JP4477627B2 - 銅箔積層板用エポキシ樹脂組成物 - Google Patents
銅箔積層板用エポキシ樹脂組成物 Download PDFInfo
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- JP4477627B2 JP4477627B2 JP2006508554A JP2006508554A JP4477627B2 JP 4477627 B2 JP4477627 B2 JP 4477627B2 JP 2006508554 A JP2006508554 A JP 2006508554A JP 2006508554 A JP2006508554 A JP 2006508554A JP 4477627 B2 JP4477627 B2 JP 4477627B2
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- 239000003822 epoxy resin Substances 0.000 title claims description 70
- 229920000647 polyepoxide Polymers 0.000 title claims description 70
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 40
- 239000011889 copper foil Substances 0.000 title claims description 39
- 239000000203 mixture Substances 0.000 title claims description 35
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 239000004593 Epoxy Substances 0.000 claims description 30
- 239000012802 nanoclay Substances 0.000 claims description 27
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 21
- 239000000945 filler Substances 0.000 claims description 16
- 229920003986 novolac Polymers 0.000 claims description 16
- -1 imidazole compound Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical group 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 235000015278 beef Nutrition 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 239000003760 tallow Substances 0.000 claims description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 claims description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical group CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004843 novolac epoxy resin Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
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- 150000002460 imidazoles Chemical class 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 description 32
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- 239000010410 layer Substances 0.000 description 14
- 239000004927 clay Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 12
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- 229910000679 solder Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
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- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
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- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000032798 delamination Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
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- 230000003247 decreasing effect Effects 0.000 description 5
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
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- 229920001342 Bakelite® Polymers 0.000 description 3
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
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- 239000011229 interlayer Substances 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
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- 238000003980 solgel method Methods 0.000 description 3
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- 239000011882 ultra-fine particle Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000009918 complex formation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
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- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
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- 238000003475 lamination Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 239000011342 resin composition Substances 0.000 description 1
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- 238000005476 soldering Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
-
- 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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0242—Shape of an individual particle
- H05K2201/0257—Nanoparticles
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明のエポキシ樹脂組成物はナノクレーを充填剤として含み、低い吸湿性及び優れた耐熱性、高温特性、耐電食性を満足しながら、高いガラス転移温度(Tg)を有する特徴がある。
