TWI516518B - An epoxy resin composition, a prepreg using the epoxy resin composition, a resin film with a support, a laminated sheet of a metal foil, and a multilayer printed circuit board - Google Patents
An epoxy resin composition, a prepreg using the epoxy resin composition, a resin film with a support, a laminated sheet of a metal foil, and a multilayer printed circuit board Download PDFInfo
- Publication number
- TWI516518B TWI516518B TW100119154A TW100119154A TWI516518B TW I516518 B TWI516518 B TW I516518B TW 100119154 A TW100119154 A TW 100119154A TW 100119154 A TW100119154 A TW 100119154A TW I516518 B TWI516518 B TW I516518B
- Authority
- TW
- Taiwan
- Prior art keywords
- epoxy resin
- phosphorus
- resin composition
- chemical formula
- prepreg
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims description 101
- 229920000647 polyepoxide Polymers 0.000 title claims description 101
- 239000000203 mixture Substances 0.000 title claims description 62
- 229920005989 resin Polymers 0.000 title claims description 42
- 239000011347 resin Substances 0.000 title claims description 42
- 229910052751 metal Inorganic materials 0.000 title claims description 14
- 239000002184 metal Substances 0.000 title claims description 14
- 239000011888 foil Substances 0.000 title claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 117
- 239000011574 phosphorus Substances 0.000 claims description 106
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 90
- 239000000126 substance Substances 0.000 claims description 72
- 239000004848 polyfunctional curative Substances 0.000 claims description 51
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 25
- 125000000962 organic group Chemical group 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- -1 phosphorus compound Chemical class 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000004437 phosphorous atom Chemical group 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 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
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 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 37
- 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
- 239000005011 phenolic resin Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 229920003986 novolac Polymers 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
- 239000002904 solvent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000945 filler Substances 0.000 description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 238000010438 heat treatment Methods 0.000 description 6
- 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 5
- 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 5
- 239000011889 copper foil Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 150000002366 halogen compounds Chemical class 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
- 239000007787 solid Substances 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 229940125810 compound 20 Drugs 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000000463 material Substances 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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-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
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-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
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 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
- 229910052799 carbon Inorganic materials 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
- 238000009833 condensation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000013078 crystal 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 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
- PBEHQFUSQJKBAS-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;phenol Chemical compound OC1=CC=CC=C1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 PBEHQFUSQJKBAS-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
- 229930185605 Bisphenol Natural products 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 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
- 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
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002788 crimping Methods 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
- 238000005194 fractionation Methods 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
- 238000003475 lamination Methods 0.000 description 1
- 239000011159 matrix material Substances 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
- 239000004745 nonwoven fabric Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 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
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 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
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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 form; Layered products 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 form; Layered products 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
-
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Description
本發明關於一種印刷電路板用環氧樹脂組成物,並且關於使用前述環氧樹脂組成物的預浸體、附支撐體之樹脂薄膜、貼金屬箔之層合板、以及多層印刷電路板。
伴隨著個人電腦或行動電話等資訊終端機器的普及,該等機器所搭載的印刷電路板的小型化、高密度化正在發展。其安裝形態由端子插入型發展成為表面安裝型,甚至發展成以採用塑膠基板的BGA(球柵陣列)為代表的面矩陣型。在如BGA般直接安裝裸晶的基板中,晶片與基板的連接一般藉由熱超音波壓接進行銲線。在熱超音波壓接中,會使安裝裸晶的基板暴露在150℃以上的高溫。因此,對於電氣絕緣性樹脂而言,會需要具有能承受熱超音波壓接的溫度條件的耐熱性。
甚至也會有需要將已安裝的晶片由基板取下,要求具有所謂的可修復性的情況。在將晶片由基板取下的時候,會進行與晶片安裝時相同程度的加熱。另外,將晶片再度安裝於基板時,又會進一步實施熱處理。因為這樣的重覆加熱,在以往絕緣性樹脂的系統中,在預浸體的纖維基材與樹脂之間會有發生剝離的情形。對於要求具有可修復性的基板而言,會需要有對於重覆暴露於高溫的耐性(耐熱衝撃性)。
藉由在環氧樹脂中添加含溴等鹵素元素的鹵素化合物,雖可確保阻燃性,然而會有因為燃燒而產生一氧化碳或氰化氫的情況。另外,添加溴等鹵素化合物的環氧樹脂,在加熱時溴會分解,而可能會使耐熱性降低或可靠度降低。因此希望開發出在環氧樹脂中不添加鹵素化合物,並可確保阻燃性的成形物。
就不添加鹵素化合物而確保阻燃性的方法而言,可列舉摻合氮、矽、氫氧化鋁等填料的方法。其中以摻合磷化合物的方法廣泛被採用。例如可使用磷酸酯系化合物的磷酸三苯酯(TPP)或磷酸三甲苯酯(TCP)(參照例如專利文獻1)。但是,由於該等磷化合物即使添加於環氧樹脂中也不會與環氧樹脂反應,因此會有所得到的成形物吸濕後的耐熱性或耐化學性等降低的問題發生。
對於此問題,有文獻提出使環氧樹脂與磷化合物反應而合成含磷環氧樹脂的方法(參照例如專利文獻2等)。但是由於使用二氰二醯胺(DICY)作為硬化劑,因而會有必須使用二甲基甲醯胺(DMF)或二甲基乙醯胺(DMAc)等對環境造成高負荷的溶劑的問題。而且也不算是能充分對應近來所需要的低吸濕性、耐熱衝撃性等。
進一步還可列舉例如使用10-(2,5-二羥苯基)-10H-9-氧雜-10-磷雜菲-10-氧化物(三光股份有限公司製,商品名:HCA-HQ)、10-(2,5-二羥萘基)-10H-9-氧雜-10-磷雜菲-10-氧化物(三光股份有限公司製,商品名:HCA-NQ)等磷化合物、或其衍生物作為硬化劑的方法。
但是,由於該等硬化劑對於溶劑的溶解性低,因而必須進行預反應,而有製造步驟變得繁雜等使用性降低的問題。
專利文獻1:日本特開2001-131393號公報
專利文獻2:日本特開2002-265562號公報
本發明係為解決以上的問題點而完成,提供了一種環氧樹脂組成物,其使用性優異、反應性高、阻燃性優異,並具有高耐熱性。
本發明關於以下項目。
[1]一種環氧樹脂組成物,其係含有(A)含磷硬化劑與(B)環氧樹脂,該(A)含磷硬化劑為下述化學式(1)所表示之磷化合物,化學式(1)中的R所表示之有機基團具有2個以上之酚性羥基,且該有機基團之分子量為190以上,
[2]如上述[1]之環氧樹脂組成物,其中化學式(1)中的R所表示之有機基團具有下述結構單位,
(上述結構單位中,*1分別鍵結於碳原子)。
[3]如上述[1]之環氧樹脂組成物,其中化學式(1)中的R所表示之有機基團具有1種或2種以上選自下述化學式(2)、(3)、(4)、(5)及(6)之結構,且具有2個以上之酚性羥基,(式(2)~(6)中的*表示直接鍵結於化學式(1)之磷原子的部位),
(式(5)中的R1為氫原子或碳數1~3之烷基,R2為碳數1~4之烷基;n為芳香環中之OR2基之數,n為1~3之任一數;另外,RA為具有2個以上酚性羥基之有機基團),
(式(6)中的R1為氫原子或碳數1~3之烷基,R2為
碳數1~4之烷基;n為芳香環中之OR2基之數,n為1~3之任一數;另外,RB為具有2個以上酚性羥基之有機基團)。
[4]如上述[2]或[3]之環氧樹脂組成物,其中化學式(1)中的R所表示之有機基團具有1種或2種以上選自下述化學式(7)、(8)及(9)之結構,且具有2個以上之酚性羥基,(式(7)~(9)中的*表示直接鍵結於化學式(1)之磷原子的部位)
[5]一種預浸體,其係使如上述[1]~[4]之環氧樹脂組成物含浸於基材而成。
[6]一種附支撐體之樹脂薄膜,其係將如上述[1]~[4]之環氧樹脂組成物層合於支撐體而成。
[7]一種貼金屬箔之層合板,其係使用如上述[5]之預浸體或如上述[6]之附支撐體之樹脂薄膜而成。
[8]一種多層印刷電路板,其係含有1層或2層以上之由如上述[5]之預浸體所構成之層、由如上述[6]之附支撐體之樹脂薄膜所構成之層、或由如上述[7]之貼金屬箔之層合板所構成之層。
依據本發明,藉由使用上述化學式(1)所表示之含磷硬化劑,可得到一種環氧樹脂組成物、預浸體、附支撐體之樹脂薄膜、貼金屬箔之層合板、多層印刷電路板,該環氧樹脂組成物使用性優異、反應性高、阻燃性優異,並具有高耐熱性。
本發明所關聯之環氧樹脂組成物,係含有下述化學式(1)所表示之(A)含磷硬化劑與(B)環氧樹脂,而(A)含磷硬化劑係下述化學式(1)所表示之磷化合物,化學式(1)中的R所表示之有機基團具有2個以上之酚性羥基,該有機基團之分子量係以190以上為佳。
若分子量為190以上,則含磷硬化劑對於溶劑的溶解性會提升,因而使用性提升。由此環氧樹脂組成物所得到的預浸體、附支撐體之樹脂薄膜、貼金屬箔之層合板等成形品的阻燃性優異,而且耐熱性、電氣特性、耐水性等特性也非常良好。
(含磷硬化劑之結構)
(A)含磷硬化劑係化學式(1)所表示之磷化合物,化學式(1)中的R所表示之有機基團,係以具有下述結構單位為佳。
(上述結構單位中,*1分別鍵結於碳原子)。
另外,(A)含磷硬化劑在化學式(1)中的R所表示之有機基團,係具有1種或2種以上選自下述化學式(2)、(3)、(4)、(5)及(6)之結構,且具有2個以上之酚性羥基。式(2)~(6)中的*表示直接鍵結於化學式(1)之磷原子的部位。
(式(5)中的R1為氫原子或碳數1~3之烷基,R2為碳數1~4之烷基;n為芳香環中之OR2基之數,n為1~3之任一數;另外,RA為具有2個以上酚性羥基之有機基團)。
(式(6)中的R1為氫原子或碳數1~3之烷基,R2為碳數1~4之烷基;n為芳香環中之OR2基之數,n為1~3之任一數;另外,RB為具有2個以上酚性羥基之有機基團)。
化學式(1)中的R所表示之有機基團可採用具有1種或2種以上選自下述化學式(7)、(8)及(9)之結構,且具有2個以上酚性羥基之有機基團。式(7)~(9)中的*表示直接鍵結於化學式(1)之磷原子的部位。
由此環氧樹脂組成物所得到的預浸體、附支撐體之樹脂薄膜、貼金屬箔之層合板等成形品阻燃性優異,而且耐熱性、電氣特性、耐水性等特性也非常良好。
(含磷硬化劑1)
(A)含磷硬化劑可採用在上述化學式(1)中之R所表示之有機基團具有上述化學式(2)之結構之磷化合物。在具有上述化學式(2)所表示之結構的情況下,含有該含磷硬化劑的環氧樹脂組成物的耐熱性會提升。另外,由於含磷硬化劑對於作為反應系統的溶劑的溶解性提升,因此使用性提升。尤其是由於具有上述化學式(2)所表示之結構的該含磷硬化劑為低黏度,因此使用性優異,並可提升生產性。
(含磷硬化劑2)
(A)含磷硬化劑可採用在上述化學式(1)中之R所表示之有機基團具有上述化學式(3)之結構之磷化合物。在具有上述化學式(3)所表示之結構的情況下,與(B)環氧樹脂的反應性會提升。
(含磷硬化劑3)
(A)含磷硬化劑可採用在上述化學式(1)中之R所表示之有機基團具有上述化學式(4)之結構之磷化合物。在具有上述化學式(4)所表示之結構的情況下,含有該含磷硬化劑的環氧樹脂組成物的耐熱性會提升。
(含磷硬化劑4)
(A)含磷硬化劑可採用具有下述化學式(10)所表示之結構單位A與化學式(11)所表示之結構單位B之樹脂
。
亦即,此樹脂可具有連續複數個結構單位A所形成的單位,亦可具有連續複數個結構單位B所形成的單位,還可具有結構單位A與結構單位B交互連結所形成的單位,也可具有前述三種單位混合存在的結構。
在使用具有上述結構單位的酚樹脂作為含磷硬化劑的情況下,含有該含磷硬化劑的環氧樹脂組成物的使用性優異,並可得到高反應性。另外,其阻燃性優異,並具有高耐熱性。
(含磷硬化劑5)
(A)含磷硬化劑可採用具有下述化學式(12)所表
示之結構單位C與化學式(13)所表示之結構單位D之樹脂。
亦即,此樹脂可具有連續複數個結構單位C所形成的單位,亦可具有連續複數個結構單位D所形成的單位,還可具有結構單位C與結構單位D交互連結所形成的單位,也可具有前述三種單位混合存在的結構。
在使用具有上述結構單位的酚樹脂作為含磷硬化劑的情況下,含有該含磷硬化劑的環氧樹脂組成物的使用性優異,並可得到高反應性。另外,其阻燃性優異,並具有高耐熱性。
(含磷硬化劑6)
(A)含磷硬化劑可採用具有下述化學式(14)所表示之結構單位E與化學式(15)所表示之結構單位F之樹脂。
亦即,此樹脂可具有連續複數個結構單位E所形成的單位,亦可具有連續複數個結構單位F所形成的單位,還
可具有結構單位E與結構單位F交互連結所形成的單位,也可具有前述三種單位混合存在的結構。
在使用具有上述結構單位的酚樹脂作為含磷硬化劑的情況下,含有該含磷硬化劑的環氧樹脂組成物的使用性優異,並可得到高反應性。另外,其阻燃性優異,並具有高耐熱性。
(含磷硬化劑之製造方法)
化學式(1)所表示之(A)含磷硬化劑,可藉由使下述化學式(16)所表示之磷化合物與具有酚性羥基的化合物反應而得到。另外還可視情況而添加對-茴香醛。
化學式(16)中之X為H原子或鹵素原子。
在製造含磷硬化劑時可使用的具有酚性羥基的化合物,係以在一分子中具有2個以上的酚性羥基的化合物為佳,已知有:使酚、甲酚、二甲酚、間苯二酚、兒茶酚、雙酚A、雙酚F等酚類或α-萘酚、β-萘酚、二羥基萘等萘酚類與甲醛、乙醛、丙醛、苯甲醛、水楊醛等醛類在酸性觸媒下進行縮合或共縮合所得到的樹脂(酚醛類)、聚對乙
烯基酚樹脂、由酚類與二甲氧基對二甲苯所合成之具有伸茬基的酚-芳烷基樹脂等,可單獨使用或併用兩種以上。
就本發明之環氧樹脂組成物所使用的(B)環氧樹脂而言,係以分子內平均具有1.8個以上的環氧基為佳。其中,在使用分子內平均具有1.8~2.5個(約2個)環氧基的環氧樹脂(雙官能之環氧樹脂)的情況下,樹脂的可塑化效果較大。作為此分子內平均具有1.8~2.5個(約2個)環氧基的環氧樹脂,在採用雙酚A型環氧樹脂的情況下,會成為接著力等良好的硬化物,在採用雙酚F型環氧樹脂的情況下,容易得到阻燃性,在採用聯苯型環氧樹脂的情況下,會成為吸水率低、高Tg(玻璃轉移溫度)的硬化物。另外,藉由採用萘型環氧樹脂,可得到高Tg的硬化物。
在(B)環氧樹脂採用分子內平均具有2.5~3.9個(約3個)環氧基的環氧樹脂(三官能之環氧樹脂)的情況下,可得到Tg更高的硬化物。
另外,在(B)環氧樹脂採用苯酚酚醛型環氧樹脂的情況下,會成為高Tg且容易得到阻燃性的硬化物。
從阻燃性的觀點看來,環氧樹脂組成物中的磷含量,係以占樹脂組成物固體成分全體的0.8~5.0質量%為佳,1.0~2.5質量%為較佳。在磷含量未達樹脂組成物固體成
分全體的0.8質量%的情況下,難以得到穩定的阻燃性,在超過5.0質量%的情況下,硬化物的特性會惡化。
此處,磷含量是指環氧樹脂中的磷原子含量,例如在分子量620的物質中具有1個磷原子,如果是含此物質50質量%的配方,則磷含量成為2.5質量%(磷原子的原子量約為31,因此31/620×0.5=0.025)。
在本發明的環氧樹脂組成物中,亦可添加無機填充劑或矽烷偶合劑作為添加劑。藉由添加無機填充劑,可得到於低熱膨脹率化或提升阻燃性方面優異的材料。另外,藉由添加矽烷偶合劑,可得到使無機填充劑的分散性提升,且耐化學性或剝離強度優異的材料。
其他還可添加會因為紫外線等而發出螢光的化學物質或樹脂。藉此,使用環氧樹脂組成物所製造的多層印刷電路板,在電路形成後作檢查時,可使銅箔圖案呈剪影狀浮現,藉此較容易地進行圖案形狀的辨識以及外觀檢查。
在得到本發明所關聯之環氧樹脂組成物時,可使用溶劑,亦可在無溶劑的情況下進行。另外,在得到該等環氧樹脂組成物時,亦可因應必要添加硬化促進劑、或其他特性賦予劑。
對於使用溶劑的環氧樹脂組成物之製造方法其中一例
作說明。在甲基乙基酮等溶劑中,摻合(A)含磷硬化劑、(B)環氧樹脂、其他硬化劑成分、磷化合物等,攪拌至系統成為均勻。然後,例如將藉由上述溶劑使氫氧化鋁成為泥漿狀之物,作為填料添加,進一步攪拌。藉此可製作出環氧樹脂組成物的清漆。
使用逗號形刮刀塗佈機、轉印塗佈機、簾幕式塗佈機、模具式塗佈機等,將本發明所關聯之環氧樹脂組成物之清漆塗佈於銅箔、鋁箔等支撐體,並連續或不連續地加熱乾燥而進行B階段化(半硬化),形成絕緣層,得到附支撐體之樹脂薄膜。前述附支撐體之樹脂薄膜的金屬箔厚度以及絕緣層樹脂厚度為任意的,但一般而言金屬箔為8~80μm,絕緣層樹脂厚度為20~200μm。
另外,將本發明所關聯之環氧樹脂組成物之清漆塗佈或使其含浸於玻璃布或玻璃不織布,並連續或不連續地加熱乾燥而進行B階段化,得到預浸體。藉由在此預浸體的單面或雙面配置金屬箔(例如銅箔),並進行層合及加熱成形,可得到貼金屬箔之層合板。
使貼金屬箔之層合板、或已形成電路圖案的內層用基板的雙面或單面,隔著預浸體而與上述附支撐體之樹脂薄膜之樹脂面呈對向,進行層合並加熱成形。進一步對外層實施電路形成,可得到多層印刷電路板。
以下藉由實施例對本發明作具體說明,然而本發明並不受其限定。
製作出雙面貼銅層合板之測試片,藉由蝕刻去除雙面貼銅層合板的銅箔,並採用以UL-94規格為基準的垂直燃燒測試(V法)評估阻燃性。若為V-0則阻燃性良好,若為V-1則阻燃性不良。
將雙面貼銅層合板製作成邊長50mm的方形測試片,並使此測試片浮在加溫至288℃的焊接耐熱測試機中,測定觀察到膨脹等異常的時間。評估方式為:「○分鐘OK」表示至○分鐘為止都沒有膨脹等異常現象,「○分鐘NG」表示在○分鐘發生膨脹等異常現象。
玻璃轉移點(Tg)係使用TMA(熱機械分析裝置)(MacScience股份有限公司製TMA-4000),在昇溫速度5℃/min的條件下進行測定。重覆昇溫、降溫兩次,將第二次昇溫的熱膨脹曲線之曲折點溫度定義為Tg。
將作為環氧樹脂的甲酚酚醛型環氧樹脂(DIC股份有限公司製,商品名:Epiclon N-673-70M)143g(樹脂固體成分:70質量%(100g))、作為硬化劑的甲酚酚醛型酚樹脂(DIC股份有限公司製,商品名:Phenolite KA-1163)35g、2-苯基咪唑0.2g、作為含磷硬化劑的以下述化學式(1)與(4)所表示之含磷酚樹脂(Dow Chemical Company製,商品名:XZ-92741)30g、作為磷化合物的1,3-伸苯基-雙-(二-2,6-二甲苯基磷酸酯)(大八化學工業股份有限公司製,商品名:PX200)5g、及甲基乙基酮(MEK)100g摻合,攪拌約1小時至樹脂成為均勻為止。然後,將作為填料的氫氧化鋁(住友化學股份有限公司製,商品名:CL-303)40g以甲基乙基酮泥漿的形式加入,進一步攪拌1小時。藉此可得到磷含量為1.6質量%的環氧樹脂組成物清漆。
(式(4)中的*表示直接鍵結於化學式(1)之磷原子的部位)。
除了不使用1,3-伸苯基-雙-(二-2,6-二甲苯基磷酸酯)(大八化學工業股份有限公司製,商品名:PX200),而且不添加填料以外,以與製造例1同樣的程序製作出環氧樹脂組成物清漆。
除了添加氫氧化鋁(昭和電工股份有限公司製,商品名:HP-360)代替CL303作為填料以外,以與製造例1同樣的程序製作出環氧樹脂組成物清漆。
除了添加水鋁石(boehmite)(河合石灰工業股份有限公司製,商品名:BMT)代替CL303作為填料以外,以與製造例1同樣的程序製作出環氧樹脂組成物清漆。
除了添加破碎二氧化矽(福島窯業股份有限公司製,商品名:F05-30)代替CL303作為填料以外,以與製造例1同樣的程序製作出環氧樹脂組成物清漆。
在製造例6~8中合成含磷硬化劑,並使用所合成的含磷硬化劑製作出環氧樹脂組成物清漆。另外,含磷硬化劑在180℃的熔融黏度及軟化點,係由以下的條件作測定。
在180℃的熔融黏度:在測定溫度180℃,依據ASTM D4287,使用ICI/錐板式黏度計所測得的黏度
軟化點:依據JIS K7234,藉由B&R法所測得的溫度
(含磷硬化劑之合成)
在裝設有溫度計、冷卻管、分餾管、氮氣導入管、攪拌機的燒瓶,裝入苯酚酚醛樹脂192.4g(1.85莫耳)、對-茴香醛68.0g(0.50莫耳)、與9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(以下略稱為HCA)108.0g(0.50莫耳),昇溫至180℃,使其在180℃反應8小時。
接下來,在加熱減壓下將水除去,得到具有下述化學式(10)所表示之結構單位A與化學式(11)所表示之結構單位B之酚樹脂(稱為含磷硬化劑X)355g。以上述方法測定含磷硬化劑X的軟化點的結果為125℃。另外,在180℃的熔融黏度為13dPa.s。另外,羥基當量為190g/eq,磷
含量為4.2質量%。
(環氧樹脂組成物清漆之製作)
接下來,使用含磷硬化劑X作為含磷硬化劑,製作出環氧樹脂組成物清漆。
將作為環氧樹脂的甲酚酚醛型環氧樹脂(DIC股份有限公司,商品名:N-673-70M)100g、作為硬化劑的甲酚酚醛型酚樹脂(DIC股份有限公司製,商品名:Phenolite KA-1163)20g、2-苯基咪唑0.2g、作為含磷硬化劑的含磷硬化劑X 60g、作為磷化合物的1,3-伸苯基-雙-(二-2,6-二甲苯基磷酸酯)(大八化學工業股份有限公司製,商品名:PX200)20g、及甲基乙基酮(MEK)80g摻合,並攪拌約1小時至樹脂成為均勻為止。然後將作為填料的氫氧化
鋁(住友化學股份有限公司製,商品名:CL303)30g以甲基乙基酮泥漿的形式加入,進一步攪拌1小時。藉此可得到磷含量為1.4質量%的環氧樹脂組成物清漆。
(含磷硬化劑之合成)
除了使用雙酚A酚醛樹脂330.4g(2.80莫耳)代替製造例6中所使用的苯酚酚醛樹脂以外,以與製造例6同樣的方式進行反應。得到具有下述化學式(12)所表示之結構單位C與化學式(13)所表示之結構單位D的酚樹脂(稱為含磷硬化劑Y)490g。含磷硬化劑Y的軟化點為139℃(B&R法)。另外,含磷硬化劑Y的熔融黏度為65dPa.s。另外,羥基當量為232g/eq、磷含量為3.1質量%。
(環氧樹脂組成物清漆之製作)
接下來,使用含磷硬化劑Y作為含磷硬化劑,製作出環氧樹脂組成物清漆。
將作為環氧樹脂的甲酚酚醛型環氧樹脂(DIC股份有限公司,商品名:N-673-70M)100g、作為硬化劑的甲酚酚醛型酚樹脂(DIC股份有限公司製,商品名:Phenolite KA-1163)25g、2-苯基咪唑0.2g、作為含磷硬化劑的含磷硬化劑Y 60g、作為磷化合物的1,3-伸苯基-雙-(二-2,6-二甲苯基磷酸酯)(大八化學工業股份有限公司製,商品名:PX200)20g、及甲基乙基酮(MEK)80g摻合,攪拌約1小時至樹脂成為均勻為止。然後將作為填料的氫氧化鋁(住友化學股份有限公司製,商品名:CL303)30g以甲基乙基酮泥漿的形式加入,進一步攪拌1小時。藉此可得到磷含量為1.3質量%的環氧樹脂組成物清漆。
(含磷硬化劑之合成)
除了使用酚芳烷基樹脂392.9g(2.35莫耳)代替在製造例6中所使用的苯酚酚醛樹脂以外,以與製造例6同樣的方式進行反應。得到具有下述化學式(14)所表示之結構單位E與化學式(15)所表示之結構單位F的酚樹脂(稱為含磷硬化劑Z)550g。含磷硬化劑Z的軟化點為102℃(B&R法)。另外,含磷硬化劑Z的熔融黏度為2.5dPa.s。另外,羥基當量為232g/eq、磷含量為2.7質量%。
(環氧樹脂組成物清漆之製作)
接下來,使用含磷硬化劑Z作為含磷硬化劑,製作出環氧樹脂組成物清漆。
將作為環氧樹脂的甲酚酚醛型環氧樹脂(DIC股份有限公司,商品名:N-673-70M)100g、作為硬化劑的甲酚酚醛型酚樹脂(DIC股份有限公司製,商品名:Phenolite KA-1163)25g、2-苯基咪唑0.2g、作為含磷硬化劑的含磷硬化劑Z 60g、作為磷化合物的1,3-伸苯基-雙-(二-2,6-二甲苯基磷酸酯)(大八化學工業股份有限公司製,商品名:PX200)20g、及甲基乙基酮(MEK)80g摻合,攪拌約1小時至樹脂成為均勻為止。然後將作為填料的氫氧化鋁(住友化學股份有限公司製,商品名:CL303)30g以甲基乙基酮泥漿的形式加入,進一步攪拌1小時。藉此可得到磷含量為1.3質量%的環氧樹脂組成物清漆。
(比較製造例1)
將作為環氧樹脂的甲酚酚醛型環氧樹脂(DIC股份有限公司製,商品名:Epiclon N-673-70M)143g(樹脂固體成分:70質量%(100g))、作為硬化劑的甲酚酚醛型酚樹脂(DIC股份有限公司製,商品名:Phenolite KA-1163)35g、2-苯基咪唑0.2g、作為磷化合物的1,3-伸苯基-雙-(二-2,6-二甲苯基磷酸酯)(大八化學工業股份有限公司製,商品名:PX200)40g、及甲基乙基酮100g摻合,攪拌約1小時至樹脂成為均勻為止。然後將作為填料的氫氧化
鋁(住友化學股份有限公司製,商品名:CL-303)40g以甲基乙基酮泥漿的形式加入,進一步攪拌1小時。藉此可得到磷含量為1.4質量%的環氧樹脂組成物清漆。
(比較製造例2)
