JPH03192112A - Modified epoxy resin composition - Google Patents
Modified epoxy resin compositionInfo
- Publication number
- JPH03192112A JPH03192112A JP33383989A JP33383989A JPH03192112A JP H03192112 A JPH03192112 A JP H03192112A JP 33383989 A JP33383989 A JP 33383989A JP 33383989 A JP33383989 A JP 33383989A JP H03192112 A JPH03192112 A JP H03192112A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- group
- bisphenol
- resin composition
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 41
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 2,2- dimethylbutyl Chemical group 0.000 claims abstract description 16
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 9
- 239000007983 Tris buffer Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 5
- 239000001273 butane Substances 0.000 claims abstract description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 abstract description 20
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052794 bromium Inorganic materials 0.000 abstract description 6
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000001294 propane Substances 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 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
- 238000009835 boiling Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- NAGFBUMGIZJKBJ-UHFFFAOYSA-N 2,3-bis(4-hydroxy-3,5-dimethylphenyl)-4-methylphenol Chemical compound C=1C(C)=C(O)C(C)=CC=1C=1C(C)=CC=C(O)C=1C1=CC(C)=C(O)C(C)=C1 NAGFBUMGIZJKBJ-UHFFFAOYSA-N 0.000 description 1
- PVKAXVYVPKVMRO-UHFFFAOYSA-N 2,3-bis(5-tert-butyl-2-ethyl-4-hydroxyphenyl)-4-methylphenol Chemical compound CCC1=CC(O)=C(C(C)(C)C)C=C1C1=C(C)C=CC(O)=C1C1=CC(C(C)(C)C)=C(O)C=C1CC PVKAXVYVPKVMRO-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- AZWPUTRWJOZXFG-UHFFFAOYSA-N 4-[3,3-bis(3,5-diethyl-4-hydroxyphenyl)propyl]-2,6-diethylphenol Chemical compound CCC1=C(O)C(CC)=CC(CCC(C=2C=C(CC)C(O)=C(CC)C=2)C=2C=C(CC)C(O)=C(CC)C=2)=C1 AZWPUTRWJOZXFG-UHFFFAOYSA-N 0.000 description 1
- NTLCYMKRCYMXGE-UHFFFAOYSA-N 4-[3,3-bis(4-hydroxy-2,5-dimethylphenyl)propyl]-2,5-dimethylphenol Chemical compound C1=C(O)C(C)=CC(CCC(C=2C(=CC(O)=C(C)C=2)C)C=2C(=CC(O)=C(C)C=2)C)=C1C NTLCYMKRCYMXGE-UHFFFAOYSA-N 0.000 description 1
- VWGFWELEAUUNAT-UHFFFAOYSA-N 4-[3,3-bis(4-hydroxy-3,5-dimethylphenyl)propyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CCC(C=2C=C(C)C(O)=C(C)C=2)C=2C=C(C)C(O)=C(C)C=2)=C1 VWGFWELEAUUNAT-UHFFFAOYSA-N 0.000 description 1
- GRAGBWDYQWZYKP-UHFFFAOYSA-N 4-[3,3-bis(4-hydroxyphenyl)propyl]phenol Chemical compound C1=CC(O)=CC=C1CCC(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 GRAGBWDYQWZYKP-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000156978 Erebia Species 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、エポキシ樹脂組成物に関し、特に、硬化物が
低誘電率を示し、かつ耐熱性と難燃性にすぐれる変性エ
ポキシ樹脂組成物に関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to an epoxy resin composition, and particularly to a modified epoxy resin composition whose cured product exhibits a low dielectric constant and has excellent heat resistance and flame retardancy. Regarding.
〈発明が解決しようとする課題〉
ビスフェノールＡ型エポキシ樹脂もしくはハロゲン含有
ビスフェノールＡ型エポキシ１１４ ｆＦｌに、芳香族
ポリアミン系、アミンアダブト、ジシアンジアミド、酸
無水物系、フェノールノボラック樹脂系等の硬化剤を配
合してなるものが塗料、成形材料、注型材料として用い
られ、また該配合物を溶剤でフェス化し、これを補強用
基材に塗布含浸させ積層板成形用に用いられることは従
来より周知である。<Problem to be solved by the invention> Bisphenol A epoxy resin or halogen-containing bisphenol A epoxy 114 fFl is blended with a curing agent such as an aromatic polyamine type, amine adduct, dicyandiamide, acid anhydride type, or phenol novolac resin type. It has been well known that the mixture can be used as a paint, a molding material, or a casting material, and that the mixture can be made into a face with a solvent, applied and impregnated onto a reinforcing base material, and used for forming laminates. .
ところで近年コンピューター分野では演算速度の向上を
目的に積層板の低誘電率化が要求されている。 これま
ではファインパターン化や高密度化で演算速度向上が図
られてきたが、物理的に限界となり、素材の低誘電率化
が着目されてきた。Incidentally, in recent years in the computer field, there has been a demand for lower dielectric constants of laminates in order to improve calculation speed. Until now, efforts have been made to improve calculation speed by creating finer patterns and increasing density, but this has reached a physical limit, and attention has been focused on lowering the dielectric constant of the material.
一方衛星通信分野で用いられる積層板についても、伝送
ロス低減を目的とした低誘電正接化の要求に加え、適切
なサイズの回路を作成するために、基板となる積層板の
素材の低誘電率化が求められている。On the other hand, regarding the laminates used in the satellite communication field, in addition to the requirement for low dielectric loss tangent for the purpose of reducing transmission loss, the material of the laminate used as the substrate must have a low dielectric constant in order to create a circuit of an appropriate size. ization is required.
