WO2011152412A1 - エポキシ樹脂組成物、このエポキシ樹脂組成物を用いたプリプレグ、支持体付き樹脂フィルム、金属箔張り積層板及び多層プリント配線板 - Google Patents
エポキシ樹脂組成物、このエポキシ樹脂組成物を用いたプリプレグ、支持体付き樹脂フィルム、金属箔張り積層板及び多層プリント配線板 Download PDFInfo
- Publication number
- WO2011152412A1 WO2011152412A1 PCT/JP2011/062516 JP2011062516W WO2011152412A1 WO 2011152412 A1 WO2011152412 A1 WO 2011152412A1 JP 2011062516 W JP2011062516 W JP 2011062516W WO 2011152412 A1 WO2011152412 A1 WO 2011152412A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- phosphorus
- resin composition
- chemical formula
- curing agent
- Prior art date
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 103
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 103
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 229920005989 resin Polymers 0.000 title claims description 45
- 239000011347 resin Substances 0.000 title claims description 45
- 239000011888 foil Substances 0.000 title description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 115
- 239000011574 phosphorus Substances 0.000 claims abstract description 107
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000000126 substance Substances 0.000 claims abstract description 74
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 125000000962 organic group Chemical group 0.000 claims abstract description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- -1 phosphorus compound Chemical class 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 82
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004437 phosphorous atom Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- 239000004848 polyfunctional curative Substances 0.000 abstract 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 63
- 238000004519 manufacturing process Methods 0.000 description 34
- 239000002966 varnish Substances 0.000 description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 229920003986 novolac Polymers 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 239000005011 phenolic resin Substances 0.000 description 14
- 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 13
- 229930003836 cresol Natural products 0.000 description 13
- 239000000945 filler Substances 0.000 description 13
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 10
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- APOXBWCRUPJDAC-UHFFFAOYSA-N bis(2,6-dimethylphenyl) hydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(=O)OC1=C(C)C=CC=C1C APOXBWCRUPJDAC-UHFFFAOYSA-N 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 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 6
- 239000011889 copper foil Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 150000002366 halogen compounds Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C)(CC(*)*)N Chemical compound CC(C)(CC(*)*)N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 150000003017 phosphorus Chemical class 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 description 1
- BLBVJHVRECUXKP-UHFFFAOYSA-N 2,3-dimethoxy-1,4-dimethylbenzene Chemical group COC1=C(C)C=CC(C)=C1OC BLBVJHVRECUXKP-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 description 1
- DWGLLTZGGCSKDQ-UHFFFAOYSA-N 5-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)naphthalene-1,6-diol Chemical compound O1C2=CC=CC=C2C2=CC=CC=C2P1(=O)C1=C2C=CC=C(O)C2=CC=C1O DWGLLTZGGCSKDQ-UHFFFAOYSA-N 0.000 description 1
- ORBLXKWVXXBLGW-UHFFFAOYSA-N CC(c(cc1)ccc1OC)I Chemical compound CC(c(cc1)ccc1OC)I ORBLXKWVXXBLGW-UHFFFAOYSA-N 0.000 description 1
- WAJCJYGIAFNBNA-UHFFFAOYSA-N CCCc1cc(C(C)(C)c(cc2)ccc2O)ccc1O Chemical compound CCCc1cc(C(C)(C)c(cc2)ccc2O)ccc1O WAJCJYGIAFNBNA-UHFFFAOYSA-N 0.000 description 1
- BYSXXRDYEGGSGK-UHFFFAOYSA-N CCc1ccc(CCc(cccc2)c2O)cc1 Chemical compound CCc1ccc(CCc(cccc2)c2O)cc1 BYSXXRDYEGGSGK-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 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
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 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
- 238000009835 boiling Methods 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 125000006839 xylylene group Chemical group 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
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- 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
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- 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
-
- 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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising 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
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
-
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
-
- 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
- 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
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
-
- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- 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
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
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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
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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
- 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
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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
- 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
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- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
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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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
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- Y10T428/24995—Two or more layers
- Y10T428/249951—Including a free metal or alloy constituent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
- Y10T428/24995—Two or more layers
- Y10T428/249952—At least one thermosetting synthetic polymeric material layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/256—Heavy metal or aluminum or compound thereof
- Y10T428/257—Iron oxide or aluminum oxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/31511—Of epoxy ether
- Y10T428/31515—As intermediate layer
- Y10T428/31522—Next to metal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31529—Next to metal
Definitions
- the present invention relates to an epoxy resin composition for a printed wiring board, and relates to a prepreg using the epoxy resin composition, a resin film with a support, a metal foil-clad laminate, and a multilayer printed wiring board.
- the mounting form is progressing from a pin insertion type to a surface mounting type, and further to an area array type represented by BGA (ball grid array) using a plastic substrate.
- BGA ball grid array
- the connection between the chip and the substrate is generally performed by wire bonding by thermosonic bonding.
- thermosonic bonding the substrate on which the bare chip is mounted is exposed to a high temperature of 150 ° C. or higher. For this reason, the electrically insulating resin is required to have heat resistance that can withstand the temperature condition of thermosonic bonding.
- repairability is required in which a chip once mounted is removed from the substrate.
- the same amount of heat as that during chip mounting is applied.
- further heat treatment is applied. This repeated heating may cause peeling between the prepreg fiber substrate and the resin in the conventional insulating resin system.
- a substrate that requires repairability is required to have resistance (thermal shock resistance) against repeated exposure to high temperatures.
- a halogen compound containing a halogen element such as bromine By adding a halogen compound containing a halogen element such as bromine to the epoxy resin, flame retardancy can be ensured, but carbon monoxide and hydrogen cyanide may be generated by combustion.
