WO2007034713A1 - Epoxy resin composition - Google Patents

Epoxy resin composition Download PDF

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Publication number
WO2007034713A1
WO2007034713A1 PCT/JP2006/318106 JP2006318106W WO2007034713A1 WO 2007034713 A1 WO2007034713 A1 WO 2007034713A1 JP 2006318106 W JP2006318106 W JP 2006318106W WO 2007034713 A1 WO2007034713 A1 WO 2007034713A1
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WO
WIPO (PCT)
Prior art keywords
group
epoxy resin
resin composition
atom
general formula
Prior art date
Application number
PCT/JP2006/318106
Other languages
French (fr)
Japanese (ja)
Inventor
Nobumasa Sasa
Original Assignee
Konica Minolta Medical & Graphic, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Medical & Graphic, Inc. filed Critical Konica Minolta Medical & Graphic, Inc.
Priority to JP2007536457A priority Critical patent/JPWO2007034713A1/en
Publication of WO2007034713A1 publication Critical patent/WO2007034713A1/en

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Classifications

    • 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
    • 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
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to an epoxy resin composition, and more specifically, for interior materials and structural adhesives for automobiles, aircraft, vehicles, etc., and for structural structures such as roofs, walls, and floors.
  • Adhesives, and adhesives for electronic materials, etc. heavy-duty anti-corrosion paints for steel structures, steel pipes, ships, marine structures, concrete structures, protective coatings for food cans, coating materials, sealing materials for electrical materials,
  • the present invention relates to an epoxy resin composition that can be applied to a semiconductor sealing material or the like.
  • Patent Document 1 JP 2005-36095 A (Claims, Examples)
  • Patent Document 2 JP-A-2005-51131 (Claims, Examples)
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2005-126658 (Claims, Examples)
  • Patent Document 4 Japanese Patent Laid-Open No. 2002-121471 (Claims, Examples)
  • Patent Document 5 Japanese Patent Laid-Open No. 2002-249532 (Claims, Examples)
  • Patent Document 6 Japanese Unexamined Patent Application Publication No. 2002-275229 (Claims and Examples)
  • Patent Document 7 JP-A-2005-95723 (Claims, Examples)
  • Patent Document 8 Japanese Patent Application Laid-Open No. 2004-83783 (Claims, Examples)
  • Patent Document 9 Japanese Patent Application Laid-Open No. 2004-256781 (Claims, Examples)
  • Patent Document 10 JP-A-2005-120357 (Claims and Examples)
  • Patent Document 11 JP-A-2003-183351 (Claims and Examples)
  • Patent Document 12 JP-A-2004-285125 Publication (Claims, Examples) Disclosure of Invention
  • the present invention has been made in view of the above problems, and its purpose is an epoxy resin having excellent curability, adhesion, heat resistance, hygiene, weather resistance, corrosion resistance, storage stability, and the like. It is to provide a composition.
  • R represents a substituent
  • mO represents an integer of 0 to 2
  • rO represents an integer of 1 to 3.
  • L is the main
  • the chain may contain an oxygen atom or a sulfur atom, and may be an rO + 1 monovalent linking group having 1 to 15 carbon atoms. Or a single bond. ]
  • R represents a substituent
  • ml represents an integer of 0 to 2
  • pl and ql each represent 0 or 1
  • L is carbon that may contain oxygen or sulfur atoms in the main chain
  • Rl + 1 represents a monovalent linking group or a single bond.
  • R represents a substituent
  • m2 represents an integer of 0 to 2
  • p2 and q2 each represents 0 or 1
  • L is carbon that may contain oxygen or sulfur atoms in the main chain
  • R and R represent a hydrogen atom or an alkyl group. However, R and R are water at the same time.
  • R represents a hydrogen atom, a halogen atom or a substituent.
  • R is the carbon source represented by C * 1 and C * 2.
  • R and R are synonymous with R and R.
  • R and R are the same as R and R
  • At least one of R and R is a hydrogen atom.
  • the epoxy resin further comprising at least one selected from a cresol novolac type epoxy resin, a biphenyl type epoxy resin, and a dicyclo type epoxy resin.
  • the epoxy resin composition according to any one of the above.
  • an epoxy resin composition excellent in curability, adhesiveness, heat resistance, hygiene, weather resistance, corrosion resistance, storage stability and the like could be provided.
  • the epoxy resin composition of the present invention is an epoxy resin composition containing an epoxy resin and a curing agent as essential components, and may further contain a curing accelerator, a filler and the like. It is a composition.
  • substituents include, for example, a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group).
  • a halogen atom eg, chlorine atom, bromine atom, fluorine atom, etc.
  • an alkyl group having 1 to 6 carbon atoms eg, methyl group, ethyl group, propyl group, isopropyl group.
  • alkoxy groups having 1 to 6 carbon atoms eg, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, etc.
  • acyl groups For example, acetyl group, propionyl group, trifluoroacetyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxy carbonyl group (for example, methoxycarbonyl group, ethoxy carbonyl group, etc.) Tert-butoxycarbonyl group, etc.).
  • Preferable substituents are an alkyl group, an alkoxy group, and an alkoxy carbo group.
  • m0, ml and m2 each represents 0 to 2, preferably 0 or 1.
  • L is an rO + monovalent chain having 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain.
  • L is the number of carbon atoms that may contain oxygen or sulfur atoms in the main chain
  • L is oxygen atom or sulfur atom in the main chain
  • Examples of the divalent linking group having 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain, include the following groups and these groups and a mono-O group, S group, CO group, CS Examples include groups formed by combining a plurality of groups.
  • Ptandyl group [CH CH CH OCH CH CH-], 3, 6 Dioxa 1, 8-Ota
  • the trivalent or higher linking group includes a hydrogen atom at any site from the divalent linking groups listed above. Groups that can be removed by removing as many children as necessary and those with —O— groups, —S— groups, —CO— groups, —CS
  • a group formed by combining a plurality of groups can be mentioned.
  • Each of L, L, and L may have a substituent! /.
  • substituents include halogen atoms
  • Child for example, chlorine atom, bromine atom, fluorine atom, etc.
  • alkyl group having 1 to 6 carbon atoms for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.
  • carbon number 1 to 6 Alkoxy groups for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.
  • acyl groups for example, acetyl group, propoxy group, Trifluoroacetyl group, etc.
  • acyloxy group eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.
  • alkoxy carbo yl group eg, methoxy carbo ol group, ethoxy carbo ol group, tert- Butoxycarbonyl group, etc.
  • Preferred as a substituent are an alkyl
  • L, L, and L may contain an oxygen atom or a sulfur atom in the main chain !, 2 having 1 to 8 carbon atoms
  • a divalent linking group having 1 to 5 carbon atoms in which the main chain preferred by the valent linking group is only carbon is more preferred.
  • pl and ql each represents 0 or 1, and pi + ql is preferably 1 or more.
  • p2 and q2 each represents 0 or 1, and 1 is preferred for each.
  • R and R each represent a hydrogen atom or an alkyl group
  • alkyl group examples include an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group), and a cycloalkyl group having 3 to 6 carbon atoms (for example, , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl Group).
  • R and R are not simultaneously hydrogen atoms, preferably one is water
  • a primary atom and the other is an alkyl group, particularly preferably a methyl group.
  • R is a hydrogen atom, halogene
  • a halogen atom specifically includes a chlorine atom, a bromine atom or a fluorine atom. Preferably they are a fluorine atom and a chlorine atom.
  • R a fluorine atom
  • R a chlorine atom
  • 3 is preferably a hydrogen atom.
  • substituents include an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group), and a cycloalkyl group having 3 to 6 carbon atoms ( For example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like, alkoxy group having 1 to 20 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso propoxy group, n butoxy group, tert butoxy group, etc.), an acyl group having 2 to 20 carbon atoms (eg, acetyl group, propionyl group, trifluoroacetyl group, etc.), an acyloxy group having 2 to 20 carbon atoms (eg, acetooxy group, propio-loxy group)
  • R and R are each represented by a force C * 1 representing a hydrogen atom, a halogen atom, or a substituent.
  • Substituents bonded to the carbon atom via a carbon atom, nitrogen atom or sulfur atom are preferred.
  • the halogen atom include a chlorine atom, a bromine atom and a fluorine atom.
  • a chlorine atom and a fluorine atom are preferred.
  • an alkyl group for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group).
  • R 4 and R are preferably an alkyl group, and an alkyl group substituted by a group represented by the following *
  • R and R are a hydrogen atom.
  • two are hydrogen atoms and the other is an alkyl group or an alkyl group substituted with a group represented by * below.
  • Specific examples of the group represented by * include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, Acyl group, carbo-loxy group, thio group, carboxyl group, carbonyl amino group, ureido group, sulfo-lumino group, sulfo group, strong rubamoyl group, sulfamoyl group, hydroxyl group, nitro group, cyano group, sulfone Amide group, amino group, sulfo group, phosphono group, sulfite group, sulfino group, sulfo-luminocarbon group, carbo amino group, aminocarbol group, sulfaluminocarbon group, etc. Are listed.
  • a group having a structure is represented.
  • a group having an alkoxy group as a partial structure is preferable.
  • hydrocarbon group constituted by these include an alkyl group having 1 to 20 carbon atoms and an aryl group having 1 to 14 carbon atoms. More preferably, it is a C1-C10 alkyl group.
  • R is a carbon atom represented by C * 1 and C * 2 via a carbon atom, nitrogen atom or sulfur atom.
  • Preferable examples include an alkylene group having 1 to 20 carbon atoms and an alkylene oxide group.
  • linking group examples include a substituent containing an oxygen atom represented by R and R, and
  • Examples thereof include those having a divalent linking group.
  • hydrocarbon group Only from hydrogen atom and carbon atom represented by R, R, R, R, R, R, R 1, R 2 and R 3
  • the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, an alkylene group, an aryl group having 1 to 14 carbon atoms, and an arylene group.
  • an alkyl group having 1 to 10 carbon atoms or an alkylene group is used.
  • the epoxy resin represented by the general formulas (1) to (4) of the present invention is contained in the epoxy resin composition.
  • the epoxy resin composition of the present invention is used in combination with the epoxy resin represented by the general formulas (1) to (4) described above to use a cresol novolac type, biphenyl type, dicyclo type epoxy.
  • rosin can be used.
  • the cresol novolac type, biphenol type, and dicyclo type epoxy resin are not particularly limited, and the power to use various conventionally known ones in liquid or solid form at 25 ° C, particularly in view of hygiene A solid form at 25 ° C to 25 ° C is preferred.
  • a polyfunctional epoxy resin having 3 or more functional groups, preferably 4 or more functional groups may be used in combination.
  • examples of such polyfunctional epoxy resins include glycidylamine epoxy resins, naphthalene type epoxy resins, novolac type epoxy resins, and polyfunctional glycidyl ethers.
  • epoxy resins are contained in the epoxy resin composition in an amount of 5 to 90% by mass, preferably 10 to 50%. It can be contained by mass%.
  • Non-photosensitive curing agents that can be used in the present invention will be described.
  • the epoxy resin hardener is not particularly limited, and examples thereof include heat-curing acid anhydride-based curing agents such as trialkyltetrahydrophthalic anhydride, phenol-based curing agents, and amine-based curing agents.
  • latent curing agents such as dicyandiamide, cationic catalyst-type curing agents, and the like, and so-called photosensitive diazonium salts, iodonium salts, sulfonium salts are outside the scope of the present invention.
  • curing agents for epoxy resin a thermosetting curing agent that is liquid at room temperature and a multi-functional, low-equivalent addition amount is acceptable!
  • a latent curing agent such as dicyandiamide is preferably used. .
  • the curing accelerator is not particularly limited. For example, an imidazole curing accelerator, a tertiary amine curing accelerator, etc. can be mentioned. Among them, the curing speed and physical properties of the cured product are adjusted.
  • an imidazole curing accelerator is preferably used because the reaction system is easily controlled.
  • the imidazole curing accelerator is not particularly limited.
  • 1-cyanoethyl 2-phenol imidazole in which the 1-position of imidazole is protected with a cyanoethyl group, or a product in which the basicity is protected with isocyanuric acid Name “2MA-0K” (manufactured by Shikoku Kasei Kogyo Co., Ltd.).
  • non-photosensitive curing agents can be contained in the epoxy resin composition in an amount of 0.01 to 50% by mass, preferably 0.1 to 10% by mass.
  • Non-photosensitive curing accelerators that can be used in the present invention include, for example, tertiary amine-based curing accelerators, urea derivative-based curing accelerators, imidazole-based curing accelerators, DBU-based curing accelerators, Organic phosphorus curing accelerators (for example, phosphine curing accelerators), salt-based curing accelerators (for example, phosphonium salt-based curing accelerators, sulfonium salt-based curing accelerators, ammonium salt-based curing agents) Accelerators, etc.), metal chelate type hardening accelerators, acid and metal salt type hardening accelerators, etc., so-called photosensitive diazo-um salt, ododonium salt, sulfonium salt are subject of the present invention.
  • the filler that can be used in the present invention will be described.
  • the inorganic filler the use of various fine particles such as silica, alumina, titania, aluminum hydroxide, aluminum hydroxide, etc.
  • the use of spherical fused silica is preferred.
  • the particle size distribution of the inorganic filler is 1 to: LOO / zm is preferred, and the average particle size is preferably 0.05 to 20 111, more preferably 0.1 to 10 m.
  • fillers can be contained in the epoxy resin composition in an amount of 10 to 90% by mass, preferably 50 to 80% by mass.
  • the epoxy resin composition of the present invention further contains, as necessary, pigments such as carbon-functional silane for improving adhesion, carbon black, dyes, antioxidants, surface treatment agents ( ⁇ -glycidoxypropyltrimethoxy). Silane etc.) and other additives can be blended within a range not to impair the purpose of the present invention.
  • pigments such as carbon-functional silane for improving adhesion, carbon black, dyes, antioxidants, surface treatment agents ( ⁇ -glycidoxypropyltrimethoxy). Silane etc.
  • other additives can be blended within a range not to impair the purpose of the present invention.
  • the epoxy resin composition of the present invention preferably contains a thermoplastic resin.
  • thermoplastic resin applicable to the present invention include polyethylene, polypropylene, polystyrene, acrylonitrile / styrene resin, acrylonitrile / butadiene / styrene resin, methallyl resin, polychlorinated butyl, polyamide, polyurethane, polyacetanol.