このため、積層板の素材にポリエチレン樹脂、弗素樹脂
を用いる試みが種々検討されているが、多くの場合、
（１）成形性が悪くなる
（２）寸法安定性に劣る
（３）銅箔との接着強度が低下する
等の問題点がある。For this reason, various attempts have been made to use polyethylene resins and fluororesins as materials for laminates, but in many cases, they (1) have poor formability, (2) have poor dimensional stability, and (3) are inferior to copper foil. There are problems such as a decrease in adhesive strength.
また、積層板の素材のガラスを石英に変えると誘電率を
下げることができるが、加工成形時、特に穿孔時にドリ
ルの消耗が激しくなるという問題がある。Furthermore, although the dielectric constant can be lowered by changing the glass material of the laminate to quartz, there is a problem in that the drill wears out rapidly during processing and forming, especially during drilling.
このような問題点を解決するために、易成形性等のエポ
キシ樹脂が従来備えている特性を保持し、さらに低誘電
率を示すエポキシ樹脂組成物が望まれている。In order to solve these problems, there is a need for an epoxy resin composition that retains the properties conventionally possessed by epoxy resins, such as easy moldability, and further exhibits a low dielectric constant.
く課題を解決するための手段〉
本発明の目的は、硬化することによって、従来のエポキ
シ樹脂に比して１．低誘電率を示し、かつ耐熱性と難燃
性にすぐれる樹脂組成物を提供しようとするものである
。Means for Solving the Problems> An object of the present invention is to cure the resin to achieve a 1. The object of the present invention is to provide a resin composition that exhibits a low dielectric constant and has excellent heat resistance and flame retardancy.
すなわち、本発明は、（Ａ）下記式［１］で表わされる
トリスフェノール化合物とビスフェノール型エポキシ樹
脂とハロゲン含有エポキシ樹脂との反応生成物、および
、
（式中、
Ｒ′およびＲ２はＨ１メチル基、エチル基、イソプロピ
ル基、ｔｅｒｔ−ブチル基、または２．２−ジメチルブ
チル基であり、少なくとも一方はＨでない、Ｒ３はＨま
たはメチル基、エチル基 Ｒ４およびＲ５はＨまたはメ
チル基、エチル基、イソプロピル基、ｎは、０または１
の数を示す、）
（Ｂ）上記式［１］で表わされるトリスフェノール化合
物を含有する変性エポキシ樹脂組成物を提供する。That is, the present invention provides (A) a reaction product of a trisphenol compound represented by the following formula [1], a bisphenol type epoxy resin, and a halogen-containing epoxy resin; , an ethyl group, an isopropyl group, a tert-butyl group, or a 2,2-dimethylbutyl group, at least one of which is not H, R3 is H or a methyl group, an ethyl group, R4 and R5 are H or a methyl group, an ethyl group, Isopropyl group, n is 0 or 1
) (B) Provides a modified epoxy resin composition containing a trisphenol compound represented by the above formula [1].
ここで、前記（Ｂ）が１．１．３−トリス（２メチル−
４−ヒドロキシ−５−ｔ−プチルフェニル）ブタンであ
る変性エポキシ樹脂組成物が良い。Here, the above (B) is 1.1.3-tris(2methyl-
A modified epoxy resin composition of 4-hydroxy-5-t-butylphenyl)butane is preferred.
また、前記（Ｂ）の水酸基当量（ＢＯ□）に対する前記
（Ａ）のエポキシ当量（ＡＥＥｗ）の比（Ａ ｔｔｗ
／ Ｂ ｏｎ）が、０．７〜１．４０である変性エポキ
シ樹脂組成物が好ましい。Furthermore, the ratio of the epoxy equivalent (AEEw) of (A) to the hydroxyl equivalent (BO□) of (B) (Attw
/Bon) is preferably 0.7 to 1.40.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の樹脂組成物は、成分（Ａ）と成分（Ｂ）を含有
することを特徴とする。The resin composition of the present invention is characterized by containing component (A) and component (B).
底虞二仁と上
成分（Ａ）は、式［１］で表わされるトリスフェノール
化合物と、ビスフェノール型エポキシ樹脂とハロゲン含
有エポキシ樹脂との反応生成物である。The bottom and top components (A) are reaction products of a trisphenol compound represented by formula [1], a bisphenol-type epoxy resin, and a halogen-containing epoxy resin.
成分（Ａ）において使用するビスフェノール型エポキシ
樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビス
フェノールＦ型エポキシ樹脂等のそれ自体公知の各種ビ
スフェノール型エポキシ樹脂が使用される。 例えば１
．１−ビス（４−ヒドロキシアリール）エタンや１−ア
リール−１，１−ビス（４−ヒドロキシアリール）エタ
ン等のビスフェノール類から話導されるビスフェノール
型エポキシ樹脂も使用し得る。 好適には、ビスフェノ
ールＡとエピクロルヒドリンとを反応させて得られるビ
スフェノールＡ型エポキシ樹脂が使用でき、最も好適に
は該ビスフェノールＡ型エポキシ樹脂の内でもエポキシ
当量が５００以下のものが使用される。As the bisphenol epoxy resin used in component (A), various bisphenol epoxy resins known per se such as bisphenol A epoxy resin and bisphenol F epoxy resin are used. For example 1
．． Bisphenol-type epoxy resins derived from bisphenols such as 1-bis(4-hydroxyaryl)ethane and 1-aryl-1,1-bis(4-hydroxyaryl)ethane may also be used. Preferably, a bisphenol A epoxy resin obtained by reacting bisphenol A and epichlorohydrin can be used, and most preferably a bisphenol A epoxy resin having an epoxy equivalent of 500 or less is used.
