-03-23 | 2018-05-16 | 가부시키가이샤 아데카 | Silicon-containing curable resin composition |
JP6135675B2 (en) | 2012-09-18 | 2017-05-31 | Jnc株式会社 | Epoxy and alkoxysilyl group-containing silsesquioxane and composition thereof |
JP5678976B2 (en) | 2013-03-07 | 2015-03-04 | Dic株式会社 | Curable resin composition, cured product thereof, and resin material for electronic parts |
JP6163803B2 (en) | 2013-03-14 | 2017-07-19 | 味の素株式会社 | Resin composition |
JPWO2014147903A1 (en) | 2013-03-22 | 2017-02-16 | 東亞合成株式会社 | Adhesive composition, coverlay film and flexible copper-clad laminate using the same |
DE102013215382A1 (en) * | 2013-08-05 | 2015-02-05 | Osram Gmbh | Fluorescent LED |
US11242476B2 (en) | 2013-12-16 | 2022-02-08 | Sumitomo Seika Chemicals Co., Ltd. | Epoxy resin adhesive agent |
CN105315615B (en) | 2014-08-05 | 2017-11-21 | 广东生益科技股份有限公司 | A kind of composition epoxy resin and the prepreg and copper-clad laminate using its making |
JP6429569B2 (en) | 2014-09-30 | 2018-11-28 | 日鉄ケミカル&マテリアル株式会社 | Epoxy resin composition and cured product thereof |
JP6458985B2 (en) | 2014-10-22 | 2019-01-30 | ナミックス株式会社 | Resin composition, insulating film using the same, and semiconductor device |
JP6502754B2 (en) | 2015-06-08 | 2019-04-17 | 信越化学工業株式会社 | PHOTO-CURABLE RESIN COMPOSITION AND PHOTO-CURABLE DRY FILM USING THE SAME |
JP6656870B2 (en) | 2015-07-10 | 2020-03-04 | 住友精化株式会社 | Benzoxazine resin composition, method for producing the same, and use of the composition |
WO2017010401A1 (en) | 2015-07-10 | 2017-01-19 | 住友精化株式会社 | Epoxy resin composition, process for producing same, and uses of said composition |
CN108291075A (en) | 2015-11-18 | 2018-07-17 | 住友精化株式会社 | The purposes of composition epoxy resin, its manufacturing method and the composition |
TWI751989B (en) | 2015-12-01 | 2022-01-11 | 日商琳得科股份有限公司 | Adhesive composition, sealing plate and sealing body |
WO2018131564A1 (en) | 2017-01-10 | 2018-07-19 | 住友精化株式会社 | Epoxy resin composition |
CN110191921B (en) | 2017-01-10 | 2022-04-26 | 住友精化株式会社 | Epoxy resin composition |
US11091627B2 (en) | 2017-01-10 | 2021-08-17 | Sumitomo Seika Chemicals Co., Ltd. | Epoxy resin composition |
US11292872B2 (en) | 2017-01-10 | 2022-04-05 | Sumitomo Seika Chemicals Co., Ltd. | Epoxy resin composition |
WO2018131569A1 (en) | 2017-01-10 | 2018-07-19 | 住友精化株式会社 | Epoxy resin composition |
EP3569626B1 (en) | 2017-01-10 | 2023-03-01 | Sumitomo Seika Chemicals Co., Ltd. | Epoxy resin composition |
TW201841968A (en) | 2017-03-31 | 2018-12-01 | 日商住友精化股份有限公司 | Epoxy resin, epoxy resin composition, and cured object obtained therefrom, use thereof, and production method therefor |
WO2019026822A1 (en) | 2017-07-31 | 2019-02-07 | 住友精化株式会社 | Epoxy resin composition |
JP6754741B2 (en) | 2017-09-07 | 2020-09-16 | 信越化学工業株式会社 | Semiconductor laminates, methods for manufacturing semiconductor laminates, and methods for manufacturing semiconductor devices |
-
2016
- 2016-07-07 WO PCT/JP2016/070158 patent/WO2017010401A1/en active Application Filing
- 2016-07-07 JP JP2017528646A patent/JP6602865B2/en active Active
- 2016-07-07 CN CN201680040520.2A patent/CN107849223B/en active Active
- 2016-07-07 EP EP16824381.4A patent/EP3321302B1/en active Active
- 2016-07-07 KR KR1020187000179A patent/KR102534679B1/en active IP Right Grant
- 2016-07-07 US US15/743,189 patent/US20190119434A1/en not_active Abandoned
- 2016-07-11 TW TW105121797A patent/TWI708810B/en active
-
2020
- 2020-05-22 US US16/882,016 patent/US11066510B2/en active Active
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5639413A (en) * | 1995-03-30 | 1997-06-17 | Crivello; James Vincent | Methods and compositions related to stereolithography |