したがって、本発明では全ての物性をバランスよく向上させるために、エポキシ樹脂組成物中のビスフェノールA型ノボラックエポキシ樹脂として平均エポキシ当量が100〜500の範囲であるものを使用し、これはメチルセロソルブ(MCS)、メチルエチルケトン(MEK)などの溶媒に溶解して使用する。前記ビスフェノールA型ノボラックエポキシ樹脂の量は全エポキシ樹脂100重量部に対して、下記の3官能基以上の多官能性エポキシ樹脂の使用量との関係において20乃至120重量比で使用することが好ましい。前記ビスフェノールA型ノボラックエポキシ樹脂の量が20重量比未満であれば、ガラス転移温度が低下する問題があり、120重量比を超えれば未反応エポキシ樹脂のために耐熱性が低下する問題がある。
上記充填剤はプラスチックに配合して製品の品質や加工性を改善する材料として使用される。プラスチックの加工性、機械的特性、電気的特性、および熱的性質に対する、プラスチックへの充填剤の添加効果は、粒子形状、例えば、繊維状、板状、あるいは球状、に応じて非常に変わる。充填剤を使用する主な目的は、熱膨張率の減少、硬化収縮率の低下、耐摩耗性の向上、難燃性の向上を含めて、機械的特性の向上のためである。無機質充填剤としてはシリカ、タルク、炭酸カルシウムなどが主に使用され、金属質充填剤としてはアルミニウム、酸化アルミニウムなどが広く使用される。また、有機物及び無機質の充填剤としてはナノクレーがある。
本発明で使用されるエポキシ樹脂は表1の化合物を使用し、フェノール系硬化剤は表2の化合物を使用した。
平均エポキシ当量が100乃至500であるビスフェノールA型エポキシ樹脂(DIC、N-865)70g、3官能以上の多官能エポキシ樹脂(Bakelite社、LER-673)30g、ビスフェノールA型ノボラックフェノール系硬化剤(江南化学社、VH-4290)35g、臭素化されたフェノール系硬化剤(Tosoh、TBBPA)40g、イミダゾール化合物を含有する硬化促進剤0.5g、添加剤である酸化防止剤1g及びUV安定剤1g、ナノクレーとしてCloisite 20A(Southern Clay Products)4gを非揮発性物質が64%になるまでメチルセロソルブ(MCS)で溶解してワニスを製造した。
上記実施例1でCloisite 20A(Southern Clay Products)の代りに、Cloisite 30B(Southern Clay Products)4gを使用したことを除いては、実施例1と同様の方法で非揮発性物質が64%であるワニスを製造した。
上記実施例1でCloisite 20A(Southern Clay Products)の代りに、Na-MMT(Southern Clay Products)4gを使用したことを除いては、実施例1と同様の方法で非揮発性物質が64%であるワニスを製造した。
上記実施例1でCloisite 20A(Southern Clay Products)の代りに、Cloisite 93A(Southern Clay Products)4gを使用したことを除いては、実施例1と同様の方法で非揮発性物質が64%であるワニスを製造した。
ナノクレーを使用しないことを除いては、上記実施例1と同様の方法でワニスを製造した。
(プリプレグの製造)
上記実施例1乃至2、及び比較例1乃至3で使用したワニスの主要成分及びその含量は下記表3に示す。表3で記載された量の単位はg(グラム)である。
(銅箔積層板の製造)
上記実施例3で得たプリプレグ6枚を互いに重ねて、厚さ36μmの銅箔を夫々複合体両面に重ねて積層し、190℃で150分間20kgf/cm2の圧力で加圧して銅箔積層板を形成した。このように得られた銅箔積層板をエッチングなどの過程を経てTg、耐半田性、5%重量損失、耐熱性テストを実施し、その結果を表4に示した。物性測定は下記のような方法を使用した。
1)ガラス転移温度(Tg):TA社のDSC(Q100)を使用して測定し、10℃/minの速度で温度を上げて測定した。
2)5%重量損失:TA社のTGA(Q500)を使用して測定し、10℃/minの速度で温度を上げて測定した。
3)耐半田性:製造された銅箔積層板を横5cm×縦5cm大きさに切断した。この試験片を288℃で浮遊させて、銅箔または層間で層間剥離する時間を測定した。
4)耐熱性:エッチングした銅箔積層板を横5cm×縦5cm大きさに切断した。この試験片を、121℃、2気圧で2時間加圧した後、288℃の半田付け槽に10秒間浸漬して積層板の外形を肉眼で観察した。外形におけるミーズリング、層間剥離などの程度で判断した。
(×:非常に悪い、△:悪い、○:普通、◎:良い、◎◎:非常に良い)
上記で耐半田性、耐熱性などの特性に優れたナノクレーであるCloisite 30Bを使用して、ワニスを製造した。
上記実施例2と同様の方法と含量で実施したが、Cloisite 30Bの量を2gに減量してMCS溶媒に非揮発性物質が64%であるワニスを製造した。
上記実施例2と同様の方法と含量で実施したが、Cloisite 30Bの量を3gに減量してMCS溶媒に非揮発性物質が64%であるワニスを製造した。
上記実施例2と同様の方法と含量で実施したが、Cloisite 30Bの量を5gに増量してMCS溶媒に非揮発性物質が64%であるワニスを製造した。
Tgを向上させるために臭素含量を下げながら(TBBPAの量を減少し、VH-4290の量を増加する)試験をした。また、前記で耐半田性、耐熱性などの特性に優れたナノクレーであるCloisite 30Bを使用してワニスを製造した。
平均エポキシ当量が100〜500であるビスフェノールA型エポキシ樹脂(DIC、N-865)70g、3官能以上の多官能性エポキシ樹脂(Bakelite社、LER-673)30g、ビスフェノールA型ノボラックフェノール系硬化剤(江南化学VH-4290)40g、臭素化されたフェノール系硬化剤(Tosoh、TBBPA)35g、イミダゾール化合物を含有する硬化促進剤0.5g、酸化防止剤及びUV安定剤各々1g、Cloisite 30B(Southern Clay Products)3gをMCS溶媒に非揮発性物質が64%になるまで溶解してワニスを製造した。
平均エポキシ当量が100〜400であるビスフェノールA型エポキシ樹脂(DIC、N-865)70g、3官能以上の多官能性エポキシ樹脂(Bakelite社、LER-673)30g、ビスフェノールA型ノボラックフェノール系硬化剤(江南化学VH-4290)45g、臭素化されたフェノール系硬化剤(Tosoh、TBBPA)30g、イミダゾール化合物を含有する硬化促進剤0.5g、酸化防止剤及びUV安定剤各々1g、Cloisite 30B(Southern clay products、ナノクレー)3gをMCS溶媒に非揮発性物質が64%になるまで溶解してワニスを製造した。
なお、図面中の記号の意味は以下のとおりである。
10・・・銅箔、20・・・ガラス、30・・・ナノクレー、40・・・エポキシ樹脂
Claims (6)
- a)平均エポキシ当量が100〜500であるビスフェノールA型ノボラックエポキシ樹脂20乃至120重量比、及び平均エポキシ当量が100〜500であるクレゾールエポキシ樹脂10乃至80重量比を含むエポキシ樹脂組成物100重量部と;
b)前記a)100重量部に対してイミダゾール化合物を含有する硬化促進剤0.001乃至4重量部と;
c)前記a)100重量部に対して充填剤として下記の化学式6及び化学式8で示される化合物からなる群から選択される有機物置換体を層状シリケートの間に含むナノクレー0.1乃至20重量部と;
d)臭素が重量で40〜70%含まれている臭素化されたフェノール系硬化剤をエポキシ当量に対して0.1乃至0.7当量の当量比と;
e)ビスフェノールA型ノボラックフェノール系硬化剤をエポキシ当量に対して0.3乃至1.0当量比で含む、
銅箔積層板用エポキシ樹脂組成物。
- 前記硬化促進剤が、2-エチル-4-メチルイミダゾール、1-(2-シアノエチル)-2-アルキルイミダゾール、2-フェニルイミダゾール、及びイソシアネート-マスキングされたイミダゾール系化合物からなる群より1種以上選択されるものである、請求項1に記載の銅箔積層板用エポキシ樹脂組成物。
- 前記組成物がエポキシ樹脂組成物100重量部当り0.01乃至7重量部の添加剤をさらに含む、請求項1又は2に記載の銅箔積層板用エポキシ樹脂組成物。
- 請求項1乃至3のいずれか一項記載の銅箔積層板用エポキシ樹脂組成物をガラス繊維に含浸して得たプリプレグ。
- 請求項4に記載のプリプレグが少なくとも1種以上積層され、前記プリプレグの一面または両面に積層された少なくとも一枚の銅箔を含む、印刷回路基板用銅箔積層板。
- 前記プリプレグと前記銅箔が加熱及び加圧によって一体化されたものである、請求項5に記載の印刷回路基板用銅箔積層板。
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