- a halogen compound such as bromine in an epoxy resin to which a halogen compound such as bromine is added, bromine is decomposed during heating, and heat resistance and reliability may be reduced. Therefore, it has been desired to develop a molded product that can ensure flame retardancy without adding a halogen compound to the epoxy resin.
- Examples of a method for ensuring flame retardancy without adding a halogen compound include a method of blending a filler such as nitrogen, silicon, or aluminum hydroxide. Among them, a method of blending a phosphorus compound is widely used.
- TPP triphenyl phosphate
- TCP tricresyl phosphate
- the present invention has been made in order to solve the above problems, and provides an epoxy resin composition having excellent handling properties, high reactivity, excellent flame retardancy, and high heat resistance. Is.
- the present invention relates to the following.
- It contains (A) a phosphorus-containing curing agent and (B) an epoxy resin, and the (A) phosphorus-containing curing agent is a phosphorus compound represented by the following chemical formula (1),
- each * 1 is bonded to a carbon atom.
- R in the chemical formula (1) is selected from the following chemical formulas (2), (3), (4), (5), and (6)
- the epoxy resin composition according to the above [1] which has 2 or more phenolic hydroxyl groups.
- R 1 in Formula (5) is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- R 2 is an alkyl group having 1 to 4 carbon atoms
- n is the number of OR 2 groups in the aromatic ring. Yes, and any one of 1 to 3.
- R A is an organic group having two or more phenolic hydroxyl groups.
- R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- R 2 is an alkyl group having 1 to 4 carbon atoms
- n is the number of OR 2 groups in the aromatic ring.
- R B is an organic group having two or more phenolic hydroxyl groups.
- the organic group represented by R in the chemical formula (1) has one or more of the structures selected from the following chemical formulas (7), (8) and (9), and has 2 phenolic hydroxyl groups.
- an epoxy resin composition having excellent handleability, high reactivity, excellent flame retardancy, and high heat resistance A prepreg, a resin film with a support, a metal foil-clad laminate, and a multilayer printed wiring board can be obtained.
- the epoxy resin composition according to the present invention contains (A) a phosphorus-containing curing agent represented by the following chemical formula (1) and (B) an epoxy resin, and (A) the phosphorus-containing curing agent is represented by the following chemical formula (1). It is preferable that the organic group represented by R in the chemical formula (1) has two or more phenolic hydroxyl groups, and the molecular weight of the organic group is 190 or more.
- the solubility of the phosphorus-containing curing agent in the solvent is improved, and the handleability is improved.
- Molded products such as prepregs, resin films with supports, and metal foil-clad laminates obtained from this epoxy resin composition are excellent in flame retardancy, and also have excellent properties such as heat resistance, electrical properties, and water resistance. It is.
- the phosphorus-containing curing agent is a phosphorus compound represented by the chemical formula (1), and the organic group represented by R in the chemical formula (1) preferably has the following structural unit.
- each * 1 is bonded to a carbon atom.
- the organic group represented by R in the chemical formula (1) is selected from the following chemical formulas (2), (3), (4), (5), and (6). It has 1 type or 2 types or more of a structure, and has 2 or more phenolic hydroxyl groups. * In the formulas (2) to (6) indicates a site directly bonded to the phosphorus atom of the chemical formula (1).
- R 1 in Formula (5) is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- R 2 is an alkyl group having 1 to 4 carbon atoms
- n is the number of OR 2 groups in the aromatic ring. Yes, and any one of 1 to 3.
- R A is an organic group having two or more phenolic hydroxyl groups.
- R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- R 2 is an alkyl group having 1 to 4 carbon atoms
- n is the number of OR 2 groups in the aromatic ring.
- R B is an organic group having two or more phenolic hydroxyl groups.
- the organic group represented by R in the chemical formula (1) has one or more of the structures selected from the following chemical formulas (7), (8) and (9), and has two or more phenolic hydroxyl groups. It can be an organic group.
- * In the formulas (7) to (9) indicates a site directly bonded to the phosphorus atom of the chemical formula (1).
- Molded products such as prepregs, resin films with supports, and metal foil-clad laminates obtained from this epoxy resin composition are excellent in flame retardancy, and also have excellent properties such as heat resistance, electrical properties, and water resistance. It is.
- curing agent can be made into the phosphorus compound which has a structure of the said Chemical formula (2) in the organic group shown by R in the said Chemical formula (1).
- curing agent improves.
- curing agent to the solvent which is a reaction system improves, a handleability improves.
- the phosphorus-containing curing agent having the structure represented by the chemical formula (2) has a low viscosity, it is excellent in handleability and can improve productivity.
- curing agent can be made into resin which has the structural unit A represented by following Chemical formula (10), and the structural unit B represented by Chemical formula (11).
- this resin may have a unit in which a plurality of structural units A are continuous, or may have a unit in which a plurality of structural units B are continuous. It may have a unit formed by alternately connecting B and may have a structure in which the three party units are mixed.
- the epoxy resin composition containing the phosphorus-containing curing agent is excellent in handleability and high reactivity is obtained. Moreover, it is excellent in flame retardancy and has high heat resistance.
- the phosphorus-containing curing agent can be a resin having a structural unit C represented by the following chemical formula (12) and a structural unit D represented by the chemical formula (13).
- this resin may have a unit in which a plurality of structural units C are continuous, or may have a unit in which a plurality of structural units D are continuous. It may have a unit formed by alternately connecting D and may have a structure in which the three party units are mixed.
- the epoxy resin composition containing the phosphorus-containing curing agent is excellent in handleability and high reactivity is obtained. Moreover, it is excellent in flame retardancy and has high heat resistance.
