CN110121532A - Resin combination, prepreg, metal-clad, printed circuit board and flexible rigid print circuit board - Google Patents
Resin combination, prepreg, metal-clad, printed circuit board and flexible rigid print circuit board Download PDFInfo
- Publication number
- CN110121532A CN110121532A CN201880005369.8A CN201880005369A CN110121532A CN 110121532 A CN110121532 A CN 110121532A CN 201880005369 A CN201880005369 A CN 201880005369A CN 110121532 A CN110121532 A CN 110121532A
- Authority
- CN
- China
- Prior art keywords
- circuit board
- resin
- composition
- epoxy resin
- flexible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920005989 resin Polymers 0.000 title claims abstract description 63
- 239000011347 resin Substances 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 84
- 239000003822 epoxy resin Substances 0.000 claims abstract description 72
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 72
- 239000013034 phenoxy resin Substances 0.000 claims abstract description 28
- 229920006287 phenoxy resin Polymers 0.000 claims abstract description 28
- 229920001971 elastomer Polymers 0.000 claims abstract description 26
- 239000005060 rubber Substances 0.000 claims abstract description 26
- 239000011258 core-shell material Substances 0.000 claims abstract description 12
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011256 inorganic filler Substances 0.000 claims abstract description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 116
- 239000004020 conductor Substances 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 40
- 239000000835 fiber Substances 0.000 claims description 15
- 230000004048 modification Effects 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 229920000800 acrylic rubber Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
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- 238000004220 aggregation Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
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- 239000000758 substrate Substances 0.000 abstract description 15
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- 238000004519 manufacturing process Methods 0.000 description 27
- 238000000034 method Methods 0.000 description 22
- 238000012360 testing method Methods 0.000 description 22
- 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 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 238000001723 curing Methods 0.000 description 19
- 239000011888 foil Substances 0.000 description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000011889 copper foil Substances 0.000 description 15
- 239000004642 Polyimide Substances 0.000 description 14
- 229920001721 polyimide Polymers 0.000 description 14
- 230000006978 adaptation Effects 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- -1 cyanogen Amine Chemical class 0.000 description 9
- 239000002356 single layer Substances 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
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- 238000010438 heat treatment Methods 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
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- 238000007711 solidification Methods 0.000 description 5
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- DVNYTAVYBRSTGK-UHFFFAOYSA-N 5-aminoimidazole-4-carboxamide Chemical compound NC(=O)C=1N=CNC=1N DVNYTAVYBRSTGK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 210000005097 arteria cerebelosa anteroinferior Anatomy 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- NQMUGNMMFTYOHK-UHFFFAOYSA-N 1-Methoxynaphthalene Natural products C1=CC=C2C(OC)=CC=CC2=C1 NQMUGNMMFTYOHK-UHFFFAOYSA-N 0.000 description 1
- ALLIZEAXNXSFGD-UHFFFAOYSA-N 1-methyl-2-phenylbenzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1 ALLIZEAXNXSFGD-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- KRUCNVFZSLHJKU-UHFFFAOYSA-N [Si].OC(O)=O Chemical compound [Si].OC(O)=O KRUCNVFZSLHJKU-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- OMUGFZNEOIWQOD-UHFFFAOYSA-N boric acid;zinc Chemical compound [Zn].OB(O)O OMUGFZNEOIWQOD-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical group NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004207 white and yellow bees wax Substances 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4028—Isocyanates; Thioisocyanates
-
- 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
-
- 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
-
- 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
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/304—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing phosphorus
-
- 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
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- 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
-
- 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
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
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- Chemical & Material Sciences (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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- Epoxy Resins (AREA)
Abstract
The present invention, which provides, can form with good mouldability and to the high adhesion of substrate and the resin combination that few prepreg and the solidfied material with low thermal expansion rate occurs of picking.Resin combination contains epoxy resin, dicyandiamide, phenoxy resin, core shell rubbers and inorganic filler.The weight average molecular weight of phenoxy resin is 30000 or more.The tensile elongation of phenoxy resin is 20% or more.The content of phenoxy resin is 5 mass parts or more and 30 below the mass relative to 100 mass parts of epoxy resin.The content of core shell rubbers is 3 mass parts or more and 20 below the mass relative to above-mentioned 100 mass parts of epoxy resin.
Description
Technical field
This application involves resin combination, prepreg, metal-clad, printed circuit board and flexible rigid print circuits
Plate.
Background technique
Prepreg for manufacturing printed circuit board etc. passes through all the time makes the resin combination containing heat-curing resin
Object is infiltrated in fiber base material, and is formed until heat drying to semi-cured state.Also, the prepreg is cut into regulation ruler
After very little, number needed for being overlapped and in its one or two sides overlapped metal foil is heated pressurization and is laminated and is formed, thus manufacture is used
In the metal-clad of manufacture printed circuit board.
But prepreg is more crisp because semi-cured state is presented, and is easy to happen when cutting prepreg or when being laminated
Powder.Due to prepreg processing when the picking that occurs, just like impact trace recess, impact occur like that for made plywood
The undesirable worry of trace.
In order to reduce from prepreg there is a situation where losing powder, for example, patent document 1 disclose it is a kind of containing epoxy resin,
The curing agent such as dicyandiamide and partial size are the resin combination of 1 μm of crosslinking rubber below.In addition, patent document 2 discloses one
Kind is containing epoxy resin and by the composition epoxy resin of anhydride modified phenoxy resin.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2001-302813 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2000-336242 bulletin
Summary of the invention
Although however, by the prepreg for the resin combination production recorded in patent document 1 and patent document 2 in certain journey
The generation of picking is reduced on degree, but not can be implemented simultaneously good mouldability and the high adhesion to substrate, in addition, patent is literary
The resin combination recorded in 1 and patent document 2 is offered to be difficult to form the solidfied material with low thermal expansion rate.
The purpose of the application, which is to provide, to be capable of forming with good mouldability and to the high adhesion of substrate and picking
The resin combination that few prepreg and the solidfied material with low thermal expansion rate occurs, the preimpregnation made by the resin combination
Metal-clad, printed circuit board and the flexible rigid print circuit board of material and the solidfied material comprising the resin combination.
Resin combination described herein contains (A) epoxy resin, (B) dicyandiamide, (C) phenoxy resin, (D) nucleocapsid
Rubber and (E) inorganic filler.(C) weight average molecular weight of phenoxy resin is 30000 or more.(C) stretching of phenoxy resin is stretched
Long rate is 20% or more.(C) content of phenoxy resin is 5 mass parts or more and 30 relative to 100 mass parts of (A) epoxy resin
Below the mass.(D) content of core shell rubbers is 3 mass parts or more and 20 mass parts relative to 100 mass parts of (A) epoxy resin
Below.
Prepreg described herein contains fiber base material and is infiltrated in the semi-solid preparation of the resin combination of fiber base material
Object.
Metal-clad described herein includes insulating layer and the setting of the solidfied material comprising resin combination
In the metal layer of insulating layer.