またハロゲン含有エポキシ樹脂としては、それ自体公知
の各種ハロゲン含有エポキシ樹脂を使用し得るが、好適
には臭素含有ビスフェノールＡ型エポキシ樹脂が使用さ
れる。 中でも、臭素含量が３０乃至５０重量％、特に
４０乃至５０重量％、およびエポキシ当量が３２８（Ｅ
ＥＷ）乃至２０００、特に３２８乃至８００の範囲にあ
るものが好適である。Further, as the halogen-containing epoxy resin, various halogen-containing epoxy resins known per se can be used, but bromine-containing bisphenol A type epoxy resin is preferably used. Among them, the bromine content is 30 to 50% by weight, especially 40 to 50% by weight, and the epoxy equivalent is 328 (E
EW) to 2000, particularly preferably 328 to 800.
最も好適にはテトラブロムビスフェノールＡとエピクロ
ルヒドリンとを反応させて得られる臭素含有ビスフェノ
ールＡ型樹脂であって、下記化学式、
で表わされるもの（エポキシ当量３２８、臭素含量４８
．７％）が使用される。The most preferred is a bromine-containing bisphenol A type resin obtained by reacting tetrabromobisphenol A and epichlorohydrin, which is represented by the following chemical formula (epoxy equivalent: 328, bromine content: 48
．． 7%) is used.
特に耐炎性を重視する用途には、最終組成物中における
ハロゲン（臭素の場合）含有量を１５乃至３０重量％と
する様に組成物を調製する。In particular, for applications where flame resistance is important, the composition is prepared so that the halogen (in the case of bromine) content in the final composition is 15 to 30% by weight.
成分（Ａ）においては、上述したビスフェノール型エポ
キシ樹脂およびハロゲン含有エポキシ樹脂を、下記−数
式［１］で示されるトリスフェノール化合物により変性
する。In component (A), the above-mentioned bisphenol type epoxy resin and halogen-containing epoxy resin are modified with a trisphenol compound represented by the following formula [1].
（式中、
Ｒ１およびＲ２はＨ１メチル基、エチル基、イソプロピ
ル基、ｔｅｒｔ−ブチル基、または２．２−ジメチルブ
チル基であり、少なくとも一方はＨでない、Ｒ３はＨま
たはメチル基、エチル基、Ｒ４およびＲ５はＨまたはメ
チル基、エチル基、イソプロピル基、ｎは、０または１
の数を示す、）
かかる式［１］で表わされるトリスフェノール化合物の
うちでも、基Ｒ４がメチル基であるタイプのものが好適
であり、最も好適には、Ｒ４がメチル基でありかつ基Ｒ
３がＨであるタイプのトリスフェノール化合物が良い。(In the formula, R1 and R2 are H1 methyl group, ethyl group, isopropyl group, tert-butyl group, or 2,2-dimethylbutyl group, at least one is not H, R3 is H or methyl group, ethyl group, R4 and R5 are H or methyl group, ethyl group, isopropyl group, n is 0 or 1
) Among the trisphenol compounds represented by the formula [1], those in which the group R4 is a methyl group are preferred, and most preferably, those in which the group R4 is a methyl group and the group R
Trisphenol compounds of the type where 3 is H are preferred.
基Ｒ４がメチル基であり、かつＲ３がＨであるタイプの
トリスフェノール化合物は、アクロレインを出発原料と
し、これに目的に応じフェノール化合物を付加させるこ
とによって得られる。A trisphenol compound in which the group R4 is a methyl group and R3 is H can be obtained by using acrolein as a starting material and adding a phenol compound thereto depending on the purpose.
また、基Ｒ４およびＲ５がメチル基等のアルキル基であ
るタイプのトリスフェノール化合物は、一般にメタクロ
レイン、クロトンアルデヒド等の脂肪族不飽和アルデヒ
ドあるいはそのアルキル置換アルデヒド類を出発原料と
して目的に応じたフェノール類を付加させることによっ
て得られる。In addition, trisphenol compounds of the type in which the groups R4 and R5 are alkyl groups such as methyl groups are generally prepared using aliphatic unsaturated aldehydes such as methacrolein and crotonaldehyde or their alkyl-substituted aldehydes as starting materials to produce phenols according to the purpose. It is obtained by adding the class.
トリスフェノール化合物としては、具体的にはこれに限
定されるものではないが次に掲げるものが使用される。Although the trisphenol compound is not specifically limited to this, the following can be used.