  • Polybutylene terephthalate polymethylpentene, polycarbonate, polyphenylene ether, polyphenylene sulfide, polyetheretherketone, polytetrafluoroethylene, polyetherimide, polyarylate, polysulfone, polyethersulfone, polyamideimide, etc.
  • polyamide and polyurethane is preferred.
  • thermoplastic resins are contained in the epoxy resin composition in an amount of 1 to 30% by mass, preferably 5 to 1.
  • Vinyl epoxy can also be mix
  • Vinyl ethers include cyclohexane dimethanol divinyl ether and diethylene glycol dibi
  • a polyester or polyether having a hydroxyl group at the terminal can be blended in the epoxy resinous fiber composition if it can be dissolved in the epoxy resin composition.
  • polyesters include PCL-205H, which is a polyester having two hydroxyl groups in the molecule, and PCL-210 (manufactured by Daicel Engineering Co., Ltd.), and PCL-3 05, which is a polyester having three hydroxyl groups in the molecule.
  • PCL-308 manufactured by Daicel Engineering Co., Ltd.
  • PCL-410D made by Daicel Engineering Co., Ltd.
  • Kurapol P 1010, P-2010, P-3010 can also be used.
  • the polyether include polyethers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • Examples of commercially available products include Adeiki polyether P-400, P-1000, P-3000, and the like.
  • the low molecular polyol include glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4 butanediol, and 1,6 hexanediol.
  • the epoxy resin composition of the present invention is preferably applied to an adhesive, a paint, a coating material or a sealing material due to its excellent properties, particularly its excellent properties.
  • Adhesives [Hanging and flicking, f row printing, JP 2000-273151, JP 2005-36095, JP 2005-51131, JP 2005-126658, etc. JP-A-8-134175, JP-A-2001-131468, JP-A-2002-121471, JP-A-2002-249532, JP-A-2002-275229, JP-A-2005-95723, etc.
  • the coating materials include lacquers such as JP2003-292568, JP2003-327660, JP2004-83783, JP2004-256781, JP2005-120357, etc.
  • Epoxy resin EP-17 24 parts by mass
  • Dicyclopentagen-type solid epoxy resin (trade name “EXA-7200HHJ manufactured by Dainippon Ink & Chemicals, Inc.”) 76 parts by mass
  • Non-photosensitive curing agent 60 parts by mass of trialkyltetrahydrophthalic anhydride
  • Non-photosensitive curing accelerator Isocyanur Modified solid dispersion type imidazole 8 parts by mass Imidazole silane coupling agent 2 parts by mass
  • Epoxy resin EP—56 40 parts by mass
  • Epicoat 1009 epoxy resin manufactured by Yuka Shell Co., Ltd.
  • Non-photosensitive curing accelerator 0.2 parts by mass of phosphoric acid
  • Epoxy resin EP— 61 50 parts by mass
  • Non-photosensitive curing agent ALCH-TR: Aluminum trisethylacetate acetate
  • Epoxy resin composition 4 For sealing materials
  • Epoxy resin EP-15 15 parts by mass
  • Non-photosensitive hardener 100 parts by weight of methylhexahydrophthalic anhydride
  • Non-photosensitive curing accelerator 1 part by weight of 2-ethyl-4-methylimidazole
  • Filler FB-48 of spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd., Product Name) 700 parts by weight No, Ido Talsite AHT-XA (Kyowa Chemical Industry Co., Ltd., trade name) 1 part by weight (Epoxy resin composition 5: Sealing material use)
  • Epoxy resin EP- 15 80 parts by mass
  • Non-photosensitive hardener 100 parts by weight of methylhexahydrophthalic anhydride
  • Non-photosensitive curing accelerator 1 part by weight of 2-ethyl-4-methylimidazole
  • Filler FB-48 of spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd., (Product name) 700 parts by weight No, IHT Talsite AHT-XA (Kyowa Chemical Industry Co., Ltd., trade name) 1 part by weight Oxetane 20 parts by weight
  • Epoxy resin Naphthalene type liquid epoxy resin (trade name “HP-4032D” manufactured by Dainippon Ink & Chemicals, Inc.) 24 parts by mass Epoxy resin: Dicyclopentagen type solid epoxy resin
  • Non-photosensitive curing agent 60 parts by weight of trialkyltetrahydrophthalic anhydride
  • Non-photosensitive curing accelerator isocyanuric modified solid dispersion type imidazole 8 parts by mass Parts Imidazolesilane coupling agent 2 parts by mass
  • Epoxy resin Epoxy Coat 1009 (epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) in xylene Z butyl solvate (1Z1) (solid content 25%) 320 parts by mass
  • Non-photosensitive curing accelerator 0.2 parts by mass of phosphoric acid
  • Epoxy resin CEL—2021P 50 parts
  • Epoxy resin GT-401 40 parts by weight
  • Non-photosensitive curing agent ALCH-TR: Aluminum trisethylacetate
  • Epoxy resin Bisphenol F type epoxy resin YL983U
  • Non-photosensitive hardener Methylhexahydrophthalic anhydride 100 quality
  • Non-photosensitive curing accelerator 2-ethyl 4-methylimidazole 1
  • Filler of spherical silica FB—48 (Denki Kagaku Kogyo Co., Ltd., trade name) 700 HT, AHT—XA of Idoguchi Talsite (Kyowa Chemical Industry Co., Ltd., trade name) 1 (Epoxy resin composition 10: Sealing material use)
  • Epoxy resin Bisphenol F type epoxy resin YL983U
  • Non-photosensitive hardener 100-methylhexahydrophthalic anhydride
  • Non-photosensitive curing accelerator 2-ethyl 4-methylimidazole 1
  • Filler spherical silica FB—48 (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.) 700 parts, AHT—XA (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) 1 oxetane 20 parts by mass
  • the epoxy resin composition was applied to a glass plate to a thickness of 100 m, the cured specimen was immersed in water, and the whitening state of the coating film treated for 30 minutes at 130 ° C was visually observed, and the following criteria were met. Therefore, the heat resistance was evaluated.
  • a predetermined amount of the epoxy resin composition was applied to the skin of a rat, and after 1 week, the skin condition was observed and judged according to the following criteria to evaluate skin irritation.
  • a test coated plate in which the epoxy resin composition was coated on a glass plate to a thickness of 100 m was tested for 300 hours using a sunshine carbon arc lamp type tester. At that time, the gloss of the coating film A weather resistance test was carried out to promote the feeling! / The weather resistance was evaluated according to the following criteria in comparison with an untreated paint surface
  • Table 1 shows the evaluation results obtained as described above.
  • the epoxy resin composition of the present invention when applied to adhesives, paints, coating agents and sealants, is all curable, adhesive, heat resistant. It can be seen that it is excellent in water, hygiene, weather resistance, corrosion resistance, and storage stability.

Abstract

An epoxy resin composition excellent in curability, adhesiveness, heat resistance, sanitariness, weather resistance, corrosion resistance, storage stability, and so on, which comprises an epoxy resin and a nonphotosensitive curing agent, characterized in that the epoxy resin is a compound represented by the general formula (1).

Description

明 細 書  Specification
エポキシ樹脂組成物  Epoxy resin composition
技術分野  Technical field
[0001] 本発明は、エポキシ榭脂組成物に関し、さら〖こ詳しくは、自動車、航空機、車輛等 の内装材接着剤や構造用接着剤、また屋根、壁、床等の建造物の構造用接着剤、 さらには電子材料用接着剤等、鋼構造物、鋼管、船舶、海洋構造物、コンクリート構 造物などの重防食塗料、食品缶用保護塗料等、コーティング材料、電気材料用封止 材、半導体封止材等に適用できるエポキシ榭脂組成物に関する。  [0001] The present invention relates to an epoxy resin composition, and more specifically, for interior materials and structural adhesives for automobiles, aircraft, vehicles, etc., and for structural structures such as roofs, walls, and floors. Adhesives, and adhesives for electronic materials, etc., heavy-duty anti-corrosion paints for steel structures, steel pipes, ships, marine structures, concrete structures, protective coatings for food cans, coating materials, sealing materials for electrical materials, The present invention relates to an epoxy resin composition that can be applied to a semiconductor sealing material or the like.
背景技術  Background art
[0002] エポキシ榭脂と硬化剤を用いたエポキシ榭脂接着剤としては、多くの技術が公開さ れて (例えば、特許文献 1〜3参照。）いる。しかし、これらも接着剤に要求される硬化 性、接着力、耐熱性等に関し、いまだ十分な特性を有していない。  [0002] Many techniques have been disclosed for epoxy resin adhesives using an epoxy resin and a curing agent (see, for example, Patent Documents 1 to 3). However, these are still not sufficient in terms of curability, adhesive strength, heat resistance, etc. required for adhesives.
[0003] また、エポキシ榭脂と硬化剤を用いたエポキシ榭脂塗料も、多くの技術が公開され て（例えば、特許文献 4〜7参照。）いる。しかし、これらも塗料に要求される硬化性、 接着力、耐熱性等に関しいまだ十分な特性を有していない。硬化性、付着性、衛生 性等に関し、いまだ十分な特性を有していない。  [0003] Further, many techniques for epoxy resin coatings using epoxy resin and a curing agent have been disclosed (see, for example, Patent Documents 4 to 7). However, these are still not sufficient in terms of curability, adhesive strength, heat resistance, etc. required for paints. It does not yet have sufficient properties with respect to curability, adhesion, hygiene, etc.
[0004] さらに、エポキシ榭脂と硬化剤を用いたエポキシ榭脂コーティング材も、多くの技術 が公開されて (例えば、特許文献 8〜10参照。）いる。しかし、これらもコーティング材 に要求される硬化性、接着力、耐熱性等に関しいまだ十分な特性を有していない。 接着性、耐候性、防食性等に関し、いまだ十分な特性を有していない。  [0004] Furthermore, many techniques for epoxy resin coating materials using epoxy resin and a curing agent have been disclosed (see, for example, Patent Documents 8 to 10). However, these also have not yet sufficient characteristics regarding curability, adhesive strength, heat resistance, etc. required for coating materials. It does not yet have sufficient characteristics with respect to adhesiveness, weather resistance, corrosion resistance, and the like.
[0005] 一方、エポキシ榭脂と硬化剤を用いたエポキシ榭脂封止材として、多くの技術が公 開されて (例えば、特許文献 11、 12参照。）いる。しかし、これらもコーティング材に要 求される信頼性、密着性、耐湿性等に関しいまだ十分な特性を有していない。接着 性、耐候性、防食性等に関しいまだ十分な特性を有していない。  [0005] On the other hand, many techniques have been disclosed as an epoxy resin sealant using an epoxy resin and a curing agent (see, for example, Patent Documents 11 and 12). However, these are still not sufficient in terms of reliability, adhesion, moisture resistance and the like required for coating materials. It does not yet have sufficient properties with respect to adhesion, weather resistance, corrosion resistance, etc.
特許文献 1 :特開 2005— 36095号公報 （特許請求の範囲、実施例）  Patent Document 1: JP 2005-36095 A (Claims, Examples)
特許文献 2 :特開 2005— 51131号公報 （特許請求の範囲、実施例）  Patent Document 2: JP-A-2005-51131 (Claims, Examples)
特許文献 3 :特開 2005— 126658号公報 （特許請求の範囲、実施例） 特許文献 4:特開 2002— 121471号公報 （特許請求の範囲、実施例） Patent Document 3: Japanese Patent Application Laid-Open No. 2005-126658 (Claims, Examples) Patent Document 4: Japanese Patent Laid-Open No. 2002-121471 (Claims, Examples)
特許文献 5 :特開 2002— 249532号公報 （特許請求の範囲、実施例）  Patent Document 5: Japanese Patent Laid-Open No. 2002-249532 (Claims, Examples)
特許文献 6 :特開 2002— 275229号公報 （特許請求の範囲、実施例）  Patent Document 6: Japanese Unexamined Patent Application Publication No. 2002-275229 (Claims and Examples)
特許文献 7 :特開 2005— 95723号公報 （特許請求の範囲、実施例）  Patent Document 7: JP-A-2005-95723 (Claims, Examples)
特許文献 8 :特開 2004— 83783号公報 （特許請求の範囲、実施例）  Patent Document 8: Japanese Patent Application Laid-Open No. 2004-83783 (Claims, Examples)
特許文献 9 :特開 2004— 256781号公報 （特許請求の範囲、実施例）  Patent Document 9: Japanese Patent Application Laid-Open No. 2004-256781 (Claims, Examples)
特許文献 10 :特開 2005— 120357号公報 （特許請求の範囲、実施例） 特許文献 11 :特開 2003— 183351号公報 （特許請求の範囲、実施例） 特許文献 12 :特開 2004— 285125号公報 （特許請求の範囲、実施例） 発明の開示  Patent Document 10: JP-A-2005-120357 (Claims and Examples) Patent Document 11: JP-A-2003-183351 (Claims and Examples) Patent Document 12: JP-A-2004-285125 Publication (Claims, Examples) Disclosure of Invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0006] 本発明は、上記課題を鑑みてなされたものであり、その目的は、硬化性、接着性、 耐熱性、衛生性、耐候性、防食性、貯蔵安定性等に優れたエポキシ榭脂組成物を 提供することにある。 [0006] The present invention has been made in view of the above problems, and its purpose is an epoxy resin having excellent curability, adhesion, heat resistance, hygiene, weather resistance, corrosion resistance, storage stability, and the like. It is to provide a composition.
課題を解決するための手段  Means for solving the problem
[0007] 本発明の上記目的は、下記構成により達成された。 [0007] The above object of the present invention has been achieved by the following constitution.
[0008] 1.エポキシ榭脂及び非感光性硬化剤を含有するエポキシ榭脂組成物において、 該エポキシ榭脂が、下記一般式（1)で表される化合物であることを特徴とするェポキ シ榭脂組成物。  [0008] 1. An epoxy resin composition containing an epoxy resin and a non-photosensitive curing agent, wherein the epoxy resin is a compound represented by the following general formula (1): A rosin composition.