- the phosphorus-containing curing agent may be a resin having a structural unit E represented by the following chemical formula (14) and a structural unit F represented by the chemical formula (15).
- this resin may have a unit in which a plurality of structural units E are continuous, or may have a unit in which a plurality of structural units F are continuous. It may have a unit formed by alternately connecting with F, and may have a structure in which the three party units are mixed.
- the epoxy resin composition containing the phosphorus-containing curing agent is excellent in handleability and high reactivity is obtained. Moreover, it is excellent in flame retardancy and has high heat resistance.
- the (A) phosphorus-containing curing agent represented by the chemical formula (1) is obtained by reacting a phosphorus compound represented by the following chemical formula (16) with a compound having a phenolic hydroxyl group. In some cases, p-anisaldehyde may be added.
- X in the chemical formula (16) is an H atom or a halogen atom.
- a compound having a phenolic hydroxyl group that can be used for the production of a phosphorus-containing curing agent a compound having two or more phenolic hydroxyl groups in one molecule is preferable, and phenol, cresol, xylenol, resorcin, catechol, bisphenol A, Obtained by condensation or cocondensation of phenols such as bisphenol F or naphthols such as ⁇ -naphthol, ⁇ -naphthol, dihydroxynaphthalene and aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde in the presence of an acidic catalyst.
- Resins (novolaks) polyparavinylphenol resins, phenol / aralkyl resins having xylylene groups synthesized from phenols and dimethoxyparaxylene, alone or in combination You may use together
- the (B) epoxy resin used in the epoxy resin composition of the present invention preferably has an average of 1.8 or more epoxy groups in the molecule.
- an epoxy resin having an average of 1.8 to 2.5 (about 2) epoxy groups in the molecule (bifunctional epoxy resin)
- the plasticizing effect of the resin is large.
- a bisphenol A type epoxy resin is used as an epoxy resin having an average of 1.8 to 2.5 (about 2) epoxy groups in the molecule, it becomes a cured product with good adhesion and the like.
- the F type epoxy resin flame retardancy is easily obtained, and when the biphenyl type epoxy resin is used, the water absorption is low and a cured product having a high Tg (glass transition temperature) is obtained.
- cured material with high Tg is obtained by using a naphthalene type epoxy resin.
- the phosphorus content in the epoxy resin composition is preferably 0.8 to 5.0% by mass, and 1.0 to 2.5% by mass based on the total solid content of the resin composition. It is more preferable that When the phosphorus content is less than 0.8% by mass of the total solid content of the resin composition, it is difficult to obtain stable flame retardancy, and when it exceeds 5.0% by mass, the properties of the cured product are deteriorated.
- the phosphorus content is the content of phosphorus atoms in the epoxy resin.
- ⁇ Other additives> You may add an inorganic filler and a silane coupling agent as an additive in the epoxy resin composition of this invention.
- an inorganic filler By adding an inorganic filler, it is possible to obtain a material excellent in lowering the thermal expansion coefficient and improving the flame retardancy. Further, by adding a silane coupling agent, the dispersibility of the inorganic filler can be improved, and a material excellent in chemical resistance and peel strength can be obtained.
- the copper foil pattern is raised in a silhouette when the multilayer printed wiring board manufactured using the epoxy resin composition is inspected after forming the circuit, thereby recognizing the pattern shape and facilitating the appearance inspection. Become.
- the varnish of the epoxy resin composition according to the present invention is applied to a support such as copper foil or aluminum foil using a comma coater, transfer coater, curtain coater, die coater, etc., and dried continuously or discontinuously.
- B-stage (semi-curing) is performed to form an insulating layer to obtain a resin film with a support.
- the thickness of the metal foil and the insulating layer resin of the resin film with a support is arbitrary, the metal foil is generally 8 to 80 ⁇ m, and the insulating layer resin thickness is generally 20 to 200 ⁇ m.
- the varnish of the epoxy resin composition according to the present invention is applied to and impregnated into a glass cloth or a glass nonwoven fabric, and continuously or non-continuously heated and dried to form a B stage to obtain a prepreg.
- a metal foil-clad laminate is obtained by placing a metal foil (for example, copper foil) on one or both sides of this prepreg, laminating, and heat forming.
- the resin surface of the resin film with a support is laminated on both sides or one side of a metal foil-clad laminate or a circuit pattern-formed inner layer substrate through a prepreg, and is heat-molded. Furthermore, a multilayer printed wiring board is obtained by forming a circuit on the outer layer.
- ⁇ Solder heat resistance> A test piece of 50 mm square was prepared from the double-sided copper-clad laminate, and the test piece was floated on a solder heat tester heated to 288 ° C., and the time until abnormality such as swelling was confirmed was measured. In the evaluation, “ ⁇ minute OK” indicates that there is no abnormality such as swelling up to ⁇ minute, and “ ⁇ minute NG” indicates that abnormality such as swelling occurs in ⁇ minute.
- Tg Glass transition point
- TMA thermomechanical analyzer
- phosphorus-containing curing agent X a phenol resin having a structural unit A represented by the following chemical formula (10) and a structural unit B represented by the chemical formula (11) is added. Obtained. It was 125 degreeC when the softening point of the phosphorus containing hardening
- an epoxy resin composition varnish was prepared using the phosphorus-containing curing agent X as a phosphorus-containing curing agent.