Printed circuit board described herein includes the insulating layer of the solidfied material comprising resin combination and is set to
The conductor wiring of insulating layer.
Flexible rigid print circuit board described herein include multiple rigid portions, the multiple rigid portions of connection flexible part,
And be set to multiple rigid portions and flexible part at least one of conductor wiring, multiple rigid portions at least one of
Solidfied material comprising resin combination.
According to the application, it can get and be capable of forming with good mouldability and to the high adhesion of substrate and the hair of picking
The resin combination of raw few prepreg and the solidfied material with low thermal expansion rate, the preimpregnation made by the resin combination
Metal-clad, printed circuit board and the flexible rigid print circuit board of material and the solidfied material comprising the resin combination.
Detailed description of the invention
Fig. 1 is the sectional view of prepreg described in the embodiment of the application.
Fig. 2 is the sectional view of metal-clad described in the embodiment of the application.
Fig. 3 A is the sectional view of the printed circuit board of single layer structure described in the embodiment of the application.
Fig. 3 B is the sectional view of the printed circuit board of multilayered structure described in the embodiment of the application.
Fig. 4 is the sectional view of flexible rigid print circuit board described in the first embodiment of the application.
Fig. 5 is the sectional view of flexible rigid print circuit board described in the second embodiment of the application.
Fig. 6 is the sectional view of flexible rigid print circuit board described in the third embodiment of the application.
Specific embodiment
Hereinafter, illustrating presently filed embodiment.
[resin combination described in present embodiment]
Resin combination described in present embodiment (hereinafter referred to as composition (X)) contains (A) epoxy resin, (B) double cyanogen
Amine, (C) phenoxy resin, (D) core shell rubbers and (E) inorganic filler.(C) weight average molecular weight of phenoxy resin be 30000 with
On.(C) tensile elongation of phenoxy resin is 20% or more.(C) content of phenoxy resin is relative to (A) epoxy resin
100 mass parts are 5 mass parts or more and 30 below the mass.(D) content of core shell rubbers is relative to 100 matter of (A) epoxy resin
Measuring part is 3 mass parts or more and 20 below the mass.
In present embodiment, composition (X) has above-mentioned composition, therefore, is had by the prepreg of composition (X) production good
Good mouldability and the high adhesion to substrate, and the generation to lose powder is few.In turn, the solidfied material of composition (X) has low-heat swollen
Swollen rate.
For the ingredient that composition (X) contains, it is illustrated in more details.
<(A) epoxy resin>
(A) epoxy resin (hereinafter referred to as (A) ingredient) can assign Thermocurable to composition (X).In addition, by making group
It closes object (X) and contains (A) ingredient, the solidfied material of composition (X) can have good heat resistance.
As (A) ingredient, such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type epoxy tree can be enumerated
The bisphenol-type epoxy resins such as rouge；The phenol aldehyde type epoxy resins such as phenol novolak type epoxy, cresol novolak type epoxy resin；Biphenyl
Type epoxy resin, phenylenedimethylidyne type epoxy resin, phenol aralkyl type epoxy resin, xenyl aralkyl type epoxy tree
Rouge, xenyl phenol aldehyde type epoxy resin, xenyl dimethylene type epoxy resin, tris-phenol phenol aldehyde type epoxy resin, four
The aryl alkenes type epoxy resin such as methyl biphenyl type epoxy resin；The naphthalene type epoxy resins such as tetrafunctional naphthalene type epoxy resin；
Naphthalene skeleton is modified cresol novolak type epoxy resin, naphthalene glycol aralkyl-type epoxy resin, naphthols aralkyl-type epoxy resin, methoxy
Base naphthalene is modified the naphthalene skeletons modified epoxies such as cresol novolak type epoxy resin, methoxynaphthalene dimethylene type epoxy resin；Three
Phenylmethane type epoxy resin；Anthracene type epoxy resin；Dicyclopentadiene-type epoxy resin；Norbornene-type epoxy resin；Fluorenes type
Epoxy resin；By flame-retarded epoxy resin obtained by above-mentioned epoxy resin halogenation；P Modification epoxy resin etc..(A) ingredient can be with
It is used alone a kind among them, can also be applied in combination two or more.
In the bisphenol A-type that composition (X) is 30000 or more containing weight average molecular weight and tensile elongation is 20% or more
In the case where epoxy resin, the bisphenol A type epoxy resin as (C) ingredient phenoxy resin and contain in composition (X).
Therefore, the bisphenol A type epoxy resin contained as (A) ingredient is bisphenol type epoxy tree of the weight average molecular weight less than 30000
Rouge, tensile elongation are less than 20% bisphenol A type epoxy resin or weight average molecular weight are less than 30000 and tensile elongation is small
In 20% bisphenol A type epoxy resin.
(A) ingredient preferably comprises P Modification epoxy resin.P Modification epoxy resin refers to the epoxy resin containing phosphorus atoms.
(A) when ingredient contains P Modification epoxy resin, the solidfied material of composition (X) can be assigned not adding halogen-system fire retardant
Anti-flammability is given, therefore is conducive to environment.
It as P Modification epoxy resin, is not particularly limited, can be used for example makes organic phosphorus compound and naphtoquinone compounds
It reacts, and P Modification epoxy resin obtained from reacting the reaction product generated in the reaction with epoxy resin.
In the case where (A) ingredient contains P Modification epoxy resin, P Modification epoxy resin preferably has following formula (1) institute
The structure shown.At this point, the solidfied material of composition (X) can have excellent anti-flammability.
[changing 1]
(A) content of ingredient relative to 100 mass parts of composition (X) be preferably 40 mass parts or more and 80 below the mass
In the range of.At this point, composition (X) can have sufficient Thermocurable.(A) content of ingredient is relative to composition (X) 100
Mass parts be more preferably 50 mass parts or more and 70 below the mass in the range of.
In the case where (A) ingredient contains P Modification epoxy resin, preferably with the phosphorus concentration in 100 mass parts of (A) ingredient
The mode for reaching 1% or more contains P Modification epoxy resin.At this point, the solidfied material of composition (X) can have it is higher fire-retardant
Property.Further preferably contain P Modification asphalt mixtures modified by epoxy resin in such a way that the phosphorus concentration in 100 mass parts of (A) ingredient reaches 1.5% or more
Rouge.
<(B) dicyandiamide>
(B) dicyandiamide (hereinafter referred to as (B) ingredient) is functioned as curing agent.If composition (X) contains (B) ingredient
As curing agent, then with for example containing phenol system curing agent the case where compared with, composition (X) is heated and curing rate when solidifying
Slack-off, therefore, the semi-solid preparation object and solidfied material of composition (X) are not easy to become fragile.Therefore, it can reduce by composition (X) production
The picking of prepreg.In turn, if composition (X) contains (B) ingredient as curing agent, with phase the case where containing phenol system curing agent
Than the semi-solid preparation object and solidfied material of composition (X) especially have the more high adhesion to polyimide base material.It is polyimide-based
Material can be suitably used as the coating etc. of printed circuit board, therefore, can effectively serve as using by the prepreg that composition (X) makes
In the baseplate material of production printed circuit board.
In composition (X), preferably with the Ahew of (B) ingredient relative to (A) ingredient epoxide equivalent 1 0.3
Above and 0.8 or less the mode within the scope of this contains (B) ingredient, more preferably with 0.4 or more and 0.7 or less within the scope of this
Mode contain (B) ingredient.It should be noted that epoxide equivalent refers to point of the molecular weight relative to epoxy resin of epoxy resin
The ratio of number for the epoxy group for including in son.In addition, Ahew refers to that the molecular weight of the compound as curing agent is opposite
The ratio of number of the reactive hydrogen being connected directly with the nitrogen-atoms of amino in the compound for being used as curing agent.
<(C) phenoxy resin>
(C) phenoxy resin (hereinafter referred to as (C) ingredient) is high by the condensation reaction of bisphenols and epoxychloropropane
The resin of molecule chemical conversion straight-chain.(C) ingredient can assign the prepreg made by composition (X) flexible, reduce picking
Occur.In addition, by making composition (X) containing (C) ingredient, the semi-solid preparation object and solidfied material of composition (X) can especially have
There is the good adaptation to polyimide base material.
(C) weight average molecular weight of ingredient is 30000 or more.By making 30000 or more the weight average molecular weight of (C) ingredient,
It can reduce the generation of the picking of the prepreg by composition (X) production.(C) upper limit of the weight average molecular weight of ingredient is not special
It limits, such as preferably 100000 or less.
(C) tensile elongation of ingredient is 20% or more.By making 20% or more the tensile elongation of (C) ingredient, energy
It is enough to assign adequately flexibility to the prepreg made by composition (X), therefore, it can reduce the preimpregnation made by composition (X)
The picking of material.AUTOGRAPH can be used to carry out in the measurement of tensile elongation.
As (C) ingredient, the model " YP-50 ", " YP50S " of such as Nippon Steel & Sumitomo Metal Corporation can be used
Deng.
(C) content of ingredient is 5~30 mass parts relative to 100 mass parts of (A) ingredient.(C) content of ingredient is in the model
In the case where in enclosing, the generation of the picking of the prepreg by composition (X) production can reduce, made without making by composition (X)
The mouldability of the prepreg of work reduces.In turn, by making the content of (C) ingredient in the range, the semi-solid preparation object of composition (X)
The adaptation of polyimide base material is not easy to reduce with solidfied material, therefore, the semi-solid preparation object and solidfied material of composition (X) are especially
It is the good adaptation that can have to polyimide base material.
<(D) core shell rubbers>
(D) core shell rubbers (hereinafter referred to as (D) ingredient) can assign the prepreg and solidfied material made by composition (X)
Flexibility causes to significantly affect without the glass transition temperature to solidfied material when solidifying composition (X).Therefore, by combining
The picking of the prepreg of object (X) production is minimized.In turn, by making composition (X) containing (D) ingredient, composition (X) has
Good substrate infiltration property, can have good mouldability by the prepreg that composition (X) makes.
(D) ingredient is the aggregation of rubber particles.Rubber particles have core portion and surround the shell portion in core portion.That is, rubber granule
It does not include the composite material of different materials that son, which is in core portion and shell parts,.
Core portion is not particularly limited, may include for example silicone-acrylic class rubber, acrylic rubber, silicone rubber,
Nitrile rubber, butadiene rubber etc..Core portion preferably comprises silicone-acrylic class rubber or acrylic rubber.At this point, can be right
Higher flexibility is assigned by the prepreg and solidfied material of composition (X) production.
Shell portion is not particularly limited, and may include the multiple grafted chains for being for example bonded to core portion.Grafted chain can have official
It can group.As functional group, such as methylacryloyl, acryloyl group, vinyl, epoxy group, amino, urea groups, mercapto can be enumerated
Base, isocyanate group.In addition, shell portion can be made of such as polymer such as polymethyl methacrylate, polystyrene.
The shape of rubber particles, partial size are not particularly limited.The average grain diameter of rubber particles is preferably such as 0.1~2.0 μ
m.The average grain diameter of rubber particles is the volume reference calculated by the measured value based on laser diffraction/scattering method size distribution
Commercially available laser analysis/scattering formula particle size distribution device can be used to obtain for median particle diameter.
As (D) ingredient, can be used the model " SRK200A " of such as Mitsubishi Rayon Co., Ltd, " S2100 ",
“SX-005”、“S-2001”、“S-2006”、“S-2030”、“S-2200”、“SX-006”、“W-450A”、“E-901”、“C-
223A"；The model " AC3816 " of AICA Industrial Co., Ltd, " AC3816N ", " AC3832 ", " AC4030 ", " AC3364 ",
"IM101"；" MX-217 " of Kaneka Corp. (JP), " MX-153 ", " MX-960 " etc..
(D) content of ingredient is 3 mass parts or more and 20 below the mass relative to 100 mass parts of (A) ingredient.(D) at
Point content in the range in the case where, by composition (X) make prepreg can have good substrate adaptation.Into
And at this point, being able to suppress the coefficient of thermal expansion of the solidfied material of composition (X) becomes excessively high.
<(E) inorganic filler>
By making composition (X) containing (E) inorganic filler (hereinafter referred to as (E) ingredient), the solidfied material of composition (X) can be with
With low thermal expansion rate.In the case where composition (X) contains (D) ingredient, the coefficient of thermal expansion of the solidfied material of composition (X) is easy
It gets higher.But by making composition (X) containing (E) ingredient, the solidfied material of composition (X) can have low thermal expansion rate, because
This, composition (X) even if solidfied material bear thermal stress, the deformations such as warpage, the generation of crackle are also few.
(E) ingredient is not particularly limited, and may include such as aluminium hydroxide, silica, barium sulfate, silica powder, breaks
Broken silica, calcined talc, zinc molybdate cover talcum, barium titanate, titanium oxide, clay, aluminium oxide, mica, boehmite, boric acid
Zinc, zinc stannate, other metal oxides or metal hydrate, calcium carbonate, magnesium hydroxide, magnesium silicate, staple glass fibre, aluminium borate
Whisker, carbonic acid silicon wafer palpus etc..As (E) ingredient, these inorganic fillers be can be used alone, and can also be applied in combination two kinds
More than.(E) ingredient preferably comprise aluminium hydroxide and silica at least one of.
(E) shape of ingredient, partial size are not particularly limited.(E) average grain diameter of ingredient is preferably such as 0.1~5.0 μm.
(E) average grain diameter of ingredient is in the volume reference calculated by the measured value based on laser diffraction/scattering method size distribution
It is worth partial size, commercially available laser analysis/scattering formula particle size distribution device can be used to obtain.
(E) ingredient can use coupling agent etc. and implement surface treatment.Thereby, it is possible to improve the solidification of composition (X)
Adaptation of the object for substrate.As coupling agent, the silane such as epoxy silane coupling agent, mercaptosilane coupling agents can be used
Coupling agent.