（ビス（３，５−ジメチル−４−ヒドロキシフェニル）
−４−ヒドロキシフェニル）メタン、（ビス、（３，５
−ジエチル−４−ヒドロキシフェニル）−４−ヒドロキ
シフェニル）メタン、（ビス（２−メチル−４−ヒドロ
キシ−５−ｔ−ブチルフェニル）−４−ヒドロキシフェ
ニル）メタン、（ビス（２−エチル−４−ヒドロキシ−
５−ｔ−ブチルフェニル）−４−ヒドロキシフェニル）
メタン、（ビス（３，５−ジーｔａｒｔ−ブチルー４−
ヒドロキシフェニル）−４−ヒドロキシフェニル）メタ
ン、（ビス（３，５−ジー１ｓｏ−プロピル−４−ヒド
ロキシフェニル）−４−ヒドロキシフェニル）メタン、
１，１．３−トリス（４−ヒドロキシフェニル）プロパ
ン、１，１．３−トリス（３，５−ジメチル−４−ヒド
ロキシフェニル）プロパン、１，１．３−トリス（３，
５−ジエチル−４−ヒドロキシフェニル）プロパン、１
，１．３−トリス（３，５−ジーｉｓ。(bis(3,5-dimethyl-4-hydroxyphenyl)
-4-hydroxyphenyl)methane, (bis, (3,5
-diethyl-4-hydroxyphenyl)-4-hydroxyphenyl)methane, (bis(2-methyl-4-hydroxy-5-t-butylphenyl)-4-hydroxyphenyl)methane, (bis(2-ethyl-4 -Hydroxy-
5-t-butylphenyl)-4-hydroxyphenyl)
Methane, (bis(3,5-di-tart-butyl-4-
hydroxyphenyl)-4-hydroxyphenyl)methane, (bis(3,5-di-1so-propyl-4-hydroxyphenyl)-4-hydroxyphenyl)methane,
1,1.3-tris(4-hydroxyphenyl)propane, 1,1.3-tris(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1.3-tris(3,
5-diethyl-4-hydroxyphenyl)propane, 1
, 1,3-tris (3,5-G is.
−プロピル−４−ヒドロキシフェニル）プロパン、１，
１．３−トリス（３，５−ジー仁ｅｒｔ−ブチルー４−
ヒドロキシフェニル）プロパン、１．１．３−トリス（
２−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルフ
ェニル）プロパン、１．１．３−トリス（２−エチル−
４−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）プロ
パン、１．１．３−）リス（２−メチル−４−ヒドロキ
シ−５−１ｓｏ−プロピルフェニル）プロパン、１，１
．３−）−リス（２−エチル−４−ヒドロキシ−５−１
ｓｏ−プロピルフェニル）プロパン、１，１．３−トリ
ス（２，５−ジメチル−４−ヒドロキシフェニル）プロ
パン、１．１．３−トリス（２，５−ジエチル−４−ヒ
ドロキシフェニル）プロパン等が使用出来る。-propyl-4-hydroxyphenyl)propane, 1,
1.3-tris(3,5-di-ert-butyl-4-
hydroxyphenyl)propane, 1.1.3-tris(
2-Methyl-4-hydroxy-5-tert-butylphenyl)propane, 1.1.3-tris(2-ethyl-
4-hydroxy-5-tert-butylphenyl)propane, 1.1.3-)lis(2-methyl-4-hydroxy-5-1so-propylphenyl)propane, 1,1
．． 3-)-Lis(2-ethyl-4-hydroxy-5-1
so-propylphenyl)propane, 1,1.3-tris(2,5-dimethyl-4-hydroxyphenyl)propane, 1.1.3-tris(2,5-diethyl-4-hydroxyphenyl)propane, etc. Can be used.
なかでもＲ′がメチル基、Ｒ２がｔ−ブチル基、Ｒ３が
Ｈ，Ｒ’がメチル基、Ｒ３がＨである１、１．３−トリ
ス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェ
ニル）ブタンが好ましい。Among them, 1,1,3-tris(2-methyl-4-hydroxy-5-t- butylphenyl)butane is preferred.
成分（Ａ）の反応に供されるトリスフェノール化合物の
量は、前述したビスフェノール型エポキシ樹脂およびハ
ロゲン含有エポキシ樹脂中のエポキシ基１個に対し、該
トリスフェノール化合物のフェノール性水酸基が０．０
２〜０．７個、好ましくは０．０５〜０．６個の割合と
なるようにする。 フェノール化合物をこの範囲とする
ことにより、所望の効果が得られ、また、取扱いに好適
なエポキシ当量範囲とすることができる。The amount of the trisphenol compound subjected to the reaction of component (A) is such that the phenolic hydroxyl group of the trisphenol compound is 0.0 per epoxy group in the above-mentioned bisphenol type epoxy resin and halogen-containing epoxy resin.
The ratio should be 2 to 0.7, preferably 0.05 to 0.6. By controlling the phenol compound within this range, the desired effect can be obtained, and the epoxy equivalent range can be set suitable for handling.
反応は、一般に約１２０〜２００℃の温度で約３〜２０
時開栓度、溶融、攪拌することにより行われる。 この
反応の際、水酸化ナトリウム、炭酸ナトリウムなどの塩
基性触媒、テトラアルキルアンモニウムハライド、アラ
ルキルトリアルキルアンモニウムハライドなどの四級ア
ンモニウム塩触媒、あるいはトリフェニルホスフィン、
エチルトリフェニルホスホニウムハライドなどのリン系
触媒など、エポキシ系とフェノール性水酸基との反応に
通常用いられる触媒を反応に供されるエポキシ樹脂量に
対し、約２０〜２００ｐＰｍ程度使用することが好まし
い。 また、必要に応じて、トルエン、キシレンなどの
芳香族炭化水素類、メチルイソブチルケトンなどのケト
ン類などを溶媒として使用し、反応させることもできる
。The reaction is generally carried out at a temperature of about 120-200°C and a temperature of about 3-20°C.
This is done by opening, melting, and stirring. During this reaction, basic catalysts such as sodium hydroxide and sodium carbonate, quaternary ammonium salt catalysts such as tetraalkylammonium halides and aralkyltrialkylammonium halides, or triphenylphosphine,
It is preferable to use a catalyst normally used for the reaction between an epoxy system and a phenolic hydroxyl group, such as a phosphorus catalyst such as ethyltriphenylphosphonium halide, in an amount of about 20 to 200 pPm based on the amount of epoxy resin to be subjected to the reaction. Further, if necessary, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl isobutyl ketone, etc. can be used as a solvent for the reaction.