- an epoxy resin 100 g of a cresol novolac type epoxy resin (DIC Corporation, trade name: N-673-70M) and as a curing agent, a cresol novolak type phenol resin (manufactured by DIC Corporation, trade name: Ferrite KA-1163) 20 g, 0.2 g of 2-phenylimidazole, 60 g of phosphorus-containing curing agent X as a phosphorus-containing curing agent, 1,3-phenylene-bis- (di-2,6-xylenyl phosphate) (as a phosphorus compound) ( 20 g of Daihachi Chemical Industry Co., Ltd., trade name: PX200) and 80 g of methyl ethyl ketone (MEK) were blended and stirred for about 1 hour until the resin
- MEK methyl ethyl ketone
- an epoxy resin composition varnish was prepared using the phosphorus-containing curing agent Y as a phosphorus-containing curing agent.
- an epoxy resin 100 g of a cresol novolac type epoxy resin (DIC Corporation, trade name: N-673-70M) and as a curing agent, a cresol novolak type phenol resin (manufactured by DIC Corporation, trade name: Ferrite KA-1163) 25 g, 0.2 g of 2-phenylimidazole, 60 g of phosphorus-containing curing agent Y as a phosphorus-containing curing agent, 1,3-phenylene-bis- (di-2,6-xylenyl phosphate) (as a phosphorus compound) ( 20 g of Daihachi Chemical Industry Co., Ltd., trade name: PX200) and 80 g of methyl ethyl ketone (MEK) were blended and stirred for about 1 hour until the resin
- MEK methyl ethyl ketone
- an epoxy resin composition varnish was prepared using the phosphorus-containing curing agent Z as a phosphorus-containing curing agent.
- an epoxy resin 100 g of a cresol novolac type epoxy resin (DIC Corporation, trade name: N-673-70M) and as a curing agent, a cresol novolak type phenol resin (manufactured by DIC Corporation, trade name: Ferrite KA-1163) 25 g, 0.2 g of 2-phenylimidazole, 60 g of phosphorus-containing curing agent Z as phosphorus-containing curing agent, 1,3-phenylene-bis- (di-2,6-xylenyl phosphate) (as phosphorus compound) ( 20 g of Daihachi Chemical Industry Co., Ltd., trade name: PX200) and 80 g of methyl ethyl ketone (MEK) were blended and stirred for about 1 hour until the resin became uniform.
- a cresol novolac type epoxy resin DIC Corporation, trade name
- Table 1 shows a recipe for the epoxy resin composition varnishes of Production Examples 1 to 5 and Comparative Production Examples 1 to 3.
- Table 2 shows a recipe for the epoxy resin varnishes of Production Examples 6-8.
- a double-sided copper-clad laminate was produced under the pressing conditions.
- Examples 6 to 8> Using the epoxy resin composition varnishes produced in Production Examples 6 to 8, prepregs were obtained by the same method as described above. Moreover, the double-sided copper clad laminated board was created.
- ⁇ Comparative Examples 1 to 3> Using the epoxy resin composition varnish prepared in Comparative Production Examples 1 to 3, a prepreg was obtained in the same manner as described above. Moreover, the double-sided copper clad laminated board was created.