(E) content of ingredient relative to 100 mass parts of (A) ingredient be preferably 5 mass parts or more and 100 below the mass.
(E) content of ingredient in the range in the case where, can reduce the coefficient of thermal expansion of the solidfied material of composition (X), without right
Adverse effect is caused by the picking of the prepreg of composition (X) production.(E) content of ingredient is relative to 100 mass of (A) ingredient
It part is more preferably 10 mass parts or more and 70 below the mass.
<other ingredients>
Composition (X) can include in the case where not damaging effect of the present invention above-mentioned (A) ingredient, (B) ingredient, (C) at
Divide, the ingredient except (D) ingredient and (E) ingredient.Composition (X) may include such as dispersing agent, colorant, adaptation and assign
Agent, curing accelerator, organic solvent, other resins and additive.
Composition (X) can be in the case where not damaging effect of the present invention including, for example, except (A) ingredient and (C) ingredient
Resin.Composition (X) may include such as phenolic resin, bimaleimide resin, cyanate ester resin.
In addition, composition (X) can contain the solidification except such as (B) ingredient in the case where not damaging effect of the present invention
Agent.As the curing agent except (B) ingredient, amine system curing agent, the urea system curing agent, acid anhydrides except such as dicyandiamide can be enumerated
It is curing agent etc..
[prepreg 1 described in present embodiment]
Referring to Fig.1, illustrate prepreg 1 described in present embodiment.
Prepreg 1 described in present embodiment has fiber base material 12 and is infiltrated in the composition (X) of fiber base material 12
Semi-solid preparation object 11.
Fiber base material 12 is not particularly limited, and can be used and is for example weaved in the substantially orthogonal mode of warp thread and weft yarn
The woven fabrics substrate such as plain weave substrate.As fiber base material 12, such as woven fabric substrate comprising inorfil can be used, include
Woven fabric substrate of machine fiber etc..As the woven fabric substrate comprising inorfil, can enumerate such as glass cloth.As including
The woven fabric substrate of machine fiber, can enumerate such as aramid fabric, mylar.
Prepreg 1 can be for example, by making composition (X) be infiltrated in fiber base material 12, and is heated dry solid to being presented half
It is formed until change state.Temperature condition when semi-cured state is made, time can be set to such as 170~200 DEG C, 30~90
Minute.It should be noted that semi-cured state refers to the B scalariform state of so-called prepreg etc..That is, being in by by A scalariform
The resin combination of state (varnish state) heats and it is made to be cured to the resin combination in the intermediate stage of C scalariform state (solid state)
Object.
The prepreg 1 formed in this way is formed using composition (X), therefore, as described above, not only having good molding
Property and to the high adhesion of substrate, and the generation to lose powder is also few.Therefore, when being able to suppress because of processing prepreg 1 or by presoaking
Recess, impact occur as impact trace for made plywood caused by the picking occurred when 1 production plywood of material
Trace is bad.For example, as described later, in the case where manufacturing flexible rigid print circuit board using prepreg 1, sometimes through
Using mold processing etc. prepreg 1 is punched out, to prepreg 1 be arranged opening portion be subject to again using.Opening portion will be provided with
Prepreg 1 be layered on the core material for manufacturing flexible rigid print circuit board in the case where, can prevent because from prepreg 1
End face, opening portion inner peripheral surface picking caused by occur due to impact trace or the powder because falling occurs on core material it is bad.
Therefore, the prepreg 1 formed using composition (X) can effectively serve as making the material of high performance printed circuit board
Material.
[metal-clad 2 described in present embodiment]
Referring to Fig. 2, illustrate metal-clad 2 described in present embodiment.
Metal-clad 2 described in present embodiment include the solidfied material comprising composition (X) insulating layer 10, with
And it is set to the metal layer 20 of insulating layer 10.
Metal layer 20 is set at least one face of insulating layer 10.That is, the composition of metal-clad 2, which can be, to be had absolutely
Edge layer 10 and in two layers of metal layer 20 composition that a face of insulating layer 10 configures, be also possible to insulating layer 10, with
And three layers of composition of two metal layers 20 configured in two faces of insulating layer 10.Fig. 2 is the metal-clad 2 of three-decker
Sectional view.
Metal-clad 2 can be for example, by the preimpregnation for being laminated with 1 or semi-solid preparation object of the multi-disc with composition (X)
The one or two sides of the material of material 1 is overlapped metal foil, carries out heating extrusion forming and makes it that integration be laminated to make.It is laminated into
The progress heat/pressure such as multistage vacuum press, hot press, biobelt (double belt) can be used to carry out in type.At this point,
Insulating layer 10 is made by making the solidification of prepreg 1.
Metal-clad 2 can be manufactured without using 1 ground of prepreg.For example, by the metal comprising metal foil
The surface of layer 20 is directly coated with the composition (X) of varnish shape, and metal layer 20 and composition (X) are carried out heat/pressure, can
The composition (X) of varnish shape is set to solidify and make insulating layer 10.
The insulating layer 10 of the metal-clad 2 formed as above thermally expands due to comprising the solidfied material of composition (X)
Rate is low.Therefore, metal-clad 2 is not susceptible to warpage, crackle bearing thermal stress.Therefore, have and include composition
(X) metal-clad 2 of the insulating layer 10 of solidfied material can effectively serve as the base of production high performance print circuit board
Plate material.
[printed circuit board 3,4 described in present embodiment]
Referring to Fig. 3 A and Fig. 3 B, illustrate printed circuit board 3,4 described in present embodiment.
Printed circuit board 3,4 described in present embodiment include the solidfied material comprising composition (X) insulating layer 10, with
And it is set to the conductor wiring 30 of insulating layer 10.
Printed circuit board 3 (hereinafter sometimes referred to core material) is the printed circuit board of single layer structure, is included comprising composition
(X) insulating layer 10 of solidfied material and the conductor wiring 30 of the one or two sides setting in insulating layer 10.Fig. 3 A is tool
The printing of a standby insulating layer 10 and the single layer structure in two conductor wirings 30 of the two sides of an insulating layer 10 setting is electric
The sectional view of road plate 3.The printed circuit board 3 of single layer structure can be formed with through-hole, via hole etc. as needed.
Printed circuit board 4 be core material 3 formation have conductor wiring 30 face on further alternately form insulating layer 10
It is constituted with conductor wiring 30, and is formed with the printed circuit board of the multilayered structure of conductor wiring 31 in outermost layer.In multilayer knot
In the printed circuit board 4 of structure, multiple insulating layers 10 at least one of include composition (X) solidfied material.In multilayered structure
Printed circuit board 4 in, solidfied material of preferably multiple insulating layers 10 all comprising composition (X).Fig. 3 B is that have three insulation
The sectional view of the printed circuit board 4 of the multilayered structure of layer 10 and four conductor wirings 30.The printed circuit board 4 of multilayered structure can root
Through-hole, via hole etc. are formed with according to needs.
The manufacturing method of printed circuit board 3 as single layer structure, is not particularly limited, and can enumerate and for example pass through etching
And it removes a part of the metal layer 20 of above-mentioned metal-clad 2 and forms the subtractive process of conductor wiring 30；By electroless
Single side or two of the plating in the non-cladding sheet (ア Application Network ラ シ De plate) of the insulating layer 10 comprising the solidfied material containing composition (X)
Face forms thin electroless coating, and after utilization plating protective layer (め っ I レ ジ ス ト) protection inverter circuit forming portion, utilizes electricity
It solves plating and thickly applies electro deposition in circuit forming portion, remove plating protective layer thereafter, circuit shape is removed by etching
At the electroless coating except portion, to form the semi-additive process etc. of conductor wiring 30.Printed circuit board 4 as multilayered structure
Manufacturing method, be not particularly limited, can enumerate such as increasing layer technique (build up process).
[flexible rigid print circuit board 5 described in first embodiment]
Referring to Fig. 4, illustrate flexible rigid print circuit board 5 described in first embodiment.
Flexible rigid print circuit board 5 described in first embodiment has multiple rigid portions 51, the multiple rigid portions of connection
51 flexible part 52 and be set to multiple rigid portions 51 and flexible part 52 at least one of conductor wiring 30 (32),
Multiple rigid portions 51 at least one of include composition (X) solidfied material.Specifically, soft described in first embodiment
Property the tool of printed circuit board 5 there are two 51, flexible parts 52 of rigid portion and conductor wiring 30 (32), be set to rigid portion 51
Multiple insulating layers 10 at least one of include composition (X) solidfied material.
Rigid portion 51 is can to bear the weight of component mounted and have the rigid of the hardness and strength for being securable to shell
Property part.Flexible part 52 is that have bent flexible flexible portion.Flexible rigid print circuit board 5 passes through in flexible part 52
Bend and be contained in shell etc. and be used for the machine of small-sized such as mobile electronic apparatus/light weight.The thickness of flexible part 52 is excellent
It is selected as in the range of such as 5~300 μm.At this point, flexible part 52 has good flexibility.
Flexible rigid print circuit board 5 can be by by the single layer for example with an insulating layer 50 and two conductor wirings 30
The flexible printed circuit board 200 of structure is used as core material to manufacture.By by core material 200 in addition to become flexible part 52 part it
Outer part carries out multiple stratification, and rigid portion 51 is consequently formed.That is, a part of core material 200 becomes flexible part 52, core material 200
Other parts become rigid portion 51.The material of insulating layer 50 in core material 200 is as long as flexible material without special
It limits, for example, may include the flexible resin such as polyimides.In addition, the method for multiple stratification is not particularly limited,
Well known method can be used.For example, the tree with metal foil with metal foil and the resin layer comprising composition (X) can be used
Rouge piece simultaneously carries out multiple stratification using Layer increasing method.Resin sheet with metal foil can be for example, by being coated on metal for composition (X)
Foil, and heat drying makes until semi-cured state (B scalariform state) is presented in composition (X).In being formed just for core material 200
Property portion 51 multiple regions in, by the two sides of core material 200 distinguish overlap zone metal foil resin sheet, and in this state into
Row heating extrusion forming, so that the resin layer comprising composition (X) of the resin sheet with metal foil is adhered to core material 200, and is wrapped
Resin layer solidification containing composition (X), is consequently formed the insulating layer 10 of rigid portion 51.Then, by from metal foil
The metal foil of resin sheet implements etching process etc., to form conductor wiring 32 in rigid portion 51.As a result, formed rigid portion 51 and
Form the flexible part 52 for connecting rigid portion 51.
In flexible rigid print circuit board 5 shown in Fig. 4, rigid portion 51 includes a part of core material 200, is arranged in core
Insulating layer 10 on material 200 and the conductor wiring 32 being arranged on insulating layer 10, however, not limited to this, rigid portion 51 can be with
Have and is for example set to outermost welding protective layer.Rigid portion 51 can be respectively provided in the two sides of core material 200 and be arranged alternately
Structure made of more than two insulating layers 10 and more than two conductor wirings 32.That is, rigid portion 51 can pass through Layer increasing method
Deng and further multiple stratification.Rigid portion 51 can be formed with through-hole, via hole etc. as needed.
In flexible rigid print circuit board 5 shown in Fig. 4, flexible part 52 includes a part, the i.e. insulating layer of core material 200
50.That is, flexible part 52 is a part of insulating layer 50.The composition of flexible part 52 is not limited to this, and flexible part 52 may include example
Such as conductor wiring 30.I.e., it is possible to be formed with conductor wiring 30 on the insulating layer 50 of flexible part 52.It is used for furthermore, it is possible to be arranged
The coating of the conductor wiring 30 of core material 200 is covered, at this point, flexible part 52 includes insulating layer 50, conductor wiring 30 and coating.
Insulating layer 50 can be the single layer structure comprising an insulating layer, be also possible to be laminated with the multilayer of multiple layers with insulating properties
Structure.In the case where not damaging the flexibility of flexible part 52, flexible part 52 can have multilayered structure, at this point, by will for example
The flexible printed circuit board of multilayered structure is used as core material, can make rigid and flexible printed circuit board.
In flexible rigid print circuit board 5 shown in Fig. 4, multiple insulating layers 10 at least one of include composition
(X) solidfied material.That is, multiple rigid portions 51 at least one of include composition (X) solidfied material.
[flexible rigid print circuit board 6 described in second embodiment]
Referring to Fig. 5, illustrate flexible rigid print circuit board 6 described in second embodiment.Hereinafter, implementing for first
The identical composition of flexible rigid print circuit board 5 described in mode marks identical symbol and detailed description will be omitted in figure.
Flexible rigid print circuit board 6 described in second embodiment has multiple rigid portions 51, the multiple rigid portions of connection
51 flexible part 52 and be set to multiple rigid portions 51 and flexible part 52 at least one of conductor wiring 30 (32),
Multiple rigid portions 51 at least one of include composition (X) solidfied material.Specifically, soft described in second embodiment
Property the tool of printed circuit board 6 there are two 51, flexible parts 52 of rigid portion and conductor wiring 30 (32), be set to rigid portion 51
Multiple insulating layers 10 at least one of include composition (X) solidfied material.
In flexible rigid print circuit board 6 described in second embodiment, the outermost layer of rigid portion 51 is provided with welding
Protective layer 60.In addition, being provided with the coating 40 of the conductor wiring 30 for covering core material 200.In turn, in the formation of rigid portion 51
There are through-hole 101 and flush type via hole 102.The composition of flexible rigid print circuit board 6 is not limited to this, flexible rigid print electricity
Road plate 6 can not have welding protective layer 60.In addition, flexible rigid print circuit board 6 can not have coating 40.Rigid portion
51 can be formed further with blind hole as needed.
Flexible rigid print circuit board 6 can be by by the single layer for example with an insulating layer 50 and two conductor wirings 30
The flexible printed circuit board 200 of structure is used as core material to manufacture.As long as the material of the insulating layer 50 in core material 200 has flexibility
Material, there is no particular limitation, may include the flexible resin such as polyimides.By the two of core material 200
Face laminate overlay film and form the coating 40 for covering conductor wiring 30.Production has core material 200 and coating as a result,
40 flexible printed circuit board 300.Other than the part in addition to becoming flexible part 52 by the flexible printed circuit board 300
Part carries out multiple stratification, to form rigid portion 51.That is, a part of flexible printed circuit board 300 becomes flexible part 52, it is flexible
The other parts of printed circuit board 300 become rigid portion 51.Method for multiple stratification is not particularly limited, and can be used known
Method, it is more to carry out to can use method for example identical with the flexible rigid print circuit board 5 of above-mentioned first embodiment
Stratification.Specifically, the resin sheet with metal foil and the utilization with metal foil and the resin layer comprising composition (X) can be used
Layer increasing method carries out multiple stratification.Resin sheet with metal foil can be by being coated on metal foil for composition (X), and heat drying is extremely
It is made until composition (X) presentation semi-cured state (B scalariform state).Rigidity is formed in flexible printed circuit board 300
In the multiple regions in portion 51, by distinguishing the resin sheet of overlap zone metal foil on the two sides of flexible printed circuit board 300, and at this
Heating extrusion forming is carried out under state, so that the resin layer comprising composition (X) of the resin sheet with metal foil is adhered to flexibility
Printed circuit board 300, and include the resin layer solidification of composition (X), it thus include the insulating layer 10 of the solidfied material of composition (X)
It is formed in rigid portion 51.Then, by implementing etching process etc. to the metal foil for being originated from the resin sheet with metal foil, thus rigid
Property portion 51 formed conductor wiring 32.The formation of insulating layer 10 and the formation of conductor wiring 32 are alternately repeated, is formed in outermost layer
Welding protective layer 60.Rigid portion 51 is consequently formed, and forms the flexible part 52 for connecting rigid portion 51.Through-hole 101 and embedment
Formula via hole 102 can be formed using known method.
As other methods of manufacture flexible rigid print circuit board 6, can enumerate has fiber base using shown in FIG. 1
The method of material 12 and the prepreg 1 of the semi-solid preparation object 11 for the composition (X) for being infiltrated in fiber base material 12.By being processed using mold
Deng being punched out to prepreg 1, to make opening portion to prepreg 1.The opening portion corresponds to flexible rigid print circuit board 6
Flexible part 52.By there will be the prepreg 1 of opening portion to be overlapped in flexible printed circuit board 300, and carry out in this state
Heating extrusion forming, prepreg 1 are cured, and form the insulating layer 10 of the solidfied material comprising composition (X) in rigid portion 51.Separately
On the one hand, since the opening portion of prepreg 1 corresponds to flexible part 52, insulating layer 10 is not formed in flexible part 52.Then, sharp
Conductor wiring 32 is formed on insulating layer 10 with well known method.Alternately reusing, there is the prepreg 1 of opening portion to carry out
Insulating layer 10 formation and conductor wiring 32 formation, outermost layer formed welding protective layer 60.Rigid portion 51 is consequently formed,
And form flexible part 52 for connecting rigid portion 51.
[flexible rigid print circuit board 7 described in third embodiment]
Referring to Fig. 6, illustrate flexible rigid print circuit board 7 described in third embodiment.Hereinafter, implementing for first
The identical structure of flexible rigid print circuit board 6 described in flexible rigid print circuit board 5 and second embodiment described in mode
At marking identical symbol and detailed description will be omitted in figure.
Flexible rigid print circuit board 7 described in third embodiment has multiple rigid portions 51, the multiple rigid portions of connection
51 flexible part 52 and be set to multiple rigid portions 51 and flexible part 52 at least one of conductor wiring 30 (32),
Multiple rigid portions 51 at least one of include composition (X) solidfied material.Specifically, soft described in third embodiment
Property the tool of printed circuit board 7 there are two 51, flexible parts 52 of rigid portion and conductor wiring 30 (32), be set to rigid portion 51
Multiple bonding sheets 70 at least one of include composition (X) solidfied material.
In flexible rigid print circuit board 7 described in third embodiment, it is provided with the conductor cloth for covering core material 200
The coating 40 of line 30.In addition, being formed with through-hole 101 and blind hole 103 in rigid portion 51.The structure of flexible rigid print circuit board 7
At this is not limited to, flexible rigid print circuit board 7 can not have coating 40.In addition, rigid portion 51 can as needed and
It is formed further with flush type via hole.In addition, rigid portion 51, which can have, is set to outermost welding protective layer.
Flexible rigid print circuit board 7 can be used for example electric with the flexible rigid print for manufacturing second embodiment
The identical flexible printed circuit board 300 of the flexible printed circuit board of road plate 6, printed circuit board 400 and preimpregnation shown in FIG. 1
1 is expected to manufacture.Flexible printed circuit board 300 include the core material 200 comprising an insulating layer 50 and two conductor wirings 30, with
And two coatings 40.Printed circuit board 400 is that there are two the multilayered structures of insulating layer 10 and three conductor wirings 32 for tool
Printed circuit board, be formed with blind hole 103 using well known method.Firstly, by utilizing mold processing etc. to prepreg 1
It is punched out, to make opening portion to prepreg 1.The opening portion corresponds to the flexible part 52 of flexible rigid print circuit board 7.
Prepreg 1 with opening portion is overlapped in flexible printed circuit board 300, printed circuit board is overlapped respectively to prepreg 1
400.By carrying out heating extrusion forming in this state, prepreg 1 is cured and forms the bonding sheet comprising composition (X)
70, and flexible printed circuit board 300 carried out with printed circuit board 400 by bonding sheet 70 it is be bonded.Thereafter, using known
Method formed through-hole 101.It should be noted that the opening portion due to prepreg 1 corresponds to flexible part 52, in flexible part
52 do not form bonding sheet 70.
The composition of printed circuit board 400 is not limited to composition shown in fig. 6.Printed circuit board 400 can have
Have for example identical as the printed circuit board 3 of single layer structure shown in Fig. 3 A with an insulating layer 10 and two conductor wirings 30
Composition.In addition, printed circuit board 400 can have, there are three Fig. 3 B of insulating layer 10 and four conductor wirings 30 with tool
Shown in multilayered structure the identical composition of printed circuit board 4, or tool is there are four insulating layer 10 and five conductor wirings
30 composition.It should be noted that in the flexible rigid print circuit board 7 of third embodiment, printed circuit board 400
Insulating layer 10 may include the solidfied material of composition (X), can also not include the solidfied material of composition (X).
Embodiment
Hereinafter, illustrating the present invention by embodiment.
1. the manufacture of resin combination
It, will be in addition to (D) ingredient, (E) ingredient and curing accelerator among ingredient shown in " composition " column of aftermentioned table 1 and 2
Except ingredient mixed using the mixed solvent of methyl ethyl ketone and dimethylformamide with ratio shown in table 1 and 2, this is mixed
Object is closed to stir 30 minutes.Then, into the mixture shown in " composition " column of the addition table 1 and 2 of ratio shown in table 1 and 2
(D) ingredient, (E) ingredient and curing accelerator make its dispersion using ball mill, thus obtain embodiment 1~11 and comparative example 1~
13 resin combination (resin varnish).