將作為環氧樹脂的含磷環氧樹脂(東都化成股份有限公司製,商品名:FX-298)100g、作為硬化劑的甲酚酚醛型酚樹脂(DIC股份有限公司製,商品名:Phenolite KA-1163)35g、2-苯基咪唑0.2g、作為磷化合物的1,3-伸苯基-雙-(二-2,6-二甲苯基磷酸酯)(大八化學工業股份有限公司製,商品名:PX200)5g、及甲基乙基酮100g摻合,攪拌約1小時至樹脂成為均勻為止。然後將作為填料的氫氧化鋁(住友化學股份有限公司製,商品名:CL-303)40g以甲基乙基酮泥漿的形式加入,進一步攪拌1小時。藉此可得到磷含量為1.5質量%的環氧樹脂組成物清漆。
(比較製造例3)
將作為環氧樹脂的含磷環氧樹脂(東都化成股份有限公司製,商品名:FX-298)100g、作為硬化劑的甲酚酚醛型酚樹脂(DIC股份有限公司製,商品名:Phenolite KA-1163)20g、二氰二醯胺(DICY)5g、2-苯基咪唑0.2g、作為磷化合物的1,3-伸苯基-雙-(二-2,6-二甲苯基磷酸酯)(大八化學工業股份有限公司製,商品名:PX200)5g、甲基乙基酮70g、及二甲基甲醯胺(DMF)30g摻合,攪
拌約1小時至樹脂成為均勻為止。然後將作為填料的氫氧化鋁(住友化學股份有限公司製,商品名:CL-303)40g以甲基乙基酮泥漿的形式加入,進一步攪拌1小時。藉此可得到磷含量為1.5質量%的環氧樹脂組成物清漆。
於表1揭示製造例1~5、比較製造例1~3之環氧樹脂組成物清漆之配方表。於表2揭示製造例6~8之環氧樹脂清漆之配方表。
將製造例1~5所製作的環氧樹脂組成物清漆含浸於厚度0.2mm的玻璃布(Asahi-Schwebel股份有限公司製,商品名:7629)後,在120℃加熱、乾燥20分鐘,得到預浸體。
在預浸體的兩側,以接著面與預浸體緊密貼合的方式疊合厚度18μm的電解銅箔:F2-WS-18(古河電氣工業股份有限公司製,商品名),以180℃、30分鐘、4MPa的真空壓延條件製作出雙面貼銅層合板。
使用製造例6~8所製作的環氧樹脂組成物清漆,藉由與上述同樣的方法得到預浸體。另外亦製作出雙面貼銅層合板。
使用比較製造例1~3所製作的環氧樹脂組成物清漆,藉由與上述同樣的方法得到預浸體。另外亦製作出雙面貼銅層合板。
將由上述方法所得到的結果揭示於表3。
使用以上述化學式(1)所表示之含磷硬化劑的實施例1~8的層合板具有阻燃性、高耐熱性,另外還發現具有高Tg。另外,相較於使用以往的潛在性硬化劑二氰二醯胺(DICY)的比較例3,實施例1~8的層合板表現出足夠的反應性。另外還發現具有優異的焊接耐熱性、高Tg以及優異的耐熱性。
在實施例1~8中,與使用以往的硬化劑二氰二醯胺(DICY)的情況相比,即使不使用沸點高並具有吸濕性的二甲基甲醯胺(DMF)(使用二甲基甲醯胺係為使二氰二醯胺(DICY)溶解),也能夠使含磷硬化劑溶於通用溶劑的甲基乙基酮(MEK)。另一方面,不使用以上述化學式(1)所表示之含磷硬化劑的比較例1~3的焊接耐熱性差,而且Tg低,耐熱性差。
Claims (6)
- 一種環氧樹脂組成物,其係含有(A)含磷硬化劑與(B)環氧樹脂;該(A)含磷硬化劑為下述化學式(1)所表示之磷化合物;
- 如請求項1之環氧樹脂組成物,其中化學式(1)中之R所表示之有機基團具有1種或2種以上選自下述化學式(4)、或(7)、(8)及(9)之結構,並且具有2個以上酚性羥基,且該有機基團之分子量為190以上;式(4)、(7)、(8)及(9)中之*係表示直接鍵結於化學式(1)之磷原子的部位;
- 一種預浸體,其係使如上述請求項1或2之環氧樹脂組成物含浸於基材而成。
- 一種附支撐體之樹脂薄膜,其係將如上述請求項1或2之環氧樹脂組成物層合於支撐體而成。
- 一種貼金屬箔之層合板,其係使用如上述請求項3之預浸體或如上述請求項4之附支撐體之樹脂薄膜而成。
- 一種多層印刷電路板,其係含有1層或2層以上之由上述請求項3之預浸體所構成之層、由上述請求項4之附支撐體之樹脂薄膜所構成之層、或由上述請求項5之貼金 屬箔之層合板所構成之層。
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EP2578632B1 (en) | 2019-10-30 |
KR20130082448A (ko) | 2013-07-19 |
US20130126218A1 (en) | 2013-05-23 |
KR20130103331A (ko) | 2013-09-23 |
TWI527850B (zh) | 2016-04-01 |
CN105669952B (zh) | 2018-05-29 |
WO2011152412A1 (ja) | 2011-12-08 |
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