- the laminates of Examples 1 to 8 using the phosphorus-containing curing agent represented by the chemical formula (1) were found to have flame retardancy, high heat resistance, and high Tg.
- the laminates of Examples 1 to 8 exhibit sufficient reactivity as compared with Comparative Example 3 using dicyandiamide (DICY), which is a conventional latent curing agent.
- DIX dicyandiamide
- the solder was excellent in heat resistance, Tg was high, and heat resistance was excellent.
- dimethylformamide (DMF) having a high boiling point and high hygroscopicity was not used to dissolve dicyandiamide (DICY).
- the phosphorus-containing curing agent can be dissolved in methyl ethyl ketone (MEK), which is a general-purpose solvent.
- MEK methyl ethyl ketone
- Comparative Examples 1 to 3 that do not use the phosphorus-containing curing agent represented by the chemical formula (1) are inferior in solder heat resistance and have low Tg and inferior heat resistance.
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Abstract
Description
ハロゲン化合物を添加せずに、難燃性を確保する方法としては、窒素、珪素、水酸化アルミニウム等のフィラーを配合する方法が挙げられる。その中でもリン化合物を配合する方法が広く用いられている。例えば、リン酸エステル系の化合物であるトリフェニルホスフェート(TPP)やトリクレジルホスフェート(TCP)が用いられる(例えば、特許文献1参照)。しかし、これらのリン化合物は、エポキシ樹脂中に添加されても、エポキシ樹脂と反応することがないため、得られた成形物の、吸湿後の耐熱性や耐薬品性等が低下するという問題が生じた。
しかし、これらの硬化剤は、溶媒への溶解性が低いため、プレ反応を必要とし、製造工程が煩雑になる等、取り扱い性が低下する問題があった。
[1](A)リン含有硬化剤と、(B)エポキシ樹脂とを含有し、該(A)リン含有硬化剤は、下記化学式(1)で示されるリン化合物であり、化学式(1)におけるRで示される有機基が、フェノール性水酸基を2個以上有し、該有機基の分子量が190以上であるエポキシ樹脂組成物。
[3]化学式(1)におけるRで示される有機基が、下記化学式(2)、(3)、(4)、(5)、及び(6)から選択される構造の1種又は2種以上を有し、フェノール性水酸基を2個以上有する、上記[1]のエポキシ樹脂組成物。
(式(2)~(6)における*は、化学式(1)のリン原子に直接結合する部位であることを示す。)
[4]化学式(1)におけるRで示される有機基が、下記化学式(7)、(8)及び(9)から選択される構造の1種又は2種以上を有し、フェノール性水酸基を2個以上有する上記[2]又は[3]のエポキシ樹脂組成物。
(式(7)~(9)における*は、化学式(1)のリン原子に直接結合する部位であることを示す。)
[6]上記[1]~[4]のエポキシ樹脂組成物を支持体に積層してなる支持体付き樹脂フィルム。
[7]上記[5]のプリプレグ又は上記[6]の支持体付き樹脂フィルムを用いてなる金属箔張り積層板。
[8]上記[5]のプリプレグよりなる層、上記[6]の支持体付き樹脂フィルムよりなる層、又は上記[7]の金属箔張り積層板よりなる層を1層又は2層以上含む多層プリント配線板。
本発明に係るエポキシ樹脂組成物は、下記化学式(1)で示される(A)リン含有硬化剤と、(B)エポキシ樹脂を含有し、(A)リン含有硬化剤は、下記化学式(1)で示されるリン化合物であり、化学式(1)におけるRで示される有機基が、フェノール性水酸基を2個以上有し、該有機基の分子量が190以上であることが好ましい。
(リン含有硬化剤の構造)
(A)リン含有硬化剤は、化学式(1)で示されるリン化合物であり、化学式(1)におけるRで示される有機基が、下記の構造単位を有することが好ましい。
また、(A)リン含有硬化剤は、化学式(1)におけるRで示される有機基が、下記化学式(2)、(3)、(4)、(5)、及び(6)から選択される構造の1種又は2種以上を有し、フェノール性水酸基を2個以上有する。式(2)~(6)における*は、化学式(1)のリン原子に直接結合する部位であることを示す。
(A)リン含有硬化剤は、上記化学式(1)中のRで示される有機基に、上記化学式(2)の構造を有するリン化合物とすることができる。上記化学式(2)で示される構造を有する場合、該リン含有硬化剤を含むエポキシ樹脂組成物の耐熱性が向上する。また、反応系である溶媒へのリン含有硬化剤の溶解性が向上するため取り扱い性が向上する。特に、上記化学式(2)で示される構造を有する該リン含有硬化剤は、低粘度であるため、取り扱い性に優れ、生産性を向上することができる。
(A)リン含有硬化剤は、上記化学式(1)中のRで示される有機基に、上記化学式(3)の構造を有するリン化合物とすることができる。上記化学式(3)で示される構造を有する場合、(B)エポキシ樹脂との反応性が向上する。
(A)リン含有硬化剤は、上記化学式(1)中のRで示される有機基に、上記化学式(4)の構造を有するリン化合物とすることができる。上記化学式(4)で示される構造を有する場合、該リン含有硬化剤を含むエポキシ樹脂組成物の耐熱性が向上する。
(A)リン含有硬化剤は、下記化学式(10)で表される構造単位Aと化学式(11)で表される構造単位Bとを有する樹脂とすることができる。