US5863970A (en) * | 1995-12-06 | 1999-01-26 | Polyset Company, Inc. | Epoxy resin composition with cycloaliphatic epoxy-functional siloxane |
US6908953B2 (en) * | 1996-11-21 | 2005-06-21 | Espe Dental Ag | Polymerizable compositions based on epoxides |
US6779656B2 (en) * | 2000-01-13 | 2004-08-24 | 3M Espe Ag | Polymerizable preparations based on epoxides that contain silicon |
US7235602B2 (en) * | 2001-02-19 | 2007-06-26 | 3M Espe Ag | Polymerizable preparations on the basis of silicon compounds comprising aliphatic and cycloaliphatic epoxide groups |
US20040122186A1 (en) * | 2002-12-20 | 2004-06-24 | Herr Donald E. | Epoxy-functional hybrid copolymers |
US7368524B2 (en) * | 2004-04-30 | 2008-05-06 | 3M Innovative Properties Company | Cationically curing two component materials containing a noble metal catalyst |
US7740482B2 (en) * | 2004-05-13 | 2010-06-22 | Bluestar Silicones France | Stable cationically crosslinkable/polymerizable dental composition with a high filler content |
US7893130B2 (en) * | 2004-05-13 | 2011-02-22 | Bluestar Silicones France Sas | Photocurable dental composition |
US7799846B2 (en) * | 2004-07-14 | 2010-09-21 | 3M Espe Ag | Dental composition containing an epoxy functional carbosilane compound |
US8715905B2 (en) * | 2010-06-18 | 2014-05-06 | Shin-Etsu Chemical Co., Ltd. | Silphenylene-containing photocurable composition, pattern formation method using same, and optical semiconductor element obtained using the method |
WO2015041325A1 (en) * | 2013-09-20 | 2015-03-26 | 信越化学工業株式会社 | Silicone-modified epoxy resin and composition and cured article thereof |
US20160237202A1 (en) * | 2013-09-20 | 2016-08-18 | Shin-Etsu Chemical Co., Ltd. | Silicone-modified epoxy resin and composition and cured article thereof |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN109554148A (en) * | 2017-09-25 | 2019-04-02 | Sika技术股份公司 | Single-component thermosetting epoxy adhesive with improved adhesiveness |
Also Published As
Publication number | Publication date |
---|---|
KR102534679B1 (en) | 2023-05-19 |
CN107849223B (en) | 2020-07-28 |
JPWO2017010401A1 (en) | 2018-04-19 |
US20200283566A1 (en) | 2020-09-10 |
US11066510B2 (en) | 2021-07-20 |
EP3321302B1 (en) | 2021-06-30 |
CN107849223A (en) | 2018-03-27 |
TWI708810B (en) | 2020-11-01 |
JP6602865B2 (en) | 2019-11-06 |
EP3321302A1 (en) | 2018-05-16 |
TW201710369A (en) | 2017-03-16 |
KR20180027491A (en) | 2018-03-14 |
WO2017010401A1 (en) | 2017-01-19 |
EP3321302A4 (en) | 2019-02-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11066510B2 (en) | Epoxy resin composition, process for producing same, and uses of said composition | |
EP3378897B1 (en) | Epoxy resin composition, method for producing same, and use of composition | |
EP3569626B1 (en) | Epoxy resin composition | |
KR102461516B1 (en) | epoxy resin composition | |
KR102461514B1 (en) | epoxy resin composition | |
JP6656870B2 (en) | Benzoxazine resin composition, method for producing the same, and use of the composition | |
US11603466B2 (en) | Epoxy resin composition | |
US7060761B2 (en) | Epoxy resin compositions | |
CN114008104B (en) | Epoxy resin composition | |
EP4092065A1 (en) | Resin composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: SUMITOMO SEIKA CHEMICALS CO., LTD., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:FUKUDA, NORIAKI;HARISAKI, RYOTA;YAMAMOTO, KATSUMASA;AND OTHERS;SIGNING DATES FROM 20171029 TO 20171030;REEL/FRAME:044580/0650 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: ADVISORY ACTION MAILED |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |