JP4682548B2 - Thermosetting resin composition and cured product thereof - Google Patents
Thermosetting resin composition and cured product thereof Download PDFInfo
- Publication number
- JP4682548B2 JP4682548B2 JP2004200464A JP2004200464A JP4682548B2 JP 4682548 B2 JP4682548 B2 JP 4682548B2 JP 2004200464 A JP2004200464 A JP 2004200464A JP 2004200464 A JP2004200464 A JP 2004200464A JP 4682548 B2 JP4682548 B2 JP 4682548B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- thermosetting resin
- composition according
- ether
- phenol
- 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.)
- Expired - Lifetime
Links
- 239000011342 resin composition Substances 0.000 title claims description 69
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 42
- 239000003822 epoxy resin Substances 0.000 claims description 75
- 229920000647 polyepoxide Polymers 0.000 claims description 75
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 42
- 229920005989 resin Polymers 0.000 claims description 41
- 239000011347 resin Substances 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 33
- -1 alkylene glycol alkyl ether Chemical class 0.000 claims description 31
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 27
- 150000002989 phenols Chemical class 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000005011 phenolic resin Substances 0.000 claims description 23
- TUZVMPXGFZSNBG-UHFFFAOYSA-N 3-aminopyrrole-2,5-dione Chemical compound NC1=CC(=O)NC1=O TUZVMPXGFZSNBG-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 10
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- 239000003566 sealing material Substances 0.000 claims description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- 238000005227 gel permeation chromatography Methods 0.000 claims description 6
- 239000011810 insulating material Substances 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 6
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 5
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 5
- YNSSPVZNXLACMW-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)-3-ethyl-5-methylphenyl]methyl]-2-ethyl-6-methylphenyl]pyrrole-2,5-dione Chemical compound C=1C(C)=C(N2C(C=CC2=O)=O)C(CC)=CC=1CC(C=C1CC)=CC(C)=C1N1C(=O)C=CC1=O YNSSPVZNXLACMW-UHFFFAOYSA-N 0.000 claims description 4
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 3
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 3
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 3
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims description 3
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 claims description 3
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 3
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- IKFPAKYBSYICFK-UHFFFAOYSA-N 1-[4-(4-propylphenoxy)phenyl]pyrrole-2,5-dione Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 IKFPAKYBSYICFK-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 31
- 239000000047 product Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 150000001299 aldehydes Chemical class 0.000 description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 16
- 229920003986 novolac Polymers 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000001723 curing Methods 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 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 9
- 239000003054 catalyst Substances 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 239000002966 varnish Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 239000004744 fabric Substances 0.000 description 7
- 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 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 5
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- 239000004760 aramid Substances 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000008393 encapsulating agent Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical class C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229960001755 resorcinol Drugs 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 description 3
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002366 halogen compounds Chemical class 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical class NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 2
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 2
- GSKNLOOGBYYDHV-UHFFFAOYSA-N 2-methylphenol;naphthalen-1-ol Chemical compound CC1=CC=CC=C1O.C1=CC=C2C(O)=CC=CC2=C1 GSKNLOOGBYYDHV-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
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- MPWGZBWDLMDIHO-UHFFFAOYSA-N 3-propylphenol Chemical compound CCCC1=CC=CC(O)=C1 MPWGZBWDLMDIHO-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000012796 inorganic flame retardant Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- VSWALKINGSNVAR-UHFFFAOYSA-N naphthalen-1-ol;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C(O)=CC=CC2=C1 VSWALKINGSNVAR-UHFFFAOYSA-N 0.000 description 2
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 2
- OENHRRVNRZBNNS-UHFFFAOYSA-N naphthalene-1,8-diol Chemical compound C1=CC(O)=C2C(O)=CC=CC2=C1 OENHRRVNRZBNNS-UHFFFAOYSA-N 0.000 description 2
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
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- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
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- 150000002013 dioxins Chemical class 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 230000008030 elimination Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- 230000005012 migration Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- HKRCIEPDCARTAM-UHFFFAOYSA-N naphthalene-1,2-diol naphthalene-1,3-diol Chemical compound OC1=CC(=CC2=CC=CC=C12)O.OC1=C(C=CC2=CC=CC=C12)O HKRCIEPDCARTAM-UHFFFAOYSA-N 0.000 description 1
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 0.000 description 1
- ZUVBIBLYOCVYJU-UHFFFAOYSA-N naphthalene-1,7-diol Chemical compound C1=CC=C(O)C2=CC(O)=CC=C21 ZUVBIBLYOCVYJU-UHFFFAOYSA-N 0.000 description 1
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent 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
- 239000006072 paste Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
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- 238000007790 scraping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical class OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-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
- QLORRTLBSJTMSN-UHFFFAOYSA-N tris(2,6-dimethylphenyl) phosphate Chemical compound CC1=CC=CC(C)=C1OP(=O)(OC=1C(=CC=CC=1C)C)OC1=C(C)C=CC=C1C QLORRTLBSJTMSN-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- 150000003739 xylenols Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Formation Of Insulating Films (AREA)
- Conductive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Description
本発明は、得られる硬化物の耐熱性、耐湿性、誘電特性（低誘電率、低誘電正接）に優れ、プリント基板用樹脂組成物、電子部品の封止材用樹脂組成物、レジストインキ、導電ペースト、塗料、接着剤、複合材料等に好適に用いることができ、さらにハロゲン系の難燃剤を使用しなくても難燃性に優れる硬化物を得る事が出来る環境対応型の熱硬化性樹脂組成物、及びその硬化物に関する。 The present invention is excellent in heat resistance, moisture resistance and dielectric properties (low dielectric constant, low dielectric loss tangent) of the cured product obtained, a resin composition for printed circuit boards, a resin composition for encapsulants for electronic components, resist ink, Environment-friendly thermosetting that can be used suitably for conductive pastes, paints, adhesives, composite materials, etc., and can obtain cured products with excellent flame resistance without using halogen-based flame retardants. The present invention relates to a resin composition and a cured product thereof.