上述した構造単位を有するフェノール樹脂をリン含有硬化剤として用いた場合に、該リン含有硬化剤を含むエポキシ樹脂組成物は、取り扱い性に優れ、高い反応性が得られる。また、難燃性に優れ、高耐熱性を有する。
(A)リン含有硬化剤は、下記化学式(12)で表される構造単位Cと化学式(13)で表される構造単位Dとを有する樹脂とすることができる。
上述した構造単位を有するフェノール樹脂をリン含有硬化剤として用いた場合に、該リン含有硬化剤を含むエポキシ樹脂組成物は、取り扱い性に優れ、高い反応性が得られる。また、難燃性に優れ、高耐熱性を有する。
(A)リン含有硬化剤は、下記化学式(14)で表される構造単位Eと化学式(15)で表される構造単位Fとを有する樹脂とすることができる。
上述した構造単位を有するフェノール樹脂をリン含有硬化剤として用いた場合に、該リン含有硬化剤を含むエポキシ樹脂組成物は、取り扱い性に優れ、高い反応性が得られる。また、難燃性に優れ、高耐熱性を有する。
化学式(1)で表される(A)リン含有硬化剤は、下記化学式(16)で表されるリン化合物に、フェノール性水酸基を有する化合物を反応して得られる。また、場合により、p-アニスアルデヒドを添加してもよい。
本発明のエポキシ樹脂組成物に用いる(B)エポキシ樹脂としては、分子内に平均1.8個以上のエポキシ基を有するものが好ましい。中でも、分子内に平均して1.8~2.5個(約2個)のエポキシ基を有するエポキシ樹脂(2官能のエポキシ樹脂)を用いた場合、樹脂の可塑化効果が大きい。この分子内に平均して1.8~2.5個(約2個)のエポキシ基を有するエポキシ樹脂として、ビスフェノールA型エポキシ樹脂を用いた場合、接着力等の良好な硬化物となり、ビスフェノールF型エポキシ樹脂を用いた場合、難燃性が得られ易くなり、ビフェニル型エポキシ樹脂を用いた場合、吸水率が低く、高Tg(ガラス転移温度)の硬化物となる。また、ナフタレン型エポキシ樹脂を用いることにより、Tgが高い硬化物が得られる。
難燃性の観点からは、エポキシ樹脂組成物中のリン含有量が、樹脂組成物固形分全体の0.8~5.0質量%であることが好ましく、1.0~2.5質量%であることがより好ましい。リン含有量が、樹脂組成物固形分全体の0.8質量%未満の場合は、安定した難燃性が得られ難く、5.0質量%を超える場合は、硬化物の特性が悪化する。
ここで、リン含有量とは、エポキシ樹脂中のリン原子の含有量であり、例えば、分子量620の物質にリン原子が1個あり、この物質を50質量%含む配合であれば、2.5質量%のリン含有量になる(リン原子の原子量が約31であるから、31/620×0.5=0.025)。
本発明のエポキシ樹脂組成物中に、添加剤として無機充填剤やシランカップリング剤を添加してもよい。無機充填剤を添加することによって、低熱膨張率化や難燃性向上に優れる材料を得ることができる。また、シランカップリング剤を添加することによって、無機充填剤の分散性を向上させ、耐薬品性やピール強度に優れる材料を得ることができる。
本発明に係るエポキシ樹脂組成物を得る際、溶媒を用いてもよいし、無溶媒で行ってもよい。また、これらのエポキシ樹脂組成物を得る際、硬化促進剤、その他特性付与剤を必要に応じて添加してもよい。
溶媒を用いたエポキシ樹脂組成物の製造方法の一例を説明する。メチルエチルケトン等の溶媒に、(A)リン含有硬化剤、(B)エポキシ樹脂、その他の硬化剤成分、リン化合物等を配合し、系が均一になるように撹拌する。この後、例えば、水酸化アルミニウムを上記溶媒によりスラリー状にしたものをフィラーとして加え、更に撹拌する。これにより、エポキシ樹脂組成物のワニスを作製することができる。
本発明に係るエポキシ樹脂組成物のワニスを、コンマコータ、転写コータ、カーテンコータ、ダイコータ等を使用して銅箔、アルミ箔等の支持体に塗布し、連続、又は非連続的に加熱乾燥してBステージ化(半硬化)し、絶縁層を形成して支持体付き樹脂フィルムを得る。前記支持体付き樹脂フィルムの金属箔厚、絶縁層樹脂厚は任意であるが、金属箔としては、8~80μm、絶縁層樹脂厚としては20~200μmが一般的である。
[評価方法]
<難燃性>
両面銅張り積層板の試験片を作製し、両面銅張り積層板の銅箔をエッチングにより取り除き、UL-94規格に基づく垂直燃焼試験(V法)に準じて、難燃性を評価した。V-0であれば難燃性が良好とし、V-1であれば難燃性が不良とした。
両面銅張り積層板を50mm角の試験片を作製し、この試験片を288℃に温めたはんだ耐熱試験機に浮かべ、膨れ等の異常が確認されるまでの時間を測定した。評価は、「○分OK」は、○分まで膨れ等の異常がないことを示し、「○分NG」は、○分で膨れ等の異常が発生したことを示す。
ガラス転移点(Tg)は、TMA(熱機械分析装置)(マックサイエンス株式会社製TMA-4000)を用いて昇温速度5℃/minの条件で測定を行った。昇温、降温を2回繰り返し、2回目の昇温の熱膨張曲線の屈曲点の温度をTgと定義した。
<製造例1>
エポキシ樹脂として、クレゾールノボラック型エポキシ樹脂(DIC株式会社製、商品名:エピクロン N-673-70M)を143g(樹脂固形分:70質量%(100g))、硬化剤として、クレゾールノボラック型フェノール樹脂(DIC株式会社製、商品名:フェノライト KA-1163)を35g、2-フェニルイミダゾールを0.2g、リン含有硬化剤として、下記化学式(1)と(4)とで示されるリン含有フェノール樹脂(ダウケミカルカンパニー製、商品名:XZ-92741)を30g、リン化合物として、1,3-フェニレン-ビス-(ジ-2,6-キシレニルホスフェート)(大八化学工業株式会社製、商品名:PX200)を5g、メチルエチルケトン(MEK)を100g配合し、樹脂が均一になるまで約1時間撹拌した。この後、フィラーとして水酸化アルミニウム(住友化学株式会社製、商品名:CL-303)40gをメチルエチルケトンのスラリーとして加え、更に1時間撹拌した。これにより、リン含有量を1.6質量%としたエポキシ樹脂組成物ワニスが得られた。
1,3-フェニレン-ビス-(ジ-2,6-キシレニルホスフェート)(大八化学工業株式会社製、商品名:PX200)を使用せず、フィラーを添加しないこと以外は、製造例1と同様の手順でエポキシ樹脂組成物ワニスを作製した。
フィラーとして、CL303の代わりに水酸化アルミニウム(昭和電工株式会社製、商品名:HP-360)を添加したこと以外は製造例1と同様の手順でエポキシ樹脂組成物ワニスを作製した。
フィラーとして、CL303の代わりにベーマイト(河合石灰工業株式会社製、商品名:BMT)を添加したこと以外は製造例1と同様の手順でエポキシ樹脂組成物ワニスを作製した。
フィラーとして、CL303の代わりに破砕シリカ(福島窯業株式会社製、商品名:F05-30)を添加したこと以外は製造例1と同様の手順でエポキシ樹脂組成物ワニスを作製した。
製造例6~8では、リン含有硬化剤を合成し、合成したリン含有硬化剤を用いてエポキシ樹脂組成物ワニスを作製した。なお、リン含有硬化剤の180℃における溶融粘度及び軟化点は、以下の条件にて測定した。
180℃における溶融粘度:測定温度180℃において、ASTM D4287に準拠して、ICI/コーンプレート粘度計を用いて測定される粘度
軟化点:JIS K7234に準拠して、B&R法により測定される温度
(リン含有硬化剤の合成)
温度計、冷却管、分留管、窒素ガス導入管、撹拌機を取り付けたフラスコにフェノールノボラック樹脂192.4g(1.85モル)と、p-アニスアルデヒド68.0g(0.50モル)と、9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキサイド(以下 HCAと略)108.0g(0.50モル)とを仕込み、180℃まで昇温し、180℃で8時間反応させた。
次いで、加熱減圧下で水を除去し、下記化学式(10)で表される構造単位Aと化学式(11)で表される構造単位Bとを有するフェノール樹脂(リン含有硬化剤Xという)355gを得た。リン含有硬化剤Xの軟化点を上述の方法で測定したところ、125℃であった。また、180℃における溶融粘度は、13dPa・sであった。また、水酸基当量は、190g/eq、リン含有量4.2質量%であった。
続いて、リン含有硬化剤Xをリン含有硬化剤として用いて、エポキシ樹脂組成物ワニスを作製した。
エポキシ樹脂として、クレゾールノボラック型エポキシ樹脂(DIC株式会社、商品名:N-673-70M)を100g、硬化剤として、クレゾールノボラック型フェノール樹脂(DIC株式会社製、商品名:フェライト KA-1163)を20g、2-フェニルイミダゾールを0.2g、リン含有硬化剤として、リン含有硬化剤Xを60g、リン化合物として、1,3-フェニレン-ビス-(ジ-2,6-キシレニルホスフェート)(大八化学工業株式会社製、商品名:PX200)を20g、メチルエチルケトン(MEK)を80g配合し、樹脂が均一になるまで約1時間撹拌した。この後、フィラーとして、水酸化アルミニウム(住友化学株式会社製、商品名:CL303)30gをメチルエチルケトンのスラリーとして加え、更に1時間撹拌した。これにより、リン含有量を1.4質量%としたエポキシ樹脂組成物ワニスが得られた。
(リン含有硬化剤の合成)
製造例6において使用したフェノールノボラック樹脂の代わりに、ビスフェノールAノボラック樹脂330.4g(2.80モル)を使用した以外は、製造例6と同様にして反応を行った。下記化学式(12)で表される構造単位Cと化学式(13)で表される構造単位Dとを有するフェノール樹脂(リン含有硬化剤Yという)490gを得た。リン含有硬化剤Yの軟化点は、139℃(B&R法)であった。また、リン含有硬化剤Yの溶融粘度は、65dPa・sであった。また、水酸基当量は、232g/eq、リン含有量3.1質量%であった。
続いて、リン含有硬化剤Yをリン含有硬化剤として用いて、エポキシ樹脂組成物ワニスを作製した。
エポキシ樹脂として、クレゾールノボラック型エポキシ樹脂(DIC株式会社、商品名:N-673-70M)を100g、硬化剤として、クレゾールノボラック型フェノール樹脂(DIC株式会社製、商品名:フェライト KA-1163)を25g、2-フェニルイミダゾールを0.2g、リン含有硬化剤として、リン含有硬化剤Yを60g、リン化合物として、1,3-フェニレン-ビス-(ジ-2,6-キシレニルホスフェート)(大八化学工業株式会社製、商品名:PX200)を20g、メチルエチルケトン(MEK)を80g配合し、樹脂が均一になるまで約1時間撹拌した。この後、フィラーとして、水酸化アルミニウム(住友化学株式会社製、商品名:CL303)30gをメチルエチルケトンのスラリーとして加え、更に1時間撹拌した。これにより、リン含有量を1.3質量%としたエポキシ樹脂組成物ワニスが得られた。
(リン含有硬化剤の合成)
製造例6において使用したフェノールノボラック樹脂の代わりに、フェノールアラルキル樹脂392.9g(2.35モル)を使用した以外は、製造例6と同様にして反応を行った。下記化学式(14)で表される構造単位Eと化学式(15)で表される構造単位Fとを有するフェノール樹脂(リン含有硬化剤Zという)550gを得た。リン含有硬化剤Zの軟化点は、102℃(B&R法)であった。また、リン含有硬化剤Zの溶融粘度は、2.5dPa・sであった。また、水酸基当量は、232g/eq、リン含有量2.7質量%であった。
続いて、リン含有硬化剤Zをリン含有硬化剤として用いて、エポキシ樹脂組成物ワニスを作製した。
エポキシ樹脂として、クレゾールノボラック型エポキシ樹脂(DIC株式会社、商品名:N-673-70M)を100g、硬化剤として、クレゾールノボラック型フェノール樹脂(DIC株式会社製、商品名:フェライト KA-1163)を25g、2-フェニルイミダゾールを0.2g、リン含有硬化剤として、リン含有硬化剤Zを60g、リン化合物として、1,3-フェニレン-ビス-(ジ-2,6-キシレニルホスフェート)(大八化学工業株式会社製、商品名:PX200)を20g、メチルエチルケトン(MEK)を80g配合し、樹脂が均一になるまで約1時間撹拌した。この後、フィラーとして、水酸化アルミニウム(住友化学株式会社製、商品名:CL303)30gをメチルエチルケトンのスラリーとして加え、更に1時間撹拌した。これにより、リン含有量を1.3質量%としたエポキシ樹脂組成物ワニスが得られた。
(比較製造例1)
エポキシ樹脂として、クレゾールノボラック型エポキシ樹脂(DIC株式会社製、商品名:エピクロン N-673-70M)を143g(樹脂固形分:70質量%(100g))、硬化剤として、クレゾールノボラック型フェノール樹脂(DIC株式会社製、商品名:フェノライト KA-1163)を35g、2-フェニルイミダゾールを0.2g、リン化合物として、1,3-フェニレン-ビス-(ジ-2,6-キシレニルホスフェート)(大八化学工業株式会社製、商品名:PX200)を40g、メチルエチルケトンを100g配合し、樹脂が均一になるまで約1時間撹拌した。この後、フィラーとして、水酸化アルミニウム(住友化学株式会社製、商品名:CL-303)40gをメチルエチルケトンのスラリーとして加え、更に1時間撹拌した。これにより、リン含有量を1.4質量%としたエポキシ樹脂組成物ワニスが得られた。