[0009] [化 1] 般式 Π>
Figure imgf000003_0001
[0009] [Chemical formula 1] General formula Π>
Figure imgf000003_0001
〔式中、 R は置換基を表し、 mOは 0〜2の整数を、 rOは 1〜3の整数を表す。 Lは主 [Wherein, R represents a substituent, mO represents an integer of 0 to 2, and rO represents an integer of 1 to 3. L is the main
100 0 鎖に酸素原子または硫黄原子を含んでも良 、炭素数 1〜 15の rO + 1価の連結基ま たは単結合を表す。〕 The chain may contain an oxygen atom or a sulfur atom, and may be an rO + 1 monovalent linking group having 1 to 15 carbon atoms. Or a single bond. ]
2.前記一般式（1)で表されるエポキシ榭脂が、下記一般式 (2)で表される化合物 であることを特徴とする前記 1に記載のエポキシ榭脂組成物。  2. The epoxy resin composition according to 1, wherein the epoxy resin represented by the general formula (1) is a compound represented by the following general formula (2):
[0011] [化 2] 般式 (2)
Figure imgf000004_0001
[0011] [Chemical formula 2] General formula (2)
Figure imgf000004_0001
[0012] 〔式中、 R は置換基を表し、 mlは 0〜2の整数を、 pl、qlはそれぞれ 0または 1を、 r [In the formula, R represents a substituent, ml represents an integer of 0 to 2, pl and ql each represent 0 or 1, r
101  101
1は 1〜3の整数を表す。 Lは主鎖に酸素原子または硫黄原子を含んでも良い炭素  1 represents an integer of 1 to 3. L is carbon that may contain oxygen or sulfur atoms in the main chain
1  1
数 1〜15の rl + 1価の連結基または単結合を表す。〕  Rl + 1 represents a monovalent linking group or a single bond. ]
3.前記一般式（1)で表されるエポキシ榭脂が、下記一般式 (3)で表される化合物 であることを特徴とする前記 1に記載のエポキシ榭脂組成物。  3. The epoxy resin composition according to 1 above, wherein the epoxy resin represented by the general formula (1) is a compound represented by the following general formula (3):
[0013] [化 3] [0013] [Chemical 3]
-般式 (3)
Figure imgf000004_0002
-General formula (3)
Figure imgf000004_0002
[0014] 〔式中、 R は置換基を表し、 m2は 0〜2の整数を、 p2、 q2はそれぞれ 0または 1を、 r [Wherein, R represents a substituent, m2 represents an integer of 0 to 2, p2 and q2 each represents 0 or 1, r
102  102
2は 1〜3の整数を表す。 Lは主鎖に酸素原子または硫黄原子を含んでも良い炭素  2 represents an integer of 1 to 3. L is carbon that may contain oxygen or sulfur atoms in the main chain
2  2
数 1〜15の r2+ l価の連結基または単結合を表す。〕  It represents an r2 + l-valent linking group or a single bond of 1 to 15. ]
4.前記一般式（1)で表されるエポキシ榭脂が、下記一般式 (4)で表される化合物 であることを特徴とする前記 1に記載のエポキシ榭脂組成物。  4. The epoxy resin composition according to 1, wherein the epoxy resin represented by the general formula (1) is a compound represented by the following general formula (4):
[0015] [化 4] 一般
Figure imgf000005_0001
[0015] [Chemical 4] General
Figure imgf000005_0001
[0016] 〔式中、 R及び Rは水素原子またはアルキル基を表す。ただし、 Rと Rが同時に水 [Wherein, R and R represent a hydrogen atom or an alkyl group. However, R and R are water at the same time.
1 2 1 2  1 2 1 2
素原子であることはない。 Rは水素原子、ハロゲン原子または置換基を表す。 R  It is not an elementary atom. R represents a hydrogen atom, a halogen atom or a substituent. R
3 4、 R  3 4, R
5 は水素原子、ハロゲン原子または置換基を表す。 Rは C*1及び C*2で表される炭素原 5 represents a hydrogen atom, a halogen atom or a substituent. R is the carbon source represented by C * 1 and C * 2.
7  7
子に炭素原子、窒素原子または硫黄原子を介して結合する 2価の連結基を表す。 R  Represents a divalent linking group bonded to a child via a carbon atom, nitrogen atom or sulfur atom. R
8 は Rと同義である。 R及び R は R及び Rと同義である。 R 及び R は R及び Rと同 8 is synonymous with R. R and R are synonymous with R and R. R and R are the same as R and R
3 9 10 1 2 11 12 4 5 義である。 R 3 9 10 1 2 11 12 4 5 Righteous. R
4、 R  4, R
5、 R 及び R の少なくとも 1つは水素原子である。〕  5. At least one of R and R is a hydrogen atom. ]
11 12  11 12
5.前記エポキシ榭脂として、さらに、クレゾ一ルノボラック型エポキシ榭脂、ビフエ- ール型エポキシ榭脂及びジシクロ型エポキシ榭脂から選ばれる少なくとも 1種を含有 することを特徴とする前記 1乃至 4のいずれか 1項に記載のエポキシ榭脂組成物。  5. The epoxy resin further comprising at least one selected from a cresol novolac type epoxy resin, a biphenyl type epoxy resin, and a dicyclo type epoxy resin. The epoxy resin composition according to any one of the above.
[0017] 6.前記クレゾ一ルノボラック型エポキシ榭脂、ビフエニール型エポキシ榭脂または ジシクロ型エポキシ榭脂が、 25°Cで固形であることを特徴とする前記 5に記載のェポ キシ榭脂組成物。 [0017] 6. The epoxy resin composition according to 5 above, wherein the cresol novolac type epoxy resin, biphenyl type epoxy resin or dicyclo type epoxy resin is solid at 25 ° C. object.
[0018] 7.非感光性硬化促進剤を含有することを特徴とする前記 1乃至 6のいずれか 1項 に記載のエポキシ榭脂組成物。  [0018] 7. The epoxy resin composition according to any one of 1 to 6, further comprising a non-photosensitive curing accelerator.
[0019] 8.充填剤を含有することを特徴とする前記 1乃至 7のいずれか 1項に記載のェポキ シ榭脂組成物。  [0019] 8. The epoxy resin composition according to any one of 1 to 7, which further comprises a filler.
[0020] 9.熱可塑性榭脂を含有することを特徴とする前記 1乃至 8のいずれか 1項に記載 のエポキシ榭脂組成物。 発明の効果  [0020] 9. The epoxy resin composition according to any one of 1 to 8 above, which contains a thermoplastic resin. The invention's effect
[0021] 本発明により、硬化性、接着性、耐熱性、衛生性、耐候性、防食性、貯蔵安定性等 に優れたエポキシ榭脂組成物を提供することができた。  [0021] According to the present invention, an epoxy resin composition excellent in curability, adhesiveness, heat resistance, hygiene, weather resistance, corrosion resistance, storage stability and the like could be provided.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0022] 本発明を更に詳しく説明する。 [0023] 本発明のエポキシ榭脂組成物は、エポキシ榭脂および硬化剤を必須成分とするェ ポキシ榭脂組成物で、さらに硬化促進剤や充填剤等を含有させてもょ ヽエポキシ榭 脂組成物である。 [0022] The present invention will be described in more detail. [0023] The epoxy resin composition of the present invention is an epoxy resin composition containing an epoxy resin and a curing agent as essential components, and may further contain a curing accelerator, a filler and the like. It is a composition.
[0024] まず、本発明に用いられる一般式（1)で表されるエポキシ榭脂と、より好ましい形態 である一般式 (2)及び一般式 (3)で表されるエポキシ榭脂につ 、て説明する。  [0024] First, the epoxy resin represented by the general formula (1) used in the present invention and the epoxy resin represented by the general formula (2) and the general formula (3), which are more preferable forms, I will explain.
[0025] 一般式（1)、一般式（2)及び一般式（3)において、 R 、R 、R はそれぞれ置換 [0025] In general formula (1), general formula (2), and general formula (3), R 1, R 2, and R 3 are each substituted.
100 101 102  100 101 102
基を表す。置換基の例としては、例えば、ハロゲン原子 (例えば、塩素原子、臭素原 子、フッ素原子等）、炭素数 1〜6個のアルキル基 (例えば、メチル基、ェチル基、プロ ピル基、イソプロピル基、ブチル基等）、炭素数 1〜6個のアルコキシ基 (例えば、メト キシ基、エトキシ基、 n—プロポキシ基、 iso プロポキシ基、 n—ブトキシ基、 tert—ブ トキシ基等）、ァシル基 (例えば、ァセチル基、プロピオニル基、トリフルォロアセチル 基等）、ァシルォキシ基 (例えば、ァセトキシ基、プロピオニルォキシ基、トリフルォロ ァセトキシ基等）、アルコキシカルボ-ル基 (例えば、メトキシカルボニル基、エトキシ カルボニル基、 tert ブトキシカルボニル基等）等が挙げられる。置換基として好まし いのは、アルキル基、アルコキシ基、アルコキシカルボ-ル基である。  Represents a group. Examples of the substituent include, for example, a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group). , Butyl, etc.), alkoxy groups having 1 to 6 carbon atoms (eg, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, etc.), acyl groups ( For example, acetyl group, propionyl group, trifluoroacetyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxy carbonyl group (for example, methoxycarbonyl group, ethoxy carbonyl group, etc.) Tert-butoxycarbonyl group, etc.). Preferable substituents are an alkyl group, an alkoxy group, and an alkoxy carbo group.
[0026] m0、 ml、 m2はそれぞれ 0〜2を表し、 0または 1が好ましい。 [0026] m0, ml and m2 each represents 0 to 2, preferably 0 or 1.
[0027] Lは主鎖に酸素原子または硫黄原子を含んでもよい炭素数 1〜15の rO+ 1価の連 [0027] L is an rO + monovalent chain having 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain.
0  0
結基あるいは単結合を、 Lは主鎖に酸素原子または硫黄原子を含んでもよい炭素数  A linking group or a single bond, L is the number of carbon atoms that may contain oxygen or sulfur atoms in the main chain
1  1
1〜15の rl + 1価の連結基あるいは単結合を、 Lは主鎖に酸素原子または硫黄原  1 to 15 rl + monovalent linking group or single bond, L is oxygen atom or sulfur atom in the main chain
2  2
子を含んでもょ 、炭素数 1〜 15の r2 + 1価の連結基ある!/ヽは単結合を表す。  Even if it contains a child, it is an r2 + one-valent linking group having 1 to 15 carbon atoms! / ヽ represents a single bond.
[0028] 主鎖に酸素原子または硫黄原子を含んでもよい炭素数 1〜15の 2価の連結基の例 としては、以下の基及びこれらの基と一 O 基、 S 基、 CO 基、 CS 基を 複数組み合わせてできる基を挙げることができる。 [0028] Examples of the divalent linking group having 1 to 15 carbon atoms, which may contain an oxygen atom or a sulfur atom in the main chain, include the following groups and these groups and a mono-O group, S group, CO group, CS Examples include groups formed by combining a plurality of groups.
[0029] メチレン基 [― CH―]、ェチリデン基 [ >CHCH ]、イソプロピリデン [ >C (CH ) ] [0029] Methylene group [—CH—], Ethylidene group [> CHCH], Isopropylidene [> C (CH)]
2 3 3 2 2 3 3 2
、 1, 2—エチレン基 [ CH CH―]、 1, 2—プロピレン基 [― CH (CH ) CH―]、 1 1, 2-ethylene group [CH CH-], 1, 2-propylene group [-CH (CH) CH-], 1
2 2 3 2 2 2 3 2
, 3 プロパンジィル基 [ CH CH CH― ]、 2, 2 ジメチルー 1, 3 プロパンジィ , 3 Propandyl group [CH CH CH-], 2, 2 Dimethyl-1,3 Propandi
2 2 2  2 2 2
ル基 [― CH C (CH ) CH― ]、 2, 2 ジメトキシ— 1, 3 プロパンジィル基 [ CH  Group [— CH C (CH) CH—], 2, 2 dimethoxy-1, 3, propanediyl group [CH
2 3 2 2 2 2 3 2 2 2
C (OCH ) CH―]、 2, 2 ジメトキシメチル— 1, 3 プロパンジィル基 [― CH C (C H OCH ) CH―]、 1—メチル 1, 3 プロパンジィル基 [— CH(CH )CH CHC (OCH) CH—], 2, 2 dimethoxymethyl— 1, 3 propanediyl group [— CH C (C H OCH) CH—], 1-methyl 1, 3 propanediyl group [— CH (CH) CH CH
2 3 2 2 3 2 2 一]、 1, 4 ブタンジィル基 [ CH CH CH CH一]、 1, 5 ペンタンジィル基 [ 2 3 2 2 3 2 2 1], 1, 4 Butanediyl group [CH CH CH CH 1], 1, 5 Pentandyl group [
2 2 2 2  2 2 2 2
CH CH CH CH CH—]、ォキシジエチレン基 [ CH CH OCH CH—]、チォジ CH CH CH CH CH—], oxydiethylene group [CH CH OCH CH—],
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
エチレン基 [― CH CH SCH CH—]、 3—ォキソチオジェチレン基 [ CH CH S Ethylene group [― CH CH SCH CH—], 3-oxothiojetylene group [CH CH S
2 2 2 2 2 2 2 2 2 2 2 2
OCH CH― ]、 3, 3 ジォキソチオジェチレン基 [ CH CH SO CH CH― ]、 1OCH CH—], 3, 3 Dioxothiojetylene group [CH CH SO CH CH—], 1
2 2 2 2 2 2 22 2 2 2 2 2 2
, 4 ジメチル— 3—ォキサ—1, 5 ペンタンジィル基 [― CH(CH )CH OCH(CH , 4 Dimethyl-3-oxa-1, 5 Pentandyl [-CH (CH) CH OCH (CH
3 2  3 2
)CH―]、 3—ォキソペンタンジィル基 [ CH CH COCH CH― ]、 1, 5 ジォキ ) CH-], 3-oxopentanediol [CH CH COCH CH-], 1, 5 dioxo
3 2 2 2 2 2 3 2 2 2 2 2
ソ一 3—ォキサペンタンジィル基 [ COCH OCH CO— ]、 4—ォキサ 1, 7 へ So 1-Oxapentanediyl [COCH OCH CO-], 4-Oxa 1, 7
2 2  twenty two
プタンジィル基 [ CH CH CH OCH CH CH―]、 3, 6 ジォキサ一 1, 8—オタ Ptandyl group [CH CH CH OCH CH CH-], 3, 6 Dioxa 1, 8-Ota
2 2 2 2 2 2  2 2 2 2 2 2
タンジィル基 [ CH CH OCH CH OCH CH―]、 1, 4, 7 トリメチル 3, 6 ジ Tandyl group [CH CH OCH CH OCH CH-], 1, 4, 7 Trimethyl 3, 6 Di
2 2 2 2 2 2  2 2 2 2 2 2
ォキサ― 1, 8 オクタンジィル基 [― CH(CH )CH 0-CH(CH )CH OCH(CH Oxa-1, 8 Octandyl [-CH (CH) CH 0-CH (CH) CH OCH (CH
3 2 3 2 3 3 2 3 2 3
)CH―]、 5, 5 ジメチル— 3, 7 ジォキサ— 1, 9 ノナンジィル基 [ CH CH O) CH-], 5, 5 Dimethyl-3, 7 Dioxa-1, 9 Nonandyl group [CH CH O
2 2 22 2 2
CH C(CH ) CH OCH CH一]、 5, 5 ジメトキシ一 3, 7 ジォキサ一 1, 9 ノナCH C (CH) CH OCH CH 1], 5, 5 Dimethoxy 1, 3, 7 Dioxa 1, 9 Nona
2 3 2 2 2 2 2 3 2 2 2 2
ンジィル基 [― CH CH OCH C(OCH ) CH OCH CH― ]、 5, 5—ジメトキシメチ Nylyl group [—CH CH OCH C (OCH) CH OCH CH—], 5,5-dimethoxymethyl
2 2 2 3 2 2 2 2  2 2 2 3 2 2 2 2
ルー 3, 7 ジォキサ— 1, 9 ノナンジィル基、 [― CH CH OCH C(CH OCH ) C Lu 3, 7 Dioxa-1, 9 Nonaneyl group, [-CH CH OCH C (CH OCH) C
2 2 2 2 3 2 2 2 2 2 3 2
H OCH CH—]、4, 7 ジォキソ一 3, 8 ジォキサ一 1, 10 デカンジィル基 [H OCH CH—], 4, 7 Dioxo 3, 8 Dioxa 1, 10 Decandyl [
2 2 2 2 2 2
CH CH O-COCH CH CO— OCH CH一]、 3, 8—ジォキソ一4, 7—ジォキサ CH CH O-COCH CH CO— OCH CH 1], 3, 8—Dioxo 1,7—Dioxa
2 2 2 2 2 2 2 2 2 2 2 2
-1, 10 デカンジィル基 [ CH CH CO-OCH CH O— COCH CH― ]、 1, 3  -1, 10 Decandyl group [CH CH CO-OCH CH O- COCH CH-], 1, 3
2 2 2 2 2 2 2 2 2 2 2 2
—シクロペンタンジィル基 [ 1, 3— CH― ]、 1, 2 シクロへキサンジィル基 [ 1, —Cyclopentadyl group [1, 3— CH—], 1, 2 cyclohexanediyl group [1,
5 8  5 8
2-C H ―]、 1, 3 シクロへキサンジィル基 [ 1, 3-CH ―]、 1, 4 シクロへ 2-C H-], 1, 3 cyclohexanediyl group [1, 3-CH-], 1, 4 cyclo
6 10 6 10 6 10 6 10
キサンジィル基 [ 1, 4-CH 一]、 2, 5—テトラヒドロフランジィル基 [2, 5-CH Xanthyl group [1, 4-CH i], 2,5-tetrahydrofuran diyl group [2, 5-CH
6 10 4 6 6 10 4 6
O— ]、 p フエ二レン基 [― p— C H一]、 m—フエ二レン基 [― m— C H一]、 a, a O—], p phenylene group [—p—CH 1], m—phenylene group [—m—CH 1], a, a
6 4 6 4  6 4 6 4
' ― o キシリレン基 [― o— CH― C H― CH― ]、 α, α' —m キシリレン基 [  '― O xylylene group [― o- CH― C H- CH-], α, α' —m xylylene group [
2 6 4 2  2 6 4 2
-m-CH -CH -CH一]、 α, α' ρ キシリレン基 [—p— CH—CH4— C  -m-CH -CH -CH i], α, α 'ρ Xylylene group [—p— CH—CH 4 — C
2 6 4 2 2 6 2 6 4 2 2 6
H―]、フラン一 2, 5 ジィル一ビスメチレン基 [2, 5-CH― C H ― CH―]、チH—], furan 2,5 diyl bismethylene [2, 5-CH—CH—CH—],
2 2 4 20 2 ォフェン一 2, 5 ジィル一ビスメチレン基 [2, 5-CH― C H S— CH―]、イソプロ 2 2 4 20 2 ophen 1,2,5 diyl bismethylene [2,5-CH—C H S—CH—], isopropyl
2 4 2 2  2 4 2 2
ピリデンビスー p フエ二レン基 [ p— CH— C(CH) — p— CH—]。 Pyridenebisu p-phenylene group [p—CH—C (CH) —p—CH—].
6 4 3 2 6 4  6 4 3 2 6 4
3価以上の連結基としては、以上に挙げた 2価の連結基から任意の部位の水素原 子を必要なだけ除いてできる基及びそれらと—O—基、—S—基、—CO—基、—CSThe trivalent or higher linking group includes a hydrogen atom at any site from the divalent linking groups listed above. Groups that can be removed by removing as many children as necessary and those with —O— groups, —S— groups, —CO— groups, —CS
—基を複数組み合わせてできる基を挙げることができる。 — A group formed by combining a plurality of groups can be mentioned.
[0031] L、 L、 Lはそれぞれ置換基を有して!/、てもよ 、。置換基の例としては、ハロゲン原  [0031] Each of L, L, and L may have a substituent! /. Examples of substituents include halogen atoms
0 1 2  0 1 2
子 (例えば、塩素原子、臭素原子、フッ素原子等）、炭素数 1〜6個のアルキル基 (例 えば、メチル基、ェチル基、プロピル基、イソプロピル基、ブチル基等）、炭素数 1〜6 個のアルコキシ基（例えば、メトキシ基、エトキシ基、 n—プロポキシ基、 iso—プロポキ シ基、 n—ブトキシ基、 tert—ブトキシ基等）、ァシル基 (例えば、ァセチル基、プロピ ォ-ル基、トリフルォロアセチル基等）、ァシルォキシ基 (例えば、ァセトキシ基、プロ ピオニルォキシ基、トリフルォロアセトキシ基等）、アルコキシカルボ-ル基 (例えば、 メトキシカルボ-ル基、エトキシカルボ-ル基、 tert—ブトキシカルボ-ル基等）等が 挙げられる。置換基として好ましいのは、アルキル基、アルコキシ基、アルコキシカル ボ-ル基である。  Child (for example, chlorine atom, bromine atom, fluorine atom, etc.), alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.), carbon number 1 to 6 Alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl groups (for example, acetyl group, propoxy group, Trifluoroacetyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxy carbo yl group (eg, methoxy carbo ol group, ethoxy carbo ol group, tert- Butoxycarbonyl group, etc.). Preferred as a substituent are an alkyl group, an alkoxy group, and an alkoxy carbo group.
[0032] L、 L、 Lとしては主鎖に酸素原子または硫黄原子を含んでもよ!、炭素数 1〜8の 2  [0032] L, L, and L may contain an oxygen atom or a sulfur atom in the main chain !, 2 having 1 to 8 carbon atoms
0 1 2  0 1 2
価の連結基が好ましぐ主鎖が炭素のみ力 なる炭素数 1〜5の 2価の連結基がより 好ましい。  A divalent linking group having 1 to 5 carbon atoms in which the main chain preferred by the valent linking group is only carbon is more preferred.
[0033] pl、 qlはそれぞれ 0または 1を表し、 pi + qlが 1以上であるのが好ましい。  [0033] pl and ql each represents 0 or 1, and pi + ql is preferably 1 or more.
[0034] p2、 q2はそれぞれ 0または 1を表し、それぞれ 1が好ましい。 [0034] p2 and q2 each represents 0 or 1, and 1 is preferred for each.
[0035] 以下、本発明に係る一般式（1)、一般式 (2)及び一般式 (3)で表されるエポキシ榭 脂の具体例を示すが、本発明はこれらに限定されるものではない。  [0035] Specific examples of the epoxy resin represented by the general formula (1), the general formula (2), and the general formula (3) according to the present invention are shown below, but the present invention is not limited thereto. Absent.
[0036] [化 5] [0036] [Chemical 5]
Figure imgf000009_0001
Figure imgf000009_0001
m m m m ■0 ■a m m m m ■ 0 ■ a
〔¾003  [¾003
1 1
Figure imgf000010_0001
Figure imgf000010_0001
Figure imgf000011_0001
8]
Figure imgf000011_0001
8]
Figure imgf000012_0001
Figure imgf000012_0001
O— CH2C — O C O— CH 2 C — OC
CH2 CH 2
t  t
— O - CH2CH2〜0- CH2 C— CH2— O— CH2CH2— O— C- -CH3 — O-CH 2 CH 2 to 0- CH 2 C— CH 2 — O— CH 2 CH 2 — O— C- —CH 3
I II CH3 O I II CH 3 O
Figure imgf000012_0002
Figure imgf000012_0002
Figure imgf000012_0003
Figure imgf000012_0003
Figure imgf000013_0001
Figure imgf000013_0001
10] 〔〕〔〕004211 Ten] [] [] 004211
Figure imgf000014_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000015_0001
Figure imgf000015_0002
Figure imgf000015_0002
[0043] 次に、本発明に係る一般式（1)で表される化合物の好ましい形態の 1つである一般 式 (4)で表される化合物につ 、て詳述する。 Next, the compound represented by the general formula (4), which is one of the preferred forms of the compound represented by the general formula (1) according to the present invention, will be described in detail.
[0044] 一般式 (4)にお！/、て、 R及び Rはそれぞれ水素原子またはアルキル基を表すが、 [0044] In general formula (4)! /, R and R each represent a hydrogen atom or an alkyl group,
1 2  1 2
アルキル基として具体的には、炭素数 1〜20個のアルキル基（例えば、メチル基、ェ チル基、プロピル基、イソプロピル基、ブチル基等）、炭素数 3〜6個のシクロアルキ ル基（例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル 基等）が挙げられる。 Rと Rは同時に水素原子であることはなぐ好ましくは一方が水 Specific examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group), and a cycloalkyl group having 3 to 6 carbon atoms (for example, , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl Group). R and R are not simultaneously hydrogen atoms, preferably one is water
1 2  1 2
素原子で他方がアルキル基、特に好ましくはメチル基である。 Rは水素原子、ハロゲ  A primary atom and the other is an alkyl group, particularly preferably a methyl group. R is a hydrogen atom, halogene
3  Three
ン原子または置換基を表すが、ハロゲン原子として具体的には塩素原子、臭素原子 またはフッ素原子が挙げられる。好ましくはフッ素原子、塩素原子である。 Rとして特  A halogen atom specifically includes a chlorine atom, a bromine atom or a fluorine atom. Preferably they are a fluorine atom and a chlorine atom. Special as R
3 に好ましくは水素原子である。  3 is preferably a hydrogen atom.
[0045] 置換基として具体的には炭素数 1〜20個のアルキル基 (例えば、メチル基、ェチル 基、プロピル基、イソプロピル基、ブチル基等）、炭素数 3〜6個のシクロアルキル基（ 例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基等） 、炭素数 1〜20個のアルコキシ基 (例えば、メトキシ基、エトキシ基、 n—プロポキシ基 、 iso プロポキシ基、 n ブトキシ基、 tert ブトキシ基等）、炭素数 2〜20のァシル 基 (例えば、ァセチル基、プロピオニル基、トリフルォロアセチル基等）、炭素数 2〜2 0のァシルォキシ基（例えば、ァセトキシ基、プロピオ-ルォキシ基、トリフルォロアセト キシ基等）、炭素数 2〜20のァシルチオ基 (例えば、ァセチルチオ基、プロピオ-ル チォ基、トリフルォロアセチルチオ基等）、炭素数 2〜20のアルコキシカルボ-ル基（ メトキシカルボ-ル基、エトキシカルボ-ル基、 tert ブトキシカルボ-ル基等）、炭 素数 2〜20のアルキルチオカルボ-ル基（例えば、メチルチオカルボ-ル基、ェチル チォカルボニル基、 tert プチルチオカルボ-ル基等)等が挙げられる。置換基とし て好ましいのは、ハロゲン原子、アルコキシ基、ァシルォキシ基、アルコキシカルボ- ル基である。 [0045] Specific examples of the substituent include an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group), and a cycloalkyl group having 3 to 6 carbon atoms ( For example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like, alkoxy group having 1 to 20 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso propoxy group, n butoxy group, tert butoxy group, etc.), an acyl group having 2 to 20 carbon atoms (eg, acetyl group, propionyl group, trifluoroacetyl group, etc.), an acyloxy group having 2 to 20 carbon atoms (eg, acetooxy group, propio-loxy group) , Trifluoroacetoxy group, etc.), an acylyl group having 2 to 20 carbon atoms (for example, acetylylthio group, propio-lthio group, trifluoroacetylthio group, etc.), carbon number 2 20 alkoxy carbonyl groups (methoxy carbo group, ethoxy carbo group, tert butoxy carbo ol group, etc.), alkyl thio carbo groups having 2 to 20 carbon atoms (eg methyl thio carbo ol group, ethyl) Thiocarbonyl group, tert butylthiocarbol group, etc.). Preferable substituents are a halogen atom, an alkoxy group, an acyloxy group, and an alkoxycarbonyl group.
[0046] R及び Rはそれぞれ水素原子、ハロゲン原子、または置換基を表す力 C*1で表さ [0046] R and R are each represented by a force C * 1 representing a hydrogen atom, a halogen atom, or a substituent.
4 5  4 5
れる炭素原子に炭素原子、窒素原子または硫黄原子を介して結合する置換基が好 ましい。ハロゲン原子として具体的には塩素原子、臭素原子またはフッ素原子が挙げ られる。好ましくは塩素原子、フッ素原子である。また C*1で表される炭素原子に炭素 原子、窒素原子または硫黄原子を介して結合する置換基として具体的にはアルキル 基（例えば、メチル基、ェチル基、プロピル基、ブチル基、ペンチル基、 iso ペンチ ル基、 2—ェチルーへキシル基、ォクチル基、デシル基等）、ァリール基 (例えば、フ ェニル基、ナフチル基、アントラ-ル基等）、複素環基 (例えば、 2—ピリジル基、 1 ピロリル基、 2 チアゾィル基、 3 チェニル基等）、シクロアルキル基 (例えば、シクロ へキシル基、シクロへプチル基等）、ァルケ-ル基（例えば、エテュルー 2—プロべ- ル基、 3 ブテュル基、 1ーメチルー 3—プロべ-ル基、 3 ペンテ-ル基、 1ーメチ ルー 3 ブテュル基等）、シクロアルケ-ル基 (例えば、 1ーシクロアルケ-ル基、 2— シクロアルケニル基等）、アルキ-ル基 (例えば、ェチュル基、 1 プロピニル基等）、 チォ基 (例えば、メチルチオ基、トリフルォロメチルチオ基、フエ二ルチオ基等）、カル ボキシル基、カルボ-ルァミノ基 (例えば、ァセチルァミノ基、ベンゾィルァミノ基等）、 ウレイド基 (例えば、メチルァミノカルボニルァミノ基等）、スルホ -ルァミノ基 (例えば、 メタンスルホ -ルァミノ基、ベンゼンスルホ -ルァミノ基等）、スルホ -ル基（例えば、メ タンスルホ-ル基、トリフルォロメタンスルホ-ル基、トルエンスルホ -ル基等）、カル バモイル基（例えば、力ルバモイル基、 N, N ジメチルカルバモイル基、 N—モルホ リノカルボ-ル基等）、スルファモイル基（例えば、スルファモイル基、 N, N ジメチル スルファモイル基、モルフオリノスルファモイル基等）、ニトロ基、シァノ基、スルホンァ ミド基（例えば、メタンスルホンアミド基、ブタンスルホンアミド基、ベンゼンスルホンアミ ド基等）、アミノ基 (例えばアミノ基、 N, N ジメチルァミノ基、 N, N ジェチルァミノ 基、ァ-リノ基等）、スルホ基、ホスフオノ基、サルファイト基、スルフィノ基、スルホ-ル ァミノカルボ-ル基（例えば、メタンスルホ -ルァミノカルボ-ル基、エタンスルホ-ル ァミノカルボ-ル基、ベンゼンスルホ -ルァミノ基等）、カルボ-ルアミノスルホ -ル基 (例えば、ァセトアミドスルホ -ル基、メトキシァセトアミドスルホ -ル基、ベンズアミドス ルホニル基等）、ァミノカルボ-ル基 (例えば、ァセトアミドカルボニル基、メトキシァセ トアミドカルボ-ル基、ベンズアミドカルボ-ル基等）、スルフィエルァミノカルボ-ル 基（例えば、メタンスルフィエルァミノカルボ-ル基、エタンスルフィエルァミノカルボ- ル基、ベンゼンスルフィエルアミノカルボ-ル基等）、下記 *で表される基が置換した アルキル基 (例えば、メトキシメチル基、エトキシメチル基、メトキシェチル基、フエノキ シェチル基、カルボキシメチル基、アミノメチル基、スルホンアミドメチル基等）、下記 *で表される基が置換したァリール基（例えば、 p—メトキシフエ-ル基、 p—スルホン アミドフエ-ル基、 2クロ口 6ピリジル基、 m—-トロフエ-ル基）等が挙げられる。 R Substituents bonded to the carbon atom via a carbon atom, nitrogen atom or sulfur atom are preferred. Specific examples of the halogen atom include a chlorine atom, a bromine atom and a fluorine atom. A chlorine atom and a fluorine atom are preferred. In addition, as a substituent bonded to the carbon atom represented by C * 1 through a carbon atom, a nitrogen atom or a sulfur atom, specifically, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group). , Iso pentyl group, 2-ethylhexyl group, octyl group, decyl group, etc.), aryl group (eg, phenyl group, naphthyl group, anthral group, etc.), heterocyclic group (eg, 2-pyridyl group, etc.) 1 pyrrolyl group, 2 thiazoyl group, 3 cenyl group, etc.), cycloalkyl group (for example, cyclo Hexyl group, cycloheptyl group, etc.), alkenyl group (eg Etul 2—Probel group, 3 Butyl group, 1-methyl-3—Probel group, 3 Pentayl group, 1-Methyl group) 3 butyr group, etc.), cycloalkenyl group (eg, 1-cycloalkenyl group, 2-cycloalkenyl group, etc.), alkyl group (eg, etulyl group, 1 propynyl group, etc.), thio group (eg, methylthio group) , Trifluoromethylthio group, phenylthio group, etc.), carboxy group, carbolamino group (eg, acetylamino group, benzoylamino group, etc.), ureido group (eg, methylaminocarbonylamino group, etc.), sulfo- Luamino group (eg, methanesulfo-lumino group, benzenesulfo-lumino group, etc.), sulfole group (eg, methanesulfo group, trifluoromethanesulfol group) Toluenesulfol group, etc.), carbamoyl group (eg, strong rubamoyl group, N, N dimethylcarbamoyl group, N-morpholinocarbol group, etc.), sulfamoyl group (eg, sulfamoyl group, N, N dimethyl sulfamoyl group, Morpholinosulfamoyl group, etc.), nitro group, cyano group, sulfonamide group (eg methanesulfonamide group, butanesulfonamide group, benzenesulfonamide group etc.), amino group (eg amino group, N, N dimethylamino) Group, N, N jetylamino group, aminoino group, etc.), sulfo group, phosphono group, sulfite group, sulfino group, sulfoaminocarbonyl group (for example, methanesulfoluminocarbon group, ethanesulfoaminocarbo group) Group, benzenesulfo-lumino group, etc.), carboaminosulfo group (for example, , Acetamidosulfol group, methoxyacetamidosulfol group, benzamidosulfonyl group, etc.), amino carbonyl group (for example, acetamidocarbonyl group, methoxyacetamidocarbol group, benzamidocarboro group, etc.) ), Sulfaluminocarbol groups (for example, methanesulfaluminocarbol group, ethanesulfaluminocarbol group, benzenesulfaminoaminocarbol group, etc.), represented by the following * An alkyl group substituted with a group (for example, a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, a phenoxycetyl group, a carboxymethyl group, an aminomethyl group, a sulfonamidomethyl group), an aryl substituted with a group represented by the following * Groups (e.g., p-methoxyphenyl group, p-sulfonamidophenol group, 2-chloro-6-pyridyl group, m--trophenol group) and the like. R
4 及び Rとして好ましくはアルキル基、及び下記 *で表される基が置換したアルキル基 4 and R are preferably an alkyl group, and an alkyl group substituted by a group represented by the following *
5 Five
であり、より好ましくはアルキル基である。また、 R及び Rの少なくとも 1つは水素原子 であるが、好ましくは 2つが水素原子でありその他がアルキル基、または下記 *で表 される基が置換したアルキル基の場合である。 And more preferably an alkyl group. And at least one of R and R is a hydrogen atom. However, it is preferable that two are hydrogen atoms and the other is an alkyl group or an alkyl group substituted with a group represented by * below.
[0047] *で表される基としては、具体的にはアルキル基、シクロアルキル基、ァルケ-ル基 、シクロアルケ-ル基、アルキニル基、ァリール基、複素環基、アルコキシ基、ァリー ルォキシ基、ァシル基、カルボ-ルォキシ基、チォ基、カルボキシル基、カルボニル アミノ基、ウレイド基、スルホ -ルァミノ基、スルホ-ル基、力ルバモイル基、スルファモ ィル基、ヒドロキシル基、ニトロ基、シァノ基、スルホンアミド基、アミノ基、スルホ基、ホ スフオノ基、サルファイト基、スルフィノ基、スルホ -ルァミノカルボ-ル基、カルボ-ル アミノスルホ -ル基、ァミノカルボ-ル基、スルフィエルァミノカルボ-ル基等が挙げら れる。 [0047] Specific examples of the group represented by * include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, Acyl group, carbo-loxy group, thio group, carboxyl group, carbonyl amino group, ureido group, sulfo-lumino group, sulfo group, strong rubamoyl group, sulfamoyl group, hydroxyl group, nitro group, cyano group, sulfone Amide group, amino group, sulfo group, phosphono group, sulfite group, sulfino group, sulfo-luminocarbon group, carbo amino group, aminocarbol group, sulfaluminocarbon group, etc. Are listed.
[0048] 上記エポキシ榭脂にお ヽて、 R及び Rで表される酸素原子を含有する置換基も好  [0048] In the above epoxy resin, a substituent containing an oxygen atom represented by R and R is also preferable.
4 5  4 5
ましい。具体的には、アルコキシ基、ァリールォキシ基、ァシル基、カルボ-ルォキシ 基、カルボキシル基、カルボ-ルァミノ基、ウレイド基、スルホ -ルァミノ基、スルホ- ル基、力ルバモイル基、スルファモイル基、ヒドロキシル基、ニトロ基、スルホンアミド基 、スルホ基、ホスフオノ基、サルファイト基、スルフィノ基、スルホ -ルァミノカルボ-ル 基、カルボ-ルアミノスルホ -ル基、ァミノカルボ-ル基、スルフィエルァミノカルボ- ル基等を部分構造として有する基を表す。好ましくはアルコキシ基を部分構造として 有する基である。  Good. Specifically, an alkoxy group, an aryloxy group, an acyl group, a carbo-loxy group, a carboxyl group, a carbo-lumino group, a ureido group, a sulfo-lumino group, a sulfo group, a strong rubamoyl group, a sulfamoyl group, a hydroxyl group, Partially include nitro group, sulfonamido group, sulfo group, phosphono group, sulfite group, sulfino group, sulfo-luminocarbon group, carboaminosulfol group, aminocarbol group, sulfeaminoamino group, etc. A group having a structure is represented. A group having an alkoxy group as a partial structure is preferable.
[0049] また、上記エポキシ榭脂にお 、て R及び Rで表される水素原子と炭素原子のみか  [0049] In the epoxy resin, only hydrogen atoms and carbon atoms represented by R and R
4 5  4 5
ら構成される炭化水素基として、好ましくは炭素数 1〜20のアルキル基、炭素数 1〜 14のァリール基等が挙げられる。より好ましくは炭素数 1〜10のアルキル基である。  Preferred examples of the hydrocarbon group constituted by these include an alkyl group having 1 to 20 carbon atoms and an aryl group having 1 to 14 carbon atoms. More preferably, it is a C1-C10 alkyl group.
[0050] Rは C*1及び C*2で表される炭素原子に炭素原子、窒素原子または硫黄原子を介し [0050] R is a carbon atom represented by C * 1 and C * 2 via a carbon atom, nitrogen atom or sulfur atom.
7  7
て結合する 2価の連結基を表す。好ましくは炭素数 1〜20のアルキレン基、アルキレ ンォキシド基等が挙げられる。  Represents a divalent linking group bonded to each other. Preferable examples include an alkylene group having 1 to 20 carbon atoms and an alkylene oxide group.
[0051] 上記エポキシ榭脂の R、 R 及び R で表される酸素原子を含有する置換基または [0051] A substituent containing an oxygen atom represented by R, R and R in the epoxy resin or
7 11 12  7 11 12
連結基として具体的には R及び Rで表される酸素原子を含有する置換基、及びそ  Specific examples of the linking group include a substituent containing an oxygen atom represented by R and R, and
4 5  4 5
れらを 2価の連結基としたものを挙げることができる。  Examples thereof include those having a divalent linking group.
[0052] R、R、R、R、R、R、R 、R 及び R で表される水素原子と炭素原子のみから 構成される炭化水素基として、具体的には炭素数 1〜20のアルキル基、アルキレン 基、炭素数 1〜14のァリール基、またはァリーレン基が挙げられる。好ましくは、炭素 数 1〜10のアルキル基またはアルキレン基が挙げられる。 [0052] Only from hydrogen atom and carbon atom represented by R, R, R, R, R, R, R 1, R 2 and R 3 Specific examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, an alkylene group, an aryl group having 1 to 14 carbon atoms, and an arylene group. Preferably, an alkyl group having 1 to 10 carbon atoms or an alkylene group is used.
[0053] 以下に、好ましい本発明の一般式 (4)で表されるエポキシ榭脂の具体例を示すが、 本発明はこれらに限定されるものではない。 [0053] Specific examples of preferred epoxy resin represented by the general formula (4) of the present invention are shown below, but the present invention is not limited thereto.
[0054] [化 12] [0054] [Chemical 12]
Figure imgf000020_0001
Figure imgf000020_0001
[0055] [化 13] [0055] [Chemical 13]
Figure imgf000021_0001
Figure imgf000021_0001
[0056] これらのエポキシ榭脂の合成は、米国特許第 2, 745, 847号、同第 2, 750, 395 号、同第 2, 853, 498号、同第 2, 853, 499号、同第 2, 863, 881号明細書に記 載の方法に準じて行うことができる。 [0056] The synthesis of these epoxy resins is described in US Pat. Nos. 2,745,847, 2,750,395, 2,853,498, 2,853,499, This can be carried out according to the method described in the specification of 2,863,881.
[0057] 本発明の一般式（1)〜 (4)で表されるエポキシ榭脂はエポキシ榭脂組成物中に 5[0057] The epoxy resin represented by the general formulas (1) to (4) of the present invention is contained in the epoxy resin composition.
〜95%、好ましくは 10〜85%含有させることができる。 It can be contained in an amount of ~ 95%, preferably 10 to 85%.
[0058] 本発明のエポキシ榭脂組成物は、上述した一般式（1)〜 (4)で表されるエポキシ榭 脂と併用してクレゾ一ルノボラック型、ビフエ-一ル型、ジシクロ型のエポキシ榭脂等 を用いることができる。 [0058] The epoxy resin composition of the present invention is used in combination with the epoxy resin represented by the general formulas (1) to (4) described above to use a cresol novolac type, biphenyl type, dicyclo type epoxy. For example, rosin can be used.
[0059] クレゾ一ルノボラック型、ビフエ-一ル型、ジシクロ型エポキシ榭脂としては特に限定 されず、 25°Cで液状又は固形状の従来公知の各種のものが用いられる力 特に衛 生性の観点から 25°Cで固形状のものが好ましい。具体的には、例えば、ビスフエノー ル A型エポキシ榭脂、ビスフエノール F型エポキシ榭脂、フエノールノボラック型ェポ キシ榭脂、クレゾ一ルノボラック型エポキシ榭脂、ビスフエノール AD型エポキシ榭脂 、ビフエニル型エポキシ榭脂、ナフタレン型エポキシ榭脂、脂環式エポキシ榭脂、ダリ シジルエステル系エポキシ榭脂、複素環式エポキシ榭脂、ジァリールスルホン型ェポ キシ榭脂、ヒドロキノン型エポキシ榭脂及びそれらの変性物等が挙げられる。また、こ れらに加えて、 3官能以上、好ましくは 4官能以上の多官能エポキシ榭脂を併用して もよい。このような多官能エポキシ榭脂としては、例えば、グリシジルァミン系エポキシ 榭脂、ナフタレン型エポキシ榭脂、ノボラック型エポキシ榭脂、多官能グリシジルエー テル等を挙げることができる。  [0059] The cresol novolac type, biphenol type, and dicyclo type epoxy resin are not particularly limited, and the power to use various conventionally known ones in liquid or solid form at 25 ° C, particularly in view of hygiene A solid form at 25 ° C to 25 ° C is preferred. Specifically, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol AD type epoxy resin, biphenyl type Epoxy resins, naphthalene type epoxy resins, cycloaliphatic epoxy resins, daricidyl ester type epoxy resins, heterocyclic epoxy resins, dialyl sulfone type epoxy resins, hydroquinone type epoxy resins And the like. In addition to these, a polyfunctional epoxy resin having 3 or more functional groups, preferably 4 or more functional groups, may be used in combination. Examples of such polyfunctional epoxy resins include glycidylamine epoxy resins, naphthalene type epoxy resins, novolac type epoxy resins, and polyfunctional glycidyl ethers.