反応生成物たるエポキシ樹脂は、エポキシ当量が１９０
乃至１８００．特に２００乃至９００の範囲となる様に
、前記反応条件を適宜選択して製造される。The epoxy resin that is the reaction product has an epoxy equivalent of 190
〜1800. In particular, the reaction conditions are appropriately selected so that the molecular weight is in the range of 200 to 900.
このエポキシ当量が上記範囲よりも低い場合は、トリス
フェノール類の構成割合が小さいために、変性による改
良効果が小となり、大きい場合には樹脂自体の分子量が
高くなる結果として、溶融粘度が高くなり過ぎて作業性
が悪くなる。 この場合、溶剤を用いてフェス化したと
しても、溶液粘度が高く、塗布、塗工工程での作業性は
低下することになる。If this epoxy equivalent is lower than the above range, the improvement effect of modification will be small because the proportion of trisphenols is small, and if it is large, the molecular weight of the resin itself will increase, resulting in a high melt viscosity. Too much will result in poor workability. In this case, even if a solvent is used to form a face, the viscosity of the solution will be high and the workability in the application and coating process will be reduced.
成」Ｌ工Ｕ
成分（Ｂ）は、式［１］で表わされるトリスフェノール
化合物である。Component (B) is a trisphenol compound represented by formula [1].
（式中、
Ｒ１およびＲ２はＨ１メチル基、エチル基、イソプロピ
ル基、ｔｅｒｔ−ブチル基、または２．２−ジメチルブ
チル基であり、少なくとも一方はＨでない Ｒ３はＨま
たはメチル基、エチル基、Ｒ４およびＲ５はＨまたはメ
チル基、エチル基、イソプロピル基、ｎは、０または１
の数を示す、）
成分（Ａ）に対する成分（Ｂ）の割合は、成分（Ｂ）の
水酸基当量（Ｂ ＯＨ）に対する成分（Ａ）のエポキシ
当量（ＡＥ！ｗ）の比（Ａ ｃｉｗ ／ Ｂ ０）Ｉ）
が、０．７〜１．４０、好ましくは、０．８〜１．２５
とするのが良い。(In the formula, R1 and R2 are H1 methyl group, ethyl group, isopropyl group, tert-butyl group, or 2,2-dimethylbutyl group, and at least one is not H. R3 is H or methyl group, ethyl group, R4 and R5 is H or methyl group, ethyl group, isopropyl group, n is 0 or 1
) The ratio of component (B) to component (A) is the ratio of the epoxy equivalent (AE!w) of component (A) to the hydroxyl equivalent (B OH) of component (B) (A ciw / B 0)I)
is 0.7 to 1.40, preferably 0.8 to 1.25
It is better to
この範囲であると、低話電率でかつガラス転移点が高い
硬化物が得られるからである。This is because within this range, a cured product with a low call rate and a high glass transition point can be obtained.
成分（Ａ）と成分（Ｂ）は、それぞれ溶媒中に溶解して
溶液として混合し、組成物とすることもできるが、ベレ
ット状で溶融混練して組成物としてもよい。Component (A) and component (B) may be dissolved in a solvent and mixed as a solution to form a composition, or may be melt-kneaded in a pellet form to form a composition.
本発明の樹脂組成物中に含まれる硬化促進剤としては、
下記のようなイミダゾール、第３級アミンなどが用いら
れる。The curing accelerator contained in the resin composition of the present invention includes:
The following imidazole, tertiary amine, etc. are used.
イミダゾールとしては、具体的には２−メチルイミダゾ
ール、２−エチル−４−メチルイミダゾール、２−フェ
ニルイミダゾール、２−ウンデシルイミダゾール、２−
エチル−４−メチルイミダゾールアジン、１−ベンジル
−２−メチルイミダゾールなどが用いられる。Specific examples of imidazole include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-
Ethyl-4-methylimidazoleazine, 1-benzyl-2-methylimidazole, etc. are used.
また第３級アミンとしては、具体的には、Ｎ、Ｎ−ベン
ジルメチルアミン、２，４．６−トリス（ジメチルアミ
ノメチル）フェノールなどが用いられる。Further, as the tertiary amine, specifically, N,N-benzylmethylamine, 2,4.6-tris(dimethylaminomethyl)phenol, etc. are used.
また硬化促進剤としては、１，８−ジアザビシクロ−（
５，４，Ｏ）ウンデセン−７のオクチル酸塩、（サンア
ボット社 ＵｃａｔＳ １０２）、モノエチルアミン
と三フッ化ボウ素の錯体などを用いることもできる。In addition, as a curing accelerator, 1,8-diazabicyclo-(
Octylate of 5,4,O) undecene-7 (UcatS 102, manufactured by San Abbott), a complex of monoethylamine and boron trifluoride, etc. can also be used.
硬化促進剤の量は成分（Ａ）中のエポキシ樹脂に対し、
１０〜０．０１ｗｔ％好ましくは３〜０．０５％である
。The amount of curing accelerator is based on the epoxy resin in component (A),
It is 10 to 0.01 wt%, preferably 3 to 0.05%.
本発明の樹脂組成物は、その目的を損わない範囲内にお
いて、他のエポキシ化合物、たとえばビスフェノールＡ
型エポキシ化合物、ビスフェノールＦ型エポキシ化合物
、１．１−ビス（グリシドキシフェニル）エタン、フェ
ノールノボラック型エポキシ化合物、０−クレゾール−
ノボラック型エポキシ化合物、グリシジルエステル型エ
ポキシ化合物、グリシジルアミン型エポキシ化合物、脂
環式エポキシ化合物などを含むことができる。The resin composition of the present invention may contain other epoxy compounds, such as bisphenol A, within a range that does not impair its purpose.
type epoxy compound, bisphenol F type epoxy compound, 1.1-bis(glycidoxyphenyl)ethane, phenol novolac type epoxy compound, 0-cresol-
It can include novolac type epoxy compounds, glycidyl ester type epoxy compounds, glycidylamine type epoxy compounds, alicyclic epoxy compounds, and the like.
本組成物は一般にはトルエン、キシレンなどの芳香族炭
化水素類、アセトン、メチルエチルケトン、メチルイソ
ブチルケトンなどの溶剤を用いてワニスの形に調製され
る。 調製された樹脂組成物は、これをガラスクロス、
カーボンファイバー グラスファイバー 紙、石綿、ポ
リエステル繊維、芳香族ポリアミド繊維などの補強用基
材に含浸させこれをプリプレグとしたあとプレスで加熱
加圧して積層板に成形される。The composition is generally prepared in the form of a varnish using an aromatic hydrocarbon such as toluene or xylene, or a solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone. The prepared resin composition is mixed with glass cloth,
Carbon fiber Glass fiber Impregnated into a reinforcing base material such as paper, asbestos, polyester fiber, or aromatic polyamide fiber, this is made into prepreg, which is then heated and pressed in a press to form a laminate.
本発明の樹脂組成物は封止剤として使用することもでき
る。 また、必要に応じて特性を損わない範囲で各種の
充填剤、例えばシリカ、アルミナ、タルク、マイカ、重
炭酸カルシウム、カオリン、ケイソウ土、グラファイト
、ボロン、シリコンカーバイト、カーボンファイバー
ガラスファイバーを配合することができる。The resin composition of the present invention can also be used as a sealant. In addition, various fillers such as silica, alumina, talc, mica, calcium bicarbonate, kaolin, diatomaceous earth, graphite, boron, silicon carbide, and carbon fiber may be added as needed to the extent that the properties are not impaired.
Glass fiber can be blended.
〈実施例〉
以下に実施例を用いて、本発明の組成物を具体的に説明
するが、本発明はこれらに限定されるものではない。<Example> The composition of the present invention will be specifically explained below using Examples, but the present invention is not limited thereto.
（実施例１）
ビスフェノールＡ型エポキシ樹脂（ＥＥＷ１８８）１２
．９ｋｇ、テトラブロムビスフェノールＡ型エポキシ樹
脂（ＥＥＷ３６７）１４．７ｋｇ、１，１．３−トリス
（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニ
ル）ブタン（アデカアーガス製、マークＡＯ３０）４．
９ｋｇ、キシレン３ｆｔを５０１攪拌付反応器に仕込ん
だ。(Example 1) Bisphenol A epoxy resin (EEW188) 12
．． 9 kg, tetrabromobisphenol A type epoxy resin (EEW367) 14.7 kg, 1,1.3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane (manufactured by Adeka Argus, mark AO30)4.
9 kg and 3 ft of xylene were charged into a 501 stirred reactor.
次いで１４０℃に昇温を開始し１３０℃で５３．２％テ
トラメチルアンモニウムクロリド１２．２ｇを加えた。Next, the temperature was started to rise to 140°C, and at 130°C, 12.2 g of 53.2% tetramethylammonium chloride was added.
その後減圧下にキシレン留去を開始し、減圧度を徐々
に高め、１４０℃でフル減圧度（３０ｍｍ）１ｇ以下）
に到達後さらに１時間この状態を保った。After that, xylene distillation was started under reduced pressure, the degree of vacuum was gradually increased, and the degree of vacuum was fully reduced at 140°C (30 mm, 1 g or less).
After reaching , this state was maintained for an additional hour.
減圧を解除後さらに６時間攪拌を続け９０℃に冷却後８
．３ｋｇのメチルエチルケトンを加え均一なエポキシ樹
脂溶液を得た。After releasing the vacuum, continue stirring for another 6 hours and cool to 90°C.
．． 3 kg of methyl ethyl ketone was added to obtain a uniform epoxy resin solution.
上記エポキシ樹脂溶液１００重量部、１゜１．３−トリ
ス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェ
ニル）ブタンのメチルエチルケト２５０％溶液４３重量
部、２−エチル−４−メチルイミダゾール０．１重量部
を混合し、５０℃で攪拌してワニスを調製した。 この
ものの１５０℃におけるゲルタイムは３５８秒であった
。100 parts by weight of the above epoxy resin solution, 43 parts by weight of 250% methyl ethyl keto solution of 1°1.3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 0 parts by weight of 2-ethyl-4-methylimidazole A varnish was prepared by mixing .1 part by weight and stirring at 50°C. The gel time of this product at 150°C was 358 seconds.
このワニスをガラスクロス（日東紡製品ＷＥ−１８にエ
ポキシシラン処理）に含浸させ、１５０℃で５分間加熱
してプリプレグを作製し、これを９プライ重ねて、プレ
ス台に置き、１８０℃無加圧で１〜２分間加熱後、同温
度で接触圧１０ ｋｇｆ／ｃｍ２ｉ時間の条件で加圧
成形し１．６ｍｍの厚みの積層板を得た。A glass cloth (Nittobo product WE-18 treated with epoxy silane) was impregnated with this varnish and heated at 150°C for 5 minutes to produce a prepreg. 9 plies of this were stacked and placed on a press stand and heated to 180°C without any heat treatment. After heating under pressure for 1 to 2 minutes, the mixture was pressure-molded at the same temperature under the conditions of a contact pressure of 10 kgf/cm2i for an hour to obtain a laminate with a thickness of 1.6 mm.