エポキシ樹脂として、リン含有エポキシ樹脂(東都化成株式会社製、商品名:FX-298)を100g、硬化剤として、クレゾールノボラック型フェノール樹脂(DIC株式会社製、商品名:フェノライト KA-1163)を35g、2-フェニルイミダゾールを0.2g、リン化合物として、1,3-フェニレン-ビス-(ジ-2,6-キシレニルホスフェート)(大八化学工業株式会社製、商品名:PX200)を5g、メチルエチルケトンを100g配合し、樹脂が均一になるまで約1時間撹拌した。この後、フィラーとして、水酸化アルミニウム(住友化学株式会社製、商品名:CL-303)40gをメチルエチルケトンのスラリーとして加え、更に1時間撹拌した。これにより、リン含有量を1.5質量%としたエポキシ樹脂組成物ワニスが得られた。
エポキシ樹脂として、リン含有エポキシ樹脂(東都化成株式会社製、商品名:FX-298)を100g、硬化剤として、クレゾールノボラック型フェノール樹脂(DIC株式会社製、商品名:フェノライト KA-1163)を20g、及びジシアンジアミド(DICY)を5g、2-フェニルイミダゾールを0.2g、リン化合物として、1,3-フェニレン-ビス-(ジ-2,6-キシレニルホスフェート)(大八化学工業株式会社製、商品名:PX200)を5g、メチルエチルケトンを70g、ジメチルホルムアミド(DMF)を30g配合し、樹脂が均一になるまで約1時間撹拌した。この後、フィラーとして、水酸化アルミニウム(住友化学株式会社製、商品名:CL-303)40gをメチルエチルケトンのスラリーとして加え、更に1時間撹拌した。これにより、リン含有量を1.5質量%としたエポキシ樹脂組成物ワニスが得られた。
<実施例1~5>
製造例1~5で作製したエポキシ樹脂組成物ワニスを厚さ:0.2mmのガラス布(旭シュエーベル株式会社製、商品名:7629)に含浸後、120℃、20分間加熱、乾燥しプリプレグを得た。
プリプレグの両側に、厚さ:18μmの電解銅箔:F2-WS-18(古河電気工業株式会社製、商品名)を接着面がプリプレグと合わさるように重ね、180℃、30分間、4MPaの真空プレス条件で両面銅張り積層板を作製した。
<実施例6~8>
製造例6~8で作成したエポキシ樹脂組成物ワニスを用いて、上述と同様の方法によりプリプレグを得た。また、両面銅張り積層板を作成した。
<比較例1~3>
比較製造例1~3で作成したエポキシ樹脂組成物ワニスを用いて、上述と同様の方法によりプリプレグを得た。また、両面銅張り積層板を作成した。
上記方法にて得られた結果を表3に示した。
実施例1~8では、従来の硬化剤であるジシアンジアミド(DICY)を用いた場合と比べて、ジシアンジアミド(DICY)を溶解させるために、沸点が高く吸湿性のあるジメチルホルムアミド(DMF)を用いなくても、リン含有硬化剤を汎用溶媒であるメチルエチルケトン(MEK)に溶解させることができる。一方、上記化学式(1)で示されるリン含有硬化剤を用いない比較例1~3は、はんだ耐熱性に劣り、Tgが低く耐熱性に劣る。
Claims (8)
- 化学式(1)におけるRで示される有機基が、下記化学式(2)、(3)、(4)、(5)、及び(6)から選択される構造の1種又は2種以上を有し、フェノール性水酸基を2個以上有する、請求項1に記載のエポキシ樹脂組成物。
(式(2)~(6)における*は、化学式(1)のリン原子に直接結合する部位であることを示す。)
- 上記請求項1~4のいずれかに記載のエポキシ樹脂組成物を基材に含浸させてなるプリプレグ。
- 上記請求項1~4のいずれかに記載のエポキシ樹脂組成物を支持体に積層してなる支持体付き樹脂フィルム。
- 上記請求項5に記載のプリプレグ又は上記請求項6に記載の支持体付き樹脂フィルムを用いてなる金属箔張り積層板。
- 上記請求項5に記載のプリプレグよりなる層、上記請求項6に記載の支持体付き樹脂フィルムよりなる層、又は上記請求項7に記載の金属箔張り積層板よりなる層を1層又は2層以上含む多層プリント配線板。
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PCT/JP2011/062516 WO2011152412A1 (ja) | 2010-05-31 | 2011-05-31 | エポキシ樹脂組成物、このエポキシ樹脂組成物を用いたプリプレグ、支持体付き樹脂フィルム、金属箔張り積層板及び多層プリント配線板 |
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EP2578613A1 (en) | 2013-04-10 |
TWI516518B (zh) | 2016-01-11 |
TW201213410A (en) | 2012-04-01 |
CN105669952A (zh) | 2016-06-15 |
CN102918076A (zh) | 2013-02-06 |
KR101803115B1 (ko) | 2017-11-29 |
EP2578613B1 (en) | 2018-11-07 |
EP2578632A1 (en) | 2013-04-10 |
EP2578632B1 (en) | 2019-10-30 |
KR20130082448A (ko) | 2013-07-19 |
KR101938895B1 (ko) | 2019-01-15 |
CN102918107A (zh) | 2013-02-06 |
CN102918107B (zh) | 2016-10-05 |
US20130126218A1 (en) | 2013-05-23 |
KR20130103331A (ko) | 2013-09-23 |
TWI527850B (zh) | 2016-04-01 |
TW201213381A (en) | 2012-04-01 |
US9215803B2 (en) | 2015-12-15 |
WO2011152413A1 (ja) | 2011-12-08 |
US20130108843A1 (en) | 2013-05-02 |
EP2578613A4 (en) | 2014-01-15 |
US8980424B2 (en) | 2015-03-17 |
HK1179290A1 (zh) | 2013-09-27 |
EP2578632A4 (en) | 2014-01-22 |
EP2578613B8 (en) | 2018-12-19 |
CN105669952B (zh) | 2018-05-29 |
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