Ingredient in " composition " column of table 1 and 2 notes at foot.
P Modification epoxy resin: Nippon Steel & Sumitomo Metal Corporation's system, model FX-289
Bisphenol A type epoxy resin 1:DIC Co. Ltd. system, model 850-S, 183~193g/eq of epoxide equivalent
Bisphenol A type epoxy resin 2: Nippon Steel & Sumitomo Metal Corporation's system, model YD-011, epoxide equivalent 450~
500g/eq
Bisphenol A type epoxy resin 3: Nippon Steel & Sumitomo Metal Corporation's system, model YD-927, epoxide equivalent 1750~
2100g/eq
Bisphenol A type epoxy resin 4: Nippon Steel & Sumitomo Metal Corporation's system, model YD-020, epoxide equivalent 4000~
6000g/eq
Phenolic resin: Dainippon Ink Chemicals's system, model TD-2093, hydroxyl equivalent 104
Phenoxy resin 1: Nippon Steel & Sumitomo Metal Corporation's system, weight average molecular weight 70000, stretches model YP-50
Elongation 33%
Phenoxy resin 2: Nippon Steel & Sumitomo Metal Corporation's system, weight average molecular weight 60000, stretches model YP50S
Elongation 30%
Phenoxy resin 3: Nippon Steel & Sumitomo Metal Corporation's system, weight average molecular weight 55000, stretches model YP-70
Elongation 10%
Phenoxy resin 4: Nippon Steel & Sumitomo Metal Corporation's system, model ZX-1356-2, weight average molecular weight 70000,
Tensile elongation 12%
Core shell rubbers 1: silicone-acrylic class rubber, Mitsubishi Rayon Co., Ltd's system, model SRK-200A
Core shell rubbers 2: acrylic rubber, AICA Industrial Co., Ltd system, model AC-3816N
Aluminium hydroxide: Sumitomo Chemical Co's system, model C L-303M
Broken silica: Sibelco Japan Co. Ltd. system, model Megasil525
Curing accelerator: 2- ethyl -4- imidazoles, Shikoku Chem's system, model 2E4MZ
It should be noted that the tensile elongation of phenoxy resin 1, phenoxy resin 2 and phenoxy resin 3 is surveyed as follows
It is fixed.Prepare the respective resin plate of phenoxy resin 1~3 (length 15cm, width 1mm, 100 μm of thickness), uses AUTOGRAPH
(Shimadzu Scisakusho Ltd's system, model AG-IS) measures the resin under conditions of 23 ± 2 DEG C, tensile speed 1mm/ minutes
The tensile elongation of plate.
2. the production of prepreg
The resin varnish of each embodiment and comparative example is set to be infiltrated in glass cloth in such a way that the thickness after solidifying reaches 80 μm
(Nitto Boseiki Co., Ltd.'s system, #1078 class, WEA1078), reach 60000 with 170 DEG C of heat drying to melt viscosities~
Until 150000 pools, the prepreg of the resin combination comprising semi-cured state is thus obtained.It should be noted that melt viscosity
Measurement use high formula flow tester (Shimadzu Scisakusho Ltd's system, CFT-100), be in the temperature of flow tester
130 DEG C, pressure be 1.96MPa (20kgf/cm2) under conditions of, the use of diameter is 1mm, carried out with a thickness of the nozzle of 1mm.
3. the production of copper-clad laminated board
18 μm of thickness of copper foil (Mitsui Metal Co., Ltd.'s mining industry strain is configured in the two sides of each embodiment and 1 prepreg of comparative example
Formula commercial firm system, 3EC-III) and be made by laminate, by this by laminate in 190 DEG C and 2.94MPa (30kgf/cm2) pressure under plus
It heat/pressurization 60 minutes, thus obtains being bonded with 80 μm of thickness of copper-clad laminated board of copper foil on two sides.In addition, being opened in stacking 10
The two sides of laminated body obtained by the prepreg of each embodiment and comparative example configure 18 μm of thickness of copper foil (Mitsui Metal Co., Ltd.'s mining industry strain formula
Commercial firm's system, 3EC-III) and be made by laminate, this is subjected to heat/pressure by laminate under conditions of same as described above, thus
It obtains being bonded with 800 μm of thickness of copper-clad laminated board of copper foil on two sides.It should be noted that being using heat by the molding of laminate
Press carries out in the state that the temperature of heat plate of molding machine is heated to 100 DEG C by the investment of laminate.
4. evaluation test
4-1. picking property
The prepreg of each embodiment and comparative example that make in above-mentioned 2 is cut into the size of 11 × 10cm (vertical × horizontal),
It is tested as test film.Firstly, the attachment such as powder, dust is removed from 10 test films using hand-held buffing roll
Object.Then, the weight of 10 test films is measured.Then, using cutter (NT Co. Ltd. system, A type cut spare knife), to 10
Piece test film is equally spaced divided into the scratch of 10 length 10cm respectively, removes powder, ash from 10 test films for being divided into scratch
The attachments such as dirt.Also, measurement is divided into the weight of 10 test films after scratch.It will be by 10 test films before cut-in scratch
Weight subtracts value obtained by the weight of 10 test films after being divided into scratch as picking amount.By picking amount relative to cut-in scratch
The percentage of the weight of 10 preceding test films is as picking property.
4-2. mouldability
For the copper foil on the two sides of 18 μm of thickness of copper-clad laminated board of each embodiment and comparative example that make in above-mentioned 3,
The pattern of clathrate is formed in such a way that residual copper ratio reaches 50% respectively and forms conductor wiring, obtains printed circuit board.At this
The prepreg made in 1 above-mentioned 2 is laminated on the conductor wiring on the two sides of printed circuit board respectively, in 190 DEG C and 2.94MPa
(30kgf/cm2) pressure under heat/pressure 60 minutes, to obtain laminated body.The laminated body is cut into 50 × 50mm's
Size and obtain test film.After the test film is boiled 4 hours, is impregnated 20 seconds in 260 DEG C of solder baths, observe test film
Appearance simultaneously evaluates its result as shown below.
A: expansion is observed.
B: expansion is not observed.
4-3. copper foil adaptation
18 μm of thickness of copper-clad laminated board of each embodiment and comparative example that make in above-mentioned 3 is used as test film.According to
IPC-TM-650-2.4.8 measures the peel strength of the copper foil of the test film.Formation width 10mm, length on test film
The copper foil pattern of 100mm removes copper foil pattern using cupping machine with 50mm/ minutes speed, and the removing measured at this time is strong
Degree.Using the peel strength as copper foil adaptation.