この積層板は、次の特性を示した。This laminate exhibited the following properties.
曲げ強度 （ｋｇ／−■ｆ） ５３．７曲
げ弾性率 （ｋｇ／ａｍ’） ２１６０３５
μ＃４箔接着強度 （ｋｇ／ ｃ■２） １．８煮
沸吸水率（％） ０．１１７ｇ（ＤＳ
Ｃｔ） １５１難燃性（ＵＬ Ｔｅ５ｔ
） Ｖ−０誘電率
６０Ｈｚ ３． ９
１ＫＨｚ ３．８
１ＭＨｚ ３．７
なお測定条件は下記の条件とした。Bending strength (kg/-■f) 53.7 Bending modulus (kg/am') 216035
μ#4 foil adhesive strength (kg/c■2) 1.8 Boiling water absorption rate (%) 0.117g (DS
Ct) 151 flame retardant (UL Te5t
) V-0 dielectric constant 60Hz 3. 9 1KHz 3.8 1MHz 3.7 The measurement conditions were as follows.
積層板の曲げ強度、曲げ弾性率、煮沸吸水率、難燃性、
誘電率、誘電正接はＪ Ｉ Ｓ−に−６９１１に従い、
３５μ銅箔接着強度は、ＪＩＳ−Ｃ−６４８１に従い測
定した。 Ｔｇは示差走査熱量計で測定した。 測定
条件は以下に示した。Bending strength, bending elastic modulus, boiling water absorption rate, flame retardance,
The dielectric constant and dielectric loss tangent are in accordance with JIS-6911.
The 35μ copper foil adhesive strength was measured according to JIS-C-6481. Tg was measured with a differential scanning calorimeter. The measurement conditions are shown below.
機器 ５ＥＩＫＯｉ８Ｅ ＤＩＳＣ’１０．５ｓｃ
７’ｓａ。Equipment 5EIKOi8E DISC'10.5sc
7'sa.
昇温開始温度 ５０℃
昇温速度 ｌＯ℃／ ｍ ｉ ｎサンプル ！
穴パンチで打ち抜いた円盤をアルミパンの本体に入れた
のち
上蓋を用い密封して使用した。Heating start temperature 50℃ Heating rate 10℃/min sample!
A disk punched with a hole punch was placed in the body of an aluminum pan, and the top lid was used to seal the pan.
（実施例２）
実施例１で得られた１５０℃におけるゲルタイム３５８
秒のワニスを、ガラスクロス（鐘紡■、テキストグラス
）に含浸させ１５０℃で５分間加熱し、プリプレグを作
製した。 これを１５ブライ重ねてプレス台に置き、１
８０℃無加圧で１〜２分間加熱後、同温度で接触圧１０
ｋｇｆ／ ｃｍ” １時間の条件で加圧成形し、
１．３ｍｍの厚みの積層板を得た。(Example 2) Gel time 358 at 150°C obtained in Example 1
A prepreg was prepared by impregnating a glass cloth (Kanebo ■, Text Glass) with the second varnish and heating it at 150° C. for 5 minutes. Layer 15 briai of this and place it on the press stand, 1
After heating at 80℃ without pressure for 1 to 2 minutes, the contact pressure was 10℃ at the same temperature.
kgf/cm” pressure molded for 1 hour,
A laminate with a thickness of 1.3 mm was obtained.
この積層板の誘電率および読電正接を実施例１の条件で
測定した。The dielectric constant and reading loss tangent of this laminate were measured under the conditions of Example 1.
（比較例１）
ビスフェノールＡ型エポキシ樹脂（ＥＥＷ１８８）８０
０ｇ、テトラブロムビスフェノールＡ４４０．７ｇ、キ
シレン３００ｍｊ２を３に撹拌付フラスコに仕込んだ。(Comparative Example 1) Bisphenol A epoxy resin (EEW188) 80
0g of tetrabromobisphenol A, 440.7g of tetrabromobisphenol A, and 300mj2 of xylene were charged into a stirring flask.
次いで、１４０℃に昇温を開始し１３０℃で５３．２％
テトラメチルアンモニウムクロリド水溶液４．９ｇを加
えた。 その後減圧下にキシレン留去を開始し、減圧度
を徐々に高め１４０℃でフル減圧度（３０ｍｍＨｇ以下
）に到達後さらに１時間この状態を保った。Next, the temperature was started to increase to 140℃, and at 130℃ it was 53.2%.
4.9 g of an aqueous solution of tetramethylammonium chloride was added. Thereafter, xylene distillation was started under reduced pressure, and the degree of vacuum was gradually increased to reach a full degree of vacuum (30 mmHg or less) at 140° C., and this state was maintained for another 1 hour.
減圧を解除後さらに４時間撹拌を続け９０℃に冷却後３
１０ｇのメチルエチルケトンを加え均一なエポキシ樹脂
溶液を得た。After releasing the vacuum, continue stirring for another 4 hours and cool to 90°C.
10 g of methyl ethyl ketone was added to obtain a uniform epoxy resin solution.
上記エポキシ樹脂溶液１００重量部、ジシアンジアミド
４重量部ベンジルジメチルアミン０．２ｍｍ量部を混合
しワニスを調製した。 このワニスを用い実施例１と同
様にして積層板を得た。A varnish was prepared by mixing 100 parts by weight of the above epoxy resin solution, 4 parts by weight of dicyandiamide, and 0.2 mm part by benzyldimethylamine. A laminate was obtained using this varnish in the same manner as in Example 1.