[0060] これらエポキシ榭脂はエポキシ榭脂組成物中に 5〜90質量％、好ましくは 10〜50 質量％含有させることができる。 [0060] These epoxy resins are contained in the epoxy resin composition in an amount of 5 to 90% by mass, preferably 10 to 50%. It can be contained by mass%.
[0061] 本発明に用いることのできる非感光性硬化剤にっ 、て述べる。エポキシ榭脂用硬 ィ匕剤としては、特に限定されるものではないが、例えば、トリアルキルテトラヒドロ無水 フタル酸等の加熱硬化型酸無水物系硬化剤、フエノール系硬化剤、アミン系硬化剤 [0061] Non-photosensitive curing agents that can be used in the present invention will be described. The epoxy resin hardener is not particularly limited, and examples thereof include heat-curing acid anhydride-based curing agents such as trialkyltetrahydrophthalic anhydride, phenol-based curing agents, and amine-based curing agents.
、ジシアンジアミド等の潜在性硬化剤、カチオン系触媒型硬化剤等が挙げられ、いわ ゆる感光性のジァゾニゥム塩、ョードニゥム塩、スルホ二ゥム塩は本発明の対象外で ある。エポキシ榭脂用硬化剤のなかでも、常温で液状の加熱硬化型硬化剤や、多官 能であり、当量的に添加量が少量で良!、ジシアンジアミド等の潜在性硬化剤が好適 に用いられる。常温で液状の加熱硬化型硬化剤の代表的なものとしては、例えば、メ チルテトラヒドロ無水フタル酸、メチルへキサヒドロ無水フタル酸、メチルナジック酸無 水物、トリアルキルテトラヒドロ無水フタル酸等の酸無水物系硬ィ匕剤が挙げられ、なか でも、疎水化されていることから、メチルナジック酸無水物やトリアルキルテトラヒドロ無 水フタル酸が好適に用いられる。硬化促進剤としては、特に限定されるものではない 力 例えば、イミダゾール系硬化促進剤、 3級ァミン系硬化促進剤等が挙げられ、な かでも、硬化速度や硬化物の物性等の調整をするための反応系の制御をしやす 、こ とから、イミダゾール系硬化促進剤が好適に用いられる。イミダゾール系硬化促進剤 としては、特に限定されるものではないが、例えば、イミダゾールの 1位をシァノエチ ル基で保護した 1 シァノエチル 2—フエ-ルイミダゾールや、イソシァヌル酸で塩 基性を保護した商品名「2MA—0K」（四国化成工業社製)等が挙げられる。 And latent curing agents such as dicyandiamide, cationic catalyst-type curing agents, and the like, and so-called photosensitive diazonium salts, iodonium salts, sulfonium salts are outside the scope of the present invention. Among curing agents for epoxy resin, a thermosetting curing agent that is liquid at room temperature and a multi-functional, low-equivalent addition amount is acceptable! A latent curing agent such as dicyandiamide is preferably used. . Typical examples of thermosetting curing agents that are liquid at room temperature include acid anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, and trialkyltetrahydrophthalic anhydride. Examples thereof include physical hardeners. Among them, methylnadic acid anhydride and trialkyltetrahydrohydrophthalic acid are preferably used because they are hydrophobized. The curing accelerator is not particularly limited. For example, an imidazole curing accelerator, a tertiary amine curing accelerator, etc. can be mentioned. Among them, the curing speed and physical properties of the cured product are adjusted. Therefore, an imidazole curing accelerator is preferably used because the reaction system is easily controlled. The imidazole curing accelerator is not particularly limited. For example, 1-cyanoethyl 2-phenol imidazole in which the 1-position of imidazole is protected with a cyanoethyl group, or a product in which the basicity is protected with isocyanuric acid. Name “2MA-0K” (manufactured by Shikoku Kasei Kogyo Co., Ltd.).
[0062] これら非感光性硬化剤はエポキシ榭脂組成物中に 0. 01〜50質量％、好ましくは 0. 1〜10質量％含有させることができる。  [0062] These non-photosensitive curing agents can be contained in the epoxy resin composition in an amount of 0.01 to 50% by mass, preferably 0.1 to 10% by mass.
[0063] 本発明で用いることのできる非感光性硬化促進剤としては、例えば、第 3アミン系硬 化促進剤、尿素誘導体系硬化促進剤、イミダゾール系硬化促進剤、 DBU系硬化促 進剤、有機りん系硬化促進剤 (例えば、ホスフィン系硬化促進剤等）、ォ-ゥム塩系 硬化促進剤（例えば、ホスホニゥム塩系硬化促進剤、スルホ二ゥム塩系硬化促進剤、 アンモニゥム塩系硬化促進剤等）、金属キレート系硬化促進剤、酸および金属塩系 硬化促進剤等を挙げることができ、いわゆる感光性のジァゾ -ゥム塩、ョードニゥム塩 、スルホ二ゥム塩は本発明の対象外である。 [0064] 本発明で用いることのできる充填剤について説明する。無機フィラーとしては、シリ 力、アルミナ、チタ二了、水酸ィ匕アルミニウム等の公知の各種微粒子が用いられる力 特に、球状溶融シリカの使用が好ましい。無機フィラーの粒度分布は 1〜： LOO /z mが 好ましぐその平均粒子径は 0. 05〜20 111が好ましぐょり好ましくは0. 1〜10 m である。 [0063] Non-photosensitive curing accelerators that can be used in the present invention include, for example, tertiary amine-based curing accelerators, urea derivative-based curing accelerators, imidazole-based curing accelerators, DBU-based curing accelerators, Organic phosphorus curing accelerators (for example, phosphine curing accelerators), salt-based curing accelerators (for example, phosphonium salt-based curing accelerators, sulfonium salt-based curing accelerators, ammonium salt-based curing agents) Accelerators, etc.), metal chelate type hardening accelerators, acid and metal salt type hardening accelerators, etc., so-called photosensitive diazo-um salt, ododonium salt, sulfonium salt are subject of the present invention. Outside. [0064] The filler that can be used in the present invention will be described. As the inorganic filler, the use of various fine particles such as silica, alumina, titania, aluminum hydroxide, aluminum hydroxide, etc. In particular, the use of spherical fused silica is preferred. The particle size distribution of the inorganic filler is 1 to: LOO / zm is preferred, and the average particle size is preferably 0.05 to 20 111, more preferably 0.1 to 10 m.
[0065] これら充填剤はエポキシ榭脂組成物中に 10〜90質量％、好ましくは 50〜80質量 %含有させることができる。  [0065] These fillers can be contained in the epoxy resin composition in an amount of 10 to 90% by mass, preferably 50 to 80% by mass.
[0066] 本発明のエポキシ榭脂組成物には、更に必要に応じ、接着向上用炭素官能性シラ ン、カーボンブラックなどの顔料、染料、酸化防止剤、表面処理剤（γ—グリシドキシ プロピルトリメトキシシランなど）、その他の添加剤を本発明の目的を損なわない範囲 で配合することができる。  [0066] The epoxy resin composition of the present invention further contains, as necessary, pigments such as carbon-functional silane for improving adhesion, carbon black, dyes, antioxidants, surface treatment agents (γ-glycidoxypropyltrimethoxy). Silane etc.) and other additives can be blended within a range not to impair the purpose of the present invention.
[0067] また、本発明のエポキシ榭脂組成物にぉ ヽては、熱可塑性榭脂を含有することが 好ましい。本発明に適用可能な熱可塑性榭脂としては、例えば、ポリエチレン、ポリプ ロピレン、ポリスチレン、アクリロニトリル/スチレン榭脂、アクリロニトリル/ブタジエン/ス チレン榭脂、メタタリル榭脂、ポリ塩化ビュル、ポリアミド、ポリウレタン、ポリアセターノレ 、ポリブチレンテレフタレート、ポリメチルペンテン、ポリカーボネイト、ポリフエ-レンェ 一テル、ポリフエ-レンサルファイド、ポリエーテルエーテルケトン、ポリテトラフロロェ チレン、ポリエーテルイミド、ポリアリレート、ポリサルフォン、ポリエーテルサルフォン、 ポリアミドイミド等の公知の各種熱可塑性榭脂が用いられる力 特に、ポリアミド、ポリ ウレタンの使用が好ましい。  [0067] The epoxy resin composition of the present invention preferably contains a thermoplastic resin. Examples of the thermoplastic resin applicable to the present invention include polyethylene, polypropylene, polystyrene, acrylonitrile / styrene resin, acrylonitrile / butadiene / styrene resin, methallyl resin, polychlorinated butyl, polyamide, polyurethane, polyacetanol. , Polybutylene terephthalate, polymethylpentene, polycarbonate, polyphenylene ether, polyphenylene sulfide, polyetheretherketone, polytetrafluoroethylene, polyetherimide, polyarylate, polysulfone, polyethersulfone, polyamideimide, etc. The power with which various known thermoplastic resins are used In particular, the use of polyamide and polyurethane is preferred.
[0068] これら熱可塑性榭脂は、エポキシ榭脂組成物中に 1〜30質量％、好ましくは 5〜1 [0068] These thermoplastic resins are contained in the epoxy resin composition in an amount of 1 to 30% by mass, preferably 5 to 1.
5質量％含有させることができる。 5 mass% can be contained.
[0069] さらには、エポキシ榭脂以外のカチオン種と反応する化合物、アルコール、ォキセ タン、ビュルエーテル、プロべ-ルエーテル等も用いることができる。 [0069] Furthermore, compounds that react with cationic species other than epoxy resin, alcohol, oxetane, butyl ether, probe ether, and the like can also be used.
[0070] これらは、非感光性硬化剤を加熱して生じるカチオン種の存在下に、これら化合物 同士やエポキシ榭脂と反応するものである。上記エポキシ榭脂組成物には、以下の ようなォキセタンィ匕合物を添加することができる。 [0070] These react with each other and with epoxy resin in the presence of cationic species generated by heating the non-photosensitive curing agent. The following oxetane compound can be added to the epoxy resin composition.
[0071] 3—ェチルー 3—ヒドロキシメチルォキセタン 3—メチル 3—ヒドロキシメチルォキセタン [0071] 3-Ethyl 3-hydroxymethyloxetane 3-Methyl 3-hydroxymethyloxetane
1 , 4 ビス [ ( 3 ェチル 3 ォキセタ -ルメトキシ)メチル]ベンゼン  1,4 bis [(3 ethyl 3 oxeta-lmethoxy) methyl] benzene
エポキシ榭脂組成物には、ビニルエーテルを配合することもできる。ビニルエーテ ルとしては、シクロへキサンジメタノールジビニルエーテル、ジエチレングリコールジビ Vinyl epoxy can also be mix | blended with an epoxy resin composition. Vinyl ethers include cyclohexane dimethanol divinyl ether and diethylene glycol dibi
-ルエーテル等が挙げられる。 -Luether etc. are mentioned.
[0072] エポキシ榭脂糸且成物には、エポキシ榭脂組成物に溶解するものであれば末端に水 酸基を持つポリエステル、ポリエーテルを配合することができる。ポリエステルとしては 、例えば分子内に 2個の水酸基を持つポリエステルである PCL— 205H、 PCL- 21 0 (ダイセルィ匕学工業製）、分子内に 3個の水酸基を持つポリエステルである PCL— 3 05, PCL— 308など (ダイセルィ匕学工業製）、分子内に 4個の水酸基を持つポリエス テルである PCL— 410Dなど (ダイセルィ匕学工業製）が挙げられる。またクラポール P 1010、 P— 2010、 P— 3010 (クラレ製）なども使用できる。ポリエーテルとしては、 ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコールなどの ポリエーテル類が挙げられる。市販品としては、例えばアデ力製ポリエーテル P— 40 0、 P— 1000、 P— 3000等が挙げられる。低分子ポリオールとしては、エチレングリコ ール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、 1, 3— プロパンジオール、 1, 4 ブタンジオール、 1, 6 へキサンジオールなどのグリコー ル類が挙げられる。  [0072] A polyester or polyether having a hydroxyl group at the terminal can be blended in the epoxy resinous fiber composition if it can be dissolved in the epoxy resin composition. Examples of polyesters include PCL-205H, which is a polyester having two hydroxyl groups in the molecule, and PCL-210 (manufactured by Daicel Engineering Co., Ltd.), and PCL-3 05, which is a polyester having three hydroxyl groups in the molecule. PCL-308 (manufactured by Daicel Engineering Co., Ltd.) and PCL-410D (made by Daicel Engineering Co., Ltd.), which is a polyester having four hydroxyl groups in the molecule. Kurapol P 1010, P-2010, P-3010 (Kuraray) can also be used. Examples of the polyether include polyethers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of commercially available products include Adeiki polyether P-400, P-1000, P-3000, and the like. Examples of the low molecular polyol include glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4 butanediol, and 1,6 hexanediol.
[0073] 本発明のエポキシ榭脂組成物は、様々な分野に適用することができる力 特に、そ の優れた特性により、接着剤、塗料、コーティング材あるいは封止材に適用すること が好ましい。  [0073] The epoxy resin composition of the present invention is preferably applied to an adhesive, a paint, a coating material or a sealing material due to its excellent properties, particularly its excellent properties.
[0074] 接着剤【こつ ヽて ίま、 f列え ίま、特開 2000— 273151号、特開 2005— 36095号、特 開 2005— 51131号、特開 2005— 126658号等、塗料 ίこつ ヽて ίま、特開平 8— 13 4175号、特開 2001— 131468号、特開 2002— 121471号、特開 2002— 24953 2号、特開 2002— 275229号、特開 2005— 95723号等、コーティング材 ίこつ ヽて は、特開 2003— 292568号、特開 2003— 327660号、特開 2004— 83783号、特 開 2004— 256781号、特開 2005— 120357号等、封止剤【こつ!ヽて ίま、特開 2002 — 294032号、特開 2003— 280188号、特開 2003— 183351号、特開 2004— 17 5825、特開 2004— 231790、特開 2004— 285125号等を挙げ、ること力 Sできる。 実施例 [0074] Adhesives [Hanging and flicking, f row printing, JP 2000-273151, JP 2005-36095, JP 2005-51131, JP 2005-126658, etc. JP-A-8-134175, JP-A-2001-131468, JP-A-2002-121471, JP-A-2002-249532, JP-A-2002-275229, JP-A-2005-95723, etc. The coating materials include lacquers such as JP2003-292568, JP2003-327660, JP2004-83783, JP2004-256781, JP2005-120357, etc. JP 2002-294032, JP 2003-280188, JP 2003-183351, JP 2004-17 5825, JP-A-2004-231790, JP-A-2004-285125, and the like. Example
[0075] 以下、実施例を挙げて本発明を詳細に説明するが、本発明は下記の実施例に制 限されるものではない。  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples.
[0076] 実施例 1 [0076] Example 1
《エポキシ榭脂組成物の調製》  << Preparation of epoxy resin composition >>
以下に示す各成分をホモディスパー型攪拌機で均一に溶解混合することにより、 1 0種の榭脂組成物を得た。  The following components were uniformly dissolved and mixed with a homodisper type stirrer to obtain 10 types of rosin compositions.
[0077] (エポキシ榭脂組成物 1：接着剤用途） [0077] (Epoxy resin composition 1: Adhesive use)
エポキシ榭脂： EP- 17 24質量部  Epoxy resin: EP-17 24 parts by mass
ジシクロペンタジェン型固形エポキシ榭脂（商品名「EXA— 7200HHJ 大日本インキ化学工業社製） 76質量部 非感光性硬化剤：トリアルキルテトラヒドロ無水フタル酸 60質量部 非感光性硬化促進剤:イソシァヌル変性固体分散型イミダゾール 8質量部 イミダゾールシランカップリング剤 2質量部  Dicyclopentagen-type solid epoxy resin (trade name “EXA-7200HHJ manufactured by Dainippon Ink & Chemicals, Inc.”) 76 parts by mass Non-photosensitive curing agent: 60 parts by mass of trialkyltetrahydrophthalic anhydride Non-photosensitive curing accelerator: Isocyanur Modified solid dispersion type imidazole 8 parts by mass Imidazole silane coupling agent 2 parts by mass
(エポキシ榭脂組成物 2：塗料用途）  (Epoxy resin composition 2: Paint application)
エポキシ榭脂： EP— 56 40質量部  Epoxy resin: EP—56 40 parts by mass
ェピコート 1009 (油化シェル (株)製エポキシ榭脂〕  Epicoat 1009 (Epoxy resin manufactured by Yuka Shell Co., Ltd.)
1Z1)溶液（固形分 25%) 160質量部  1Z1) Solution (solid content 25%) 160 parts by mass
非感光性硬化剤：クレゾ一ルノボラック榭脂（Mn= 1000、
Figure imgf000025_0001
Non-photosensitive curing agent: Cresol novolac resin (Mn = 1000,
Figure imgf000025_0001
20質量部  20 parts by mass
非感光性硬化促進剤：リン酸 0. 2質量部  Non-photosensitive curing accelerator: 0.2 parts by mass of phosphoric acid
(エポキシ榭脂組成物 3：コーティング材用途）  (Epoxy resin composition 3: Coating materials)
エポキシ榭脂： EP— 61 50質量部  Epoxy resin: EP— 61 50 parts by mass
非感光性硬化剤： ALCH-TR：アルミニウムトリスェチルァセトアセテート Non-photosensitive curing agent: ALCH-TR: Aluminum trisethylacetate acetate
(川研ファインケミカル製） 0. 5質量部 (Manufactured by Kawaken Fine Chemicals) 0.5 parts by mass
ポリ力プロラタトンポリオール (ダイセルィ匕学工業製） 10質量部 Poly force prolatathon polyol (manufactured by Daicel Engineering Co., Ltd.) 10 parts by mass
(エポキシ榭脂組成物 4：封止材用途） エポキシ榭脂： EP- 15 100質量部 (Epoxy resin composition 4: For sealing materials) Epoxy resin: EP-15 15 parts by mass
非感光性硬ィ匕剤:メチルへキサヒドロ無水フタル酸 100質量部 非感光性硬化促進剤： 2—ェチルー 4ーメチルイミダゾール 1質量部 充填剤:球状シリカの FB— 48 (電気化学工業社製、商品名） 700質量部 ノ、イド口タルサイトの AHT—XA (協和化学工業社製、商品名） 1質量部 (エポキシ榭脂組成物 5：封止材用途） Non-photosensitive hardener: 100 parts by weight of methylhexahydrophthalic anhydride Non-photosensitive curing accelerator: 1 part by weight of 2-ethyl-4-methylimidazole Filler: FB-48 of spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd., Product Name) 700 parts by weight No, Ido Talsite AHT-XA (Kyowa Chemical Industry Co., Ltd., trade name) 1 part by weight (Epoxy resin composition 5: Sealing material use)
エポキシ榭脂： EP- 15 80質量部 Epoxy resin: EP- 15 80 parts by mass
非感光性硬ィ匕剤:メチルへキサヒドロ無水フタル酸 100質量部 非感光性硬化促進剤： 2—ェチルー 4ーメチルイミダゾール 1質量部 充填剤:球状シリカの FB— 48 (電気化学工業社製、商品名） 700質量部 ノ、イド口タルサイトの AHT—XA (協和化学工業社製、商品名） 1質量部 ォキセタン 20質量部 Non-photosensitive hardener: 100 parts by weight of methylhexahydrophthalic anhydride Non-photosensitive curing accelerator: 1 part by weight of 2-ethyl-4-methylimidazole Filler: FB-48 of spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd., (Product name) 700 parts by weight No, IHT Talsite AHT-XA (Kyowa Chemical Industry Co., Ltd., trade name) 1 part by weight Oxetane 20 parts by weight
(エポキシ榭脂組成物 6 :接着剤用途）  (Epoxy resin composition 6: Adhesive use)
エポキシ榭脂：ナフタレン型液状エポキシ榭脂（商品名「HP— 4032D」 大日本インキ化学工業社製） 24質量部 エポキシ榭脂：ジシクロペンタジェン型固形エポキシ榭脂 Epoxy resin: Naphthalene type liquid epoxy resin (trade name “HP-4032D” manufactured by Dainippon Ink & Chemicals, Inc.) 24 parts by mass Epoxy resin: Dicyclopentagen type solid epoxy resin
(商品名「EXA— 7200HH」、大日本インキ化学工業社製） 76質量部 非感光性硬化剤：トリアルキルテトラヒドロ無水フタル酸 60質量部 非感光性硬化促進剤:イソシァヌル変性固体分散型イミダゾール 8質量部 イミダゾールシランカップリング剤 2質量部  (Product name "EXA-7200HH", manufactured by Dainippon Ink and Chemicals, Inc.) 76 parts by weight Non-photosensitive curing agent: 60 parts by weight of trialkyltetrahydrophthalic anhydride Non-photosensitive curing accelerator: isocyanuric modified solid dispersion type imidazole 8 parts by mass Parts Imidazolesilane coupling agent 2 parts by mass
(エポキシ榭脂組成物 7：塗料用途）  (Epoxy resin composition 7: Paint application)
エポキシ榭脂：ェピコート 1009 (油化シェルエポキシ (株)製エポキシ榭脂）の キシレン Zプチルセ口ソルブ（1Z1)溶液（固形分 25%) 320質量部 非感光性硬化剤：クレゾ一ルノボラック榭脂（Mn= 1000、 Mw/Mn= 2) Epoxy resin: Epoxy Coat 1009 (epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) in xylene Z butyl solvate (1Z1) (solid content 25%) 320 parts by mass Non-photosensitive curing agent: Cresol novolac resin ( (Mn = 1000, Mw / Mn = 2)
20質量部  20 parts by mass
非感光性硬化促進剤：リン酸 0. 2質量部 Non-photosensitive curing accelerator: 0.2 parts by mass of phosphoric acid
(エポキシ榭脂組成物 8：コーティング材用途）  (Epoxy resin composition 8: For coating materials)
エポキシ榭脂： CEL— 2021P 50質暈部 エポキシ榭脂： GT-401 40質量部 非感光性硬化剤： ALCH-TR：アルミニウムトリスェチルァセトァセテEpoxy resin: CEL—2021P 50 parts Epoxy resin: GT-401 40 parts by weight Non-photosensitive curing agent: ALCH-TR: Aluminum trisethylacetate
(川研ファインケミカル製） 0. 5質量部 ポリ力プロラタトンポリオール (ダイセルィ匕学工業製） 10質量(Made by Kawaken Fine Chemical) 0.5 part by mass Poly-force prolataton polyol (Daicel Sugaku Kogyo) 10 mass
(エポキシ榭脂組成物 9：封止材用途） (Epoxy resin composition 9: For sealing materials)
エポキシ榭脂：ビスフエノール F型エポキシ榭脂の YL983U Epoxy resin: Bisphenol F type epoxy resin YL983U
(油化シェル社製、商品名） 100質量部 非感光性硬ィ匕剤:メチルへキサヒドロ無水フタル酸 100質 非感光性硬化促進剤： 2—ェチルー 4ーメチルイミダゾール 1 充填剤:球状シリカの FB— 48 (電気化学工業社製、商品名） 700 ノ、イド口タルサイトの AHT—XA (協和化学工業社製、商品名） 1 (エポキシ榭脂組成物 10：封止材用途） (Product name, manufactured by Yuka Shell Co., Ltd.) 100 parts by mass Non-photosensitive hardener: Methylhexahydrophthalic anhydride 100 quality Non-photosensitive curing accelerator: 2-ethyl 4-methylimidazole 1 Filler: of spherical silica FB—48 (Denki Kagaku Kogyo Co., Ltd., trade name) 700 HT, AHT—XA of Idoguchi Talsite (Kyowa Chemical Industry Co., Ltd., trade name) 1 (Epoxy resin composition 10: Sealing material use)
エポキシ榭脂：ビスフエノール F型エポキシ榭脂の YL983U Epoxy resin: Bisphenol F type epoxy resin YL983U
(油化シェル社製、商品名） 80質量部 非感光性硬ィ匕剤:メチルへキサヒドロ無水フタル酸 100質 非感光性硬化促進剤： 2—ェチルー 4ーメチルイミダゾール 1 充填剤:球状シリカの FB— 48 (電気化学工業社製、商品名） 700 ノ、イド口タルサイトの AHT—XA (協和化学工業社製、商品名） 1 ォキセタン 20質量部 (Product name made by Yuka Shell Co., Ltd.) 80 parts by mass Non-photosensitive hardener: 100-methylhexahydrophthalic anhydride Non-photosensitive curing accelerator: 2-ethyl 4-methylimidazole 1 Filler: spherical silica FB—48 (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.) 700 parts, AHT—XA (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) 1 oxetane 20 parts by mass
[化 14] ォキセタン
Figure imgf000027_0001
[Chemical 14] Oxetane
Figure imgf000027_0001
[0079] 《エポキシ榭脂組成物の評価》 [0079] <Evaluation of epoxy resin composition>
これらの榭脂組成物を用いて、以下に示す試験を行った。  The test shown below was done using these rosin compositions.
[0080] 〔硬化性〕 各エポキシ榭脂組成物をガラス板上に 100 m厚に塗布し、ゲルィ匕時間を 150°C の熱板上で測定した。 [0080] [Curing property] Each epoxy resin composition was coated on a glass plate to a thickness of 100 m, and the gel time was measured on a hot plate at 150 ° C.
[0081] 〔接着性〕 [0081] [Adhesiveness]
T字剥離試験方法 (剥離接着強度： kN/25mm)  T-peeling test method (peeling adhesive strength: kN / 25mm)
150 X 25 X 0. 5mmの SPCC - D (軟鋼板）を # 120のサンドペーパーでサンディ ングし、アセトン脱脂した後、 PHOTO SURFACE PROCESSOR PL12— 20 0 (低圧水銀灯、 SEN社製)を用いて UV照射 (照射距離： 10mm、照射時間：120秒 )により表面処理した。その後、エポキシ榭脂組成物を塗布し、 100 /z mのスぺーサ 一を挟んで貼り合せ、クリップで圧締して、硬化条件 180°Cで 1時間加熱して硬化さ せた。測定はインストロン万能試験機 (インストロン社製)を用いてクロスヘッドスピード 200mmZminで行って、剥離接着強度 (kNZ25mm)を測定し、これを接着性の 尺度とした。  150 x 25 x 0.5 mm SPCC-D (mild steel plate) sanded with # 120 sandpaper, degreased with acetone, then UV using PHOTO SURFACE PROCESSOR PL12—20 0 (low pressure mercury lamp, manufactured by SEN) Surface treatment was performed by irradiation (irradiation distance: 10 mm, irradiation time: 120 seconds). Thereafter, an epoxy resin composition was applied, bonded with a 100 / zm spacer, clamped with a clip, and cured by heating at 180 ° C for 1 hour. The measurement was performed using an Instron universal testing machine (Instron) at a crosshead speed of 200 mmZmin, and the peel adhesion strength (kNZ25 mm) was measured. This was used as a measure of adhesion.
[0082] 〔耐熱性〕 [0082] [Heat resistance]
エポキシ榭脂組成物をガラス板上に 100 m厚に塗布し、硬化させた試験片を水 に浸漬し、 130°Cで 30分間処理した塗膜の白化状態を目視観察し、下記の基準に 従って耐熱性を評価した。  The epoxy resin composition was applied to a glass plate to a thickness of 100 m, the cured specimen was immersed in water, and the whitening state of the coating film treated for 30 minutes at 130 ° C was visually observed, and the following criteria were met. Therefore, the heat resistance was evaluated.
[0083] 〇：全く白化なし [0083] ○: No whitening
△:若干白化あり  Δ: Slightly whitened
X：著しい白化あり  X: Significant whitening
〔衛生性〕  [Hygiene]
エポキシ榭脂組成物の所定量をラットの皮膚に塗布し、 1週間後の皮膚の状態を観 察し、下記の基準に従って判定して、皮膚刺激性の評価を行った。  A predetermined amount of the epoxy resin composition was applied to the skin of a rat, and after 1 week, the skin condition was observed and judged according to the following criteria to evaluate skin irritation.