4-4. polyimides adaptation
By single-sided flexible metal-clad (SK Innovation Co. Ltd. system, Enflex (R), 12 μ of copper thickness
M, 20 μm of polyimide thickness) with 1 above-mentioned 2 in the prepreg of each embodiment and comparative example that makes metal is covered with single-sided flexible
The mode that the polyimide layer of plywood connects with prepreg is laminated, in 190 DEG C and 2.94MPa (30kgf/cm2) pressure
Heat/pressure 60 minutes, thus make laminated body under power.The laminated body is cut into the size of 10 × 100mm, is tested
Piece.Using cupping machine, single-sided flexible metal-clad was removed from the test film with 50mm/ minutes speed, measures this
When peel strength.Using the peel strength as polyimides adaptation.
4-5. glass transition temperature (Tg)
The copper foil on the two sides of 80 μm of thickness of copper-clad laminated board of each embodiment and comparative example that make in above-mentioned 3 is removed,
Obtain test film.According to IPC-TM-650-2.4.25, measure (DSC) using differential scanning calorimetry, heating rate be 20 DEG C/
The glass transition temperature (Tg) of the test film is measured under conditions of minute.It should be noted that the glass transition of table 1 and 2
Numerical value in parantheses shown in one column of temperature indicates the glass of low temperature side when measuring glass transition temperature at the 2 of test film
Glass transition temperature.
4-6. coefficient of thermal expansion (CTE)
The copper foil on the two sides of 800 μm of thickness of copper-clad laminated board of each embodiment and comparative example that make in above-mentioned 3 is removed,
Obtain test film.According to JIS C 6481, surveyed using thermo-mechanical analysis (Thermo-mechanical analysis) (TMA) method
The coefficient of thermal expansion (CTE) in the face direction (thickness direction) of the fixed test film.It should be noted that coefficient of thermal expansion is being lower than above-mentioned 4-
It is measured at a temperature of the glass transition temperature measured in 5.
[table 1]
[table 2]
If embodiment 2 and comparative example 13 are compared, falling for the embodiment 2 of (B) ingredient is contained as curing agent
Mealiness is lower than as curing agent the picking of the comparative example containing phenolic resin 13, in turn, to the close of copper foil and polyimides
Conjunction property is higher than comparative example 13.In addition, if embodiment 1 and comparative example 10 are compared, the embodiment 1 containing (C) ingredient
Picking property is less than half of the picking of the comparative example 10 without (C) ingredient.In addition, if embodiment 3 and comparative example 7 are carried out
Comparison, then the picking of the embodiment 3 containing (D) ingredient is the half of the picking of the comparative example 7 without (D) ingredient.As above
It can be confirmed that (B) ingredient, (C) ingredient and (D) make to be reduced by the picking of composition (X) prepreg made at branch.This
Outer confirmation: (B) makes to improve the adaptation of copper foil and polyimides at branch.
In addition, can clearly be confirmed by table 1 and 2: compared with comparative example, embodiment is obtained with good horizontal, good balance
Obtain picking property, formability, the characteristic of copper foil and polyimides adaptation, glass transition temperature and coefficient of thermal expansion.On the other hand,
In comparative example, it cannot get the good resin combination of these characteristics.
Description of symbols
1 prepreg
11 semi-solid preparation objects
12 fiber base materials
2 metal-clads
10,50 insulating layer
20 metal layers
3,4 printed circuit board
30,31,32 conductor wiring
5,6,7 flexible rigid print circuit board
51 rigid portions
52 flexible parts
Claims (8)
1. a kind of resin combination, contain (A) epoxy resin, (B) dicyandiamide, (C) phenoxy resin, (D) core shell rubbers and
(E) inorganic filler,
The weight average molecular weight of (C) phenoxy resin is 30000 or more,
The tensile elongation of (C) phenoxy resin is 20% or more,
The content of (C) phenoxy resin is 5 mass parts or more and 30 matter relative to 100 mass parts of (A) epoxy resin
Measure part hereinafter,
The content of (D) core shell rubbers is 3 mass parts or more and 20 mass relative to 100 mass parts of (A) epoxy resin
Part or less.
2. resin combination according to claim 1, wherein (D) core shell rubbers are the aggregation of rubber particles,
The rubber particles have core portion and surround the shell portion in the core portion,
The core portion includes silicone-acrylic class rubber or acrylic rubber.
3. resin combination according to claim 1 or 2, wherein (A) epoxy resin contains P Modification asphalt mixtures modified by epoxy resin
Rouge.
4. resin combination according to claim 3, wherein the P Modification epoxy resin has shown in following formula (1)
Structure,
5. a kind of prepreg, includes
Fiber base material；And
It is infiltrated in the semi-solid preparation object of the resin combination according to any one of claims 1 to 4 of the fiber base material.
6. a kind of metal-clad, includes
The insulating layer of solidfied material comprising resin combination according to any one of claims 1 to 4；And
It is set to the metal layer of the insulating layer.
7. a kind of printed circuit board, includes
The insulating layer of solidfied material comprising resin combination according to any one of claims 1 to 4；And
It is set to the conductor wiring of the insulating layer.
8. a kind of flexible rigid print circuit board, includes
Multiple rigid portions；
Connect the flexible part of the multiple rigid portion；And
Be set to the multiple rigid portion and the flexible part at least one of conductor wiring,
The multiple rigid portion at least one of consolidating comprising resin combination according to any one of claims 1 to 4
Compound.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017077043A JP6928908B2 (en) | 2017-04-07 | 2017-04-07 | Prepreg, metal-clad laminate, printed wiring board and flex rigid printed wiring board |
| JP2017-077043 | 2017-04-07 | ||
| PCT/JP2018/005422 WO2018186030A1 (en) | 2017-04-07 | 2018-02-16 | Resin composition, prepreg, metal-clad laminate, printed wiring board, and flex-rigid printed wiring board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110121532A true CN110121532A (en) | 2019-08-13 |
Family
ID=63713494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880005369.8A Pending CN110121532A (en) | 2017-04-07 | 2018-02-16 | Resin combination, prepreg, metal-clad, printed circuit board and flexible rigid print circuit board |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6928908B2 (en) |
| KR (1) | KR102480537B1 (en) |
| CN (1) | CN110121532A (en) |
| TW (1) | TWI829631B (en) |
| WO (1) | WO2018186030A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114302907A (en) * | 2019-09-06 | 2022-04-08 | 松下知识产权经营株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and printed wiring board |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020050797A (en) * | 2018-09-27 | 2020-04-02 | パナソニックＩｐマネジメント株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and printed wiring board |
| JP6904441B1 (en) * | 2020-01-30 | 2021-07-14 | 横浜ゴム株式会社 | Epoxy resin composition for prepreg and prepreg |
| KR102424462B1 (en) * | 2021-03-31 | 2022-07-25 | 주식회사 자연바이오 | Glass fiber reinforcement and manufacturing device thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI829631B (en) | 2024-01-21 |
| TW201842045A (en) | 2018-12-01 |
| JP6928908B2 (en) | 2021-09-01 |
| KR102480537B1 (en) | 2022-12-22 |
| JP2018177906A (en) | 2018-11-15 |
| WO2018186030A1 (en) | 2018-10-11 |
| KR20190130121A (en) | 2019-11-21 |
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