この積層板は、次の特性を示した。This laminate exhibited the following properties.
Ｔｇ（ＤＳＣ） １３０℃
誘電率 ６０Ｈｚ ５．３
１ にＨｚ ５ 、 ２
１ＭＨｚ ５．０
誕電正接 ６０Ｈｚ ０．６８
１ＫＨｚ ０．６１
１ＭＨｚ １．６６
〈発明の効果〉
本発明の樹脂組成物は、硬化すると、従来のエポキシ樹
脂硬化物に比して、誘電率が低く、かつ耐熱性および難
燃性に優れる。 しかも機械的性質、加工性等の従来の
エポキシ樹脂硬化物のもつ特性を失わない。Tg (DSC) 130°C Dielectric constant 60Hz 5.3 1 to Hz 5, 2 1MHz 5.0 Birth tangent 60Hz 0.68 1KHz 0.61 1MHz 1.66 <Effects of the invention> The resin composition of the present invention has the following properties: When cured, it has a lower dielectric constant and excellent heat resistance and flame retardancy than conventional cured epoxy resins. Furthermore, the properties of conventional cured epoxy resins, such as mechanical properties and workability, are not lost.
手続ネ甫正書（自発）Procedure Nefu Seisho (self-motivated)
Claims (3)
ル化合物とビスフェノール型エポキシ樹脂とハロゲン含
有エポキシ樹脂との反応生成物、および、 ▲数式、化学式、表等があります▼…［１］ （式中、 Ｒ＾１およびＲ＾２はＨ、メチル基、エチル基、イソプ
ロピル基、ｔｅｒｔ−ブチル基、または２，２−ジメチ
ルブチル基であり、少なくとも一方はＨでない、Ｒ＾３
はＨまたはメチル基、エチル基、Ｒ＾４およびＲ＾５は
Ｈまたはメチル基、エチル基、イソプロピル基、ｎは、
０または１の数を示す。） （Ｂ）上記式［１］で表わされるトリスフェノール化合
物を含有することを特徴とする変性エポキシ樹脂組成物
。(1) (A) A reaction product of a trisphenol compound represented by the following formula [1], a bisphenol type epoxy resin, and a halogen-containing epoxy resin, and ▲Mathematical formulas, chemical formulas, tables, etc.▼... [1] ( In the formula, R^1 and R^2 are H, methyl group, ethyl group, isopropyl group, tert-butyl group, or 2,2-dimethylbutyl group, and at least one is not H, R^3
is H or methyl group, ethyl group, R^4 and R^5 are H or methyl group, ethyl group, isopropyl group, n is,
Indicates the number 0 or 1. ) (B) A modified epoxy resin composition characterized by containing a trisphenol compound represented by the above formula [1].
−ヒドロキシ−５−ｔ−ブチルフェニル）ブタンである
請求項１記載の変性エポキシ樹脂組成物。(2) The above (B) is 1,1,3-tris(2methyl-4
The modified epoxy resin composition according to claim 1, which is -hydroxy-5-t-butylphenyl)butane.
前記（Ａ）のエポキシ当量（Ａ＿Ｅ＿Ｅ＿Ｗ）の比（Ａ
＿Ｅ＿Ｅ＿Ｗ／Ｂ＿Ｏ＿Ｈ）が、０．７〜１．４０であ
る請求項１または２に記載の変性エポキシ樹脂組成物。(3) Ratio (A
The modified epoxy resin composition according to claim 1 or 2, wherein _E_E_W/B_O_H) is 0.7 to 1.40.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33383989A JPH03192112A (en) | 1989-12-22 | 1989-12-22 | Modified epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33383989A JPH03192112A (en) | 1989-12-22 | 1989-12-22 | Modified epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03192112A true JPH03192112A (en) | 1991-08-22 |
Family
ID=18270520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33383989A Pending JPH03192112A (en) | 1989-12-22 | 1989-12-22 | Modified epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03192112A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0590463A2 (en) * | 1992-09-22 | 1994-04-06 | Sumitomo Chemical Company, Limited | Halogen containing epoxy resin composition and copper-clad laminate |
| EP0660398A1 (en) * | 1993-12-21 | 1995-06-28 | Shell Internationale Researchmaatschappij B.V. | Flame-retardant epoxy resin composition for semiconductor encapsulation |
| JPH08325355A (en) * | 1995-03-30 | 1996-12-10 | Mitsui Petrochem Ind Ltd | Epoxy resin composition for laminate board having high heat resistance and low dielectric constant |
-
1989
- 1989-12-22 JP JP33383989A patent/JPH03192112A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0590463A2 (en) * | 1992-09-22 | 1994-04-06 | Sumitomo Chemical Company, Limited | Halogen containing epoxy resin composition and copper-clad laminate |
| EP0590463A3 (en) * | 1992-09-22 | 1994-10-19 | Sumitomo Chemical Co | Halogen containing epoxy resin composition and copper-clad laminate. |
| EP0660398A1 (en) * | 1993-12-21 | 1995-06-28 | Shell Internationale Researchmaatschappij B.V. | Flame-retardant epoxy resin composition for semiconductor encapsulation |
| JPH08325355A (en) * | 1995-03-30 | 1996-12-10 | Mitsui Petrochem Ind Ltd | Epoxy resin composition for laminate board having high heat resistance and low dielectric constant |
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