[0084] 〇：皮膚に付着させても、ほとんど変化が認められない  [0084] ○: Almost no change is observed even if it is attached to the skin
△:皮膚に付着させると、僅かに発赤する  △: Slight redness when attached to skin
X：皮膚に付着すると、水泡できる  X: Water bubbles can form on the skin
〔耐候性〕  〔Weatherability〕
エポキシ榭脂組成物をガラス板上に 100 m厚に塗布した試験塗板を、サンシャイ ンカーボンアーク灯式試験機を用いて 300時間試験を行った。その時、塗膜の光沢 感を促進耐候性試験を行って!/ヽな 、未処理の塗面と比較し、下記の基準に従って 耐候性を評価した A test coated plate in which the epoxy resin composition was coated on a glass plate to a thickness of 100 m was tested for 300 hours using a sunshine carbon arc lamp type tester. At that time, the gloss of the coating film A weather resistance test was carried out to promote the feeling! / The weather resistance was evaluated according to the following criteria in comparison with an untreated paint surface
〇：変化がほとんどない  ○: Almost no change
△:やや低下  △: Slightly decreased
X：著しく低下  X: Remarkably reduced
〔防食性〕  [Anti-corrosion]
サンドブラスト板に各エポキシ榭脂組成物を 100 μ m厚に塗布した塗膜試験片を、 500時間 SST (塩水噴霧試験）にかけて行った後、試験片表面を目視観察し、下記 の基準に従って防食性を評価した。  After coating specimens with 100 μm thickness of each epoxy resin composition on sandblasted plate are subjected to SST (salt spray test) for 500 hours, the specimen surface is visually observed and anticorrosive according to the following criteria. Evaluated.
[0085] 〇：さび、ふくれ無し [0085] ○: No rust, no blister
△:さび、ふくれ無しやや見られる  △: Rust, no blistering
X：さび、ふくれ無し多く見られる  X: Many rust and no blisters
〔貯蔵安定性〕  [Storage stability]
エポキシ榭脂組成物を、ガラス瓶に入れ密栓し、 70°Cの恒温槽で 1週間保存した 後のインクの状態を目？見観察し、下記の基準に従って貯蔵安定性の評価を行った。  What is the state of the ink after the epoxy resin composition is sealed in a glass bottle and stored in a thermostat at 70 ° C for 1 week? Observing and observing, the storage stability was evaluated according to the following criteria.
[0086] 〇： 80°C、 24時間保存しても、インク液に変化は認められな!/、 [0086] ○: No change in ink liquid was observed even after storage at 80 ° C for 24 hours! /,
△ : 80°C、 24時間保存した結果、 2割以上の増粘上昇が認められた  △: Increased viscosity by 20% or more after storage at 80 ° C for 24 hours
X : 80°C、 24時間保存した後、ゲルィ匕を起こした  X: Gely wrinkles occurred after storage at 80 ° C for 24 hours
以上により得られた各評価結果を、表 1に示す。  Table 1 shows the evaluation results obtained as described above.
[0087] [表 1] [0087] [Table 1]
エポキシ 各評価結果 Epoxy evaluation results
樹脂組成物硬化性 備考  Resin composition curability
耐熱性衛生性耐候性防食性  Heat resistance Hygiene Weather resistance Corrosion resistance
(分） (kN/25mra) 安定性  (Min) (kN / 25mra) Stability
1 1 .0 0.172 〇 〇 〇 〇 〇 本発明 1 1 .0 0.172 ○ ○ ○ ○ ○ The present invention
2 2.0 0.165 O 〇 〇 O 〇 本発明2 2.0 0.165 O ○ ○ O ○ The present invention
3 1 .0 0.168 〇 〇 〇 〇 〇 本発明3 1 .0 0.168 ○ ○ ○ ○ ○ The present invention
4 1.0 0. 169 〇 〇 〇 〇 〇 本発明4 1.0 0. 169 ○ ○ ○ ○ ○ The present invention
5 0.5 0.158 〇 〇 〇 〇 〇 本発明5 0.5 0.158 ○ ○ ○ ○ ○ This invention
6 5.0 0.056 Δ X Δ Δ Δ 本発明6 5.0 0.056 Δ X Δ Δ Δ The present invention
7 10.0 0.078 Δ Δ Δ Δ Δ 本発明7 10.0 0.078 Δ Δ Δ Δ Δ The present invention
8 5.0 0.081 Δ X Δ Δ △ 本発明8 5.0 0.081 Δ X Δ Δ Δ The present invention
9 5.0 0.067 Δ X Δ Δ △ 本発明9 5.0 0.067 Δ X Δ Δ Δ The present invention
10 4.0 0.056 Δ X △ △ △ 本発明 表 1から、本発明のエポキシ榭脂組成物は、接着剤、塗料、コーティング剤及び封 止剤に適用した場合、いずれも、硬化性、接着性、耐熱性、衛生性、耐候性、防食 性、貯蔵安定性に優れていることが分かる。 10 4.0 0.056 Δ X △ △ △ The present invention From Table 1, the epoxy resin composition of the present invention, when applied to adhesives, paints, coating agents and sealants, is all curable, adhesive, heat resistant. It can be seen that it is excellent in water, hygiene, weather resistance, corrosion resistance, and storage stability.

Claims

請求の範囲 エポキシ榭脂及び非感光性硬化剤を含有するエポキシ榭脂組成物にお！ヽて、該 エポキシ榭脂が、下記一般式（1)で表される化合物であることを特徴とするエポキシ 榭脂組成物。 Claims Epoxy resin composition containing epoxy resin and non-photosensitive curing agent! The epoxy resin composition is characterized in that the epoxy resin is a compound represented by the following general formula (1).
[化 1]  [Chemical 1]
Figure imgf000031_0001
Figure imgf000031_0001
〔式中、 R は置換基を表し、 mOは 0〜2の整数を、 rOは 1〜3の整数を表す。 Lは主 [Wherein, R represents a substituent, mO represents an integer of 0 to 2, and rO represents an integer of 1 to 3. L is the main
100 0 鎖に酸素原子または硫黄原子を含んでも良 、炭素数 1〜 15の rO + 1価の連結基ま たは単結合を表す。〕  The chain may contain an oxygen atom or a sulfur atom, and represents an rO + 1 monovalent linking group having 1 to 15 carbon atoms or a single bond. ]
前記一般式（1)で表されるエポキシ榭脂が、下記一般式 (2)で表される化合物であ ることを特徴とする請求の範囲第 1項に記載のエポキシ榭脂組成物。  2. The epoxy resin composition according to claim 1, wherein the epoxy resin represented by the general formula (1) is a compound represented by the following general formula (2).
[化 2] [Chemical 2]
Figure imgf000031_0002
Figure imgf000031_0002
〔式中、 R は置換基を表し、 mlは 0〜2の整数を、 pl、 qlはそれぞれ 0または 1を、 r [Wherein, R represents a substituent, ml represents an integer of 0 to 2, pl and ql each represent 0 or 1, r
101  101
1は 1〜3の整数を表す。 Lは主鎖に酸素原子または硫黄原子を含んでも良い炭素  1 represents an integer of 1 to 3. L is carbon that may contain oxygen or sulfur atoms in the main chain
1  1
数 1〜15の rl + 1価の連結基または単結合を表す。〕 Rl + 1 represents a monovalent linking group or a single bond. ]
前記一般式（1)で表されるエポキシ榭脂が、下記一般式 (3)で表される化合物であ ることを特徴とする請求の範囲第 1項に記載のエポキシ榭脂組成物。  2. The epoxy resin composition according to claim 1, wherein the epoxy resin represented by the general formula (1) is a compound represented by the following general formula (3).
[化 3] 一般式 (3)
Figure imgf000032_0001
[Chemical 3] General formula (3)
Figure imgf000032_0001
〔式中、 R は置換基を表し、 m2は 0 [Wherein R represents a substituent, and m2 is 0.
102 〜2の整数を、 p2、 q2はそれぞれ 0または 1を、 r An integer from 102 to 2, p2 and q2 are 0 or 1, respectively, r
2は 1〜3の整数を表す。 Lは主鎖に酸素原子または硫黄原子を含んでも良い炭素 2 represents an integer of 1 to 3. L is carbon that may contain oxygen or sulfur atoms in the main chain
2  2
数 1〜15の r2+ l価の連結基または単結合を表す。〕  It represents an r2 + l-valent linking group or a single bond of 1 to 15. ]
前記一般式（1)で表されるエポキシ榭脂が、下記一般式 (4)で表される化合物であ ることを特徴とする請求の範囲第 1項に記載のエポキシ榭脂組成物。  2. The epoxy resin composition according to claim 1, wherein the epoxy resin represented by the general formula (1) is a compound represented by the following general formula (4).
[化 4]  [Chemical 4]
-般
Figure imgf000032_0002
-General
Figure imgf000032_0002
〔式中、 R及び Rは水素原子またはアルキル基を表す。ただし、 Rと Rが同時に水 [Wherein, R and R represent a hydrogen atom or an alkyl group. However, R and R are water at the same time.
1 2 1 2  1 2 1 2
素原子であることはない。 Rは水素原子、ハロゲン原子または置換基を表す。 R  It is not an elementary atom. R represents a hydrogen atom, a halogen atom or a substituent. R
3 4、 R  3 4, R
5 は水素原子、ハロゲン原子または置換基を表す。 Rは C*1及び C*2で表される炭素原 5 represents a hydrogen atom, a halogen atom or a substituent. R is the carbon source represented by C * 1 and C * 2.
7  7
子に炭素原子、窒素原子または硫黄原子を介して結合する 2価の連結基を表す。 R  Represents a divalent linking group bonded to a child via a carbon atom, nitrogen atom or sulfur atom. R
8 は Rと同義である。 R及び R は R及び Rと同義である。 R 及び R は R及び Rと同 8 is synonymous with R. R and R are synonymous with R and R. R and R are the same as R and R
3 9 10 1 2 11 12 4 5 義である。 R 3 9 10 1 2 11 12 4 5 Righteous. R
4、 R  4, R
5、 R 及び R の少なくとも 1つは水素原子である。〕  5. At least one of R and R is a hydrogen atom. ]
11 12  11 12
[5] 前記エポキシ榭脂として、さらに、クレゾ一ルノボラック型エポキシ榭脂、ビフエ-一 ル型エポキシ榭脂及びジシクロ型エポキシ榭脂から選ばれる少なくとも 1種を含有す ることを特徴とする請求の範囲第 1項乃至第 4項のいずれか 1項に記載のエポキシ榭 脂組成物。  [5] The epoxy resin further comprises at least one selected from a cresol novolac type epoxy resin, a biphenol type epoxy resin and a dicyclo type epoxy resin. 5. The epoxy resin composition according to any one of items 1 to 4 in the range.
[6] 前記クレゾ一ルノボラック型エポキシ榭脂、ビフエニール型エポキシ榭脂またはジシ クロ型エポキシ榭脂が、 25°Cで固形であることを特徴とする請求の範囲第 5項に記載 のエポキシ榭脂組成物。 [6] The cresol novolac type epoxy resin, biphenyl type epoxy resin or disinfectant The epoxy resin composition according to claim 5, wherein the black epoxy resin is solid at 25 ° C.
[7] 非感光性硬化促進剤を含有することを特徴とする請求の範囲第 1項乃至第 6項の[7] The method according to any one of claims 1 to 6, further comprising a non-photosensitive curing accelerator.
Vヽずれか 1項に記載のエポキシ榭脂組成物。 2. The epoxy resin composition according to item 1, wherein
[8] 充填剤を含有することを特徴とする請求の範囲第 1項乃至第 7項のいずれか 1項に 記載のエポキシ榭脂組成物。 [8] The epoxy resin composition according to any one of claims 1 to 7, further comprising a filler.
[9] 熱可塑性榭脂を含有することを特徴とする請求の範囲第 1項乃至第 8項のいずれ 力 1項に記載のエポキシ榭脂組成物。 [9] The epoxy resin composition according to any one of [1] to [8], which comprises a thermoplastic resin.
PCT/JP2006/318106 2005-09-21 2006-09-13 Epoxy resin composition WO2007034713A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010539288A (en) * 2007-09-13 2010-12-16 ブルーワー サイエンス アイ エヌ シー． Spin-on protective coating for wet etching of microelectronic substrates
JP5352087B2 (en) * 2005-12-26 2013-11-27 株式会社フジシールインターナショナル Shrink label

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003064530A1 (en) * 2002-01-25 2003-08-07 Sumitomo Bakelite Co., Ltd. Transparent composite composition
JP2004204228A (en) * 2002-12-13 2004-07-22 Daicel Chem Ind Ltd Curable epoxy resin composition and cured material
JP2004315778A (en) * 2003-02-24 2004-11-11 Konica Minolta Holdings Inc Active energy ray-curable composition
JP2004339267A (en) * 2003-05-13 2004-12-02 Konica Minolta Medical & Graphic Inc Active energy radiation-curing inkjet ink and recording method and printed matter using the same
JP2006089715A (en) * 2004-08-27 2006-04-06 Konica Minolta Medical & Graphic Inc Composition curable by active light, ink curable by active light, method for forming image and epoxy compound

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003064530A1 (en) * 2002-01-25 2003-08-07 Sumitomo Bakelite Co., Ltd. Transparent composite composition
JP2004204228A (en) * 2002-12-13 2004-07-22 Daicel Chem Ind Ltd Curable epoxy resin composition and cured material
JP2004315778A (en) * 2003-02-24 2004-11-11 Konica Minolta Holdings Inc Active energy ray-curable composition
JP2004339267A (en) * 2003-05-13 2004-12-02 Konica Minolta Medical & Graphic Inc Active energy radiation-curing inkjet ink and recording method and printed matter using the same
JP2006089715A (en) * 2004-08-27 2006-04-06 Konica Minolta Medical & Graphic Inc Composition curable by active light, ink curable by active light, method for forming image and epoxy compound

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5352087B2 (en) * 2005-12-26 2013-11-27 株式会社フジシールインターナショナル Shrink label
JP2010539288A (en) * 2007-09-13 2010-12-16 ブルーワー サイエンス アイ エヌ シー． Spin-on protective coating for wet etching of microelectronic substrates
US8445591B2 (en) 2007-09-13 2013-05-21 Brewer Science Inc. Spin-on protective coatings for wet-etch processing of microelectronic substrates
KR101573946B1 (en) * 2007-09-13 2015-12-02 브레우어 사이언스 인코포레이션 Spin-on protective coatings for wet-etch processing of microelectronic substrates

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