従来、厳しい耐熱性、耐湿性、誘電特性（低誘電率、低誘電正接）を要求される高耐熱プリント配線基板分野ではポリイミド系樹脂が使用されてきた。しかしながら、このポリイミド系樹脂は溶剤溶解性に乏しいため、溶剤を使用しワニス化するためには化審法指定化学物質であるＮ，Ｎ−ジメチルホルムアミドや、沸点が２００℃以上あるために硬化物の物性を低下させる溶剤残留が問題となるＮ−メチルピロリドン等を使用しなければならないため、極めて作業性が悪く、耐湿性、難燃性等の要求特性に悪影響を与えていた。 Conventionally, polyimide-based resins have been used in the field of high heat-resistant printed wiring boards that require severe heat resistance, moisture resistance, and dielectric properties (low dielectric constant, low dielectric loss tangent). However, since this polyimide resin is poor in solvent solubility, N, N-dimethylformamide, which is a chemical substance designated by the Chemical Substances Control Law, and a cured product because it has a boiling point of 200 ° C. or higher in order to use a solvent to form a varnish Since N-methylpyrrolidone or the like, which has a problem of residual solvent that lowers the physical properties of the resin, has to be used, the workability is extremely poor and the required properties such as moisture resistance and flame retardancy are adversely affected.
一方、エポキシ樹脂は、耐熱性、密着性、電気絶縁性等に優れた硬化物が得られることから、半導体封止材、プリント配線基板、塗料、注型材料用途等に好適に用いられているが、技術革新に伴う耐熱性、耐湿性、難燃性、低誘電率、低熱膨張等の高い要求レベルに対して、充分に対応できなくなってきている。 On the other hand, epoxy resins are suitably used for semiconductor sealing materials, printed wiring boards, paints, casting materials, and the like because cured products having excellent heat resistance, adhesion, electrical insulation, and the like are obtained. However, it has become impossible to sufficiently cope with high demand levels such as heat resistance, moisture resistance, flame retardancy, low dielectric constant and low thermal expansion associated with technological innovation.
また、近年の環境問題への取り組みの中で、ダイオキシン発生が懸念されるハロゲン系の難燃剤を用いた難燃化方法を改めて、新たにハロゲンフリー系の難燃化方法の開発が強く要求されている。 In addition, in recent efforts to address environmental issues, there is a strong demand for the development of new halogen-free flame retardant methods by renewing flame retardant methods that use halogen-based flame retardants, which are feared to generate dioxins. ing.
上記の問題を解決する手段として、特定条件下でビスイミド化合物とジアミン化合物とを特定溶媒中でプレポリマー化し、溶剤溶解性を上げる技術方法が提案されている（例えば、特許文献１参照。）が、硬化物の物性を使用できるレベルまで向上させるためにエポキシ樹脂で変性し、ビスイミド化合物とエポキシ樹脂の共通の硬化剤としてジシアンジアミドなど硬化剤として用いている。一般にエポキシ樹脂の硬化剤としてジシアンジアミドを使用する場合には、得られる硬化物の耐湿性、誘電特性等において、エポキシ樹脂をフェノール系ノボラック樹脂で硬化させて得られる硬化物より劣るため、上記要求特性を満たすことが困難である。 As a means for solving the above problem, a technical method has been proposed in which a bisimide compound and a diamine compound are prepolymerized in a specific solvent under specific conditions to increase the solvent solubility (see, for example, Patent Document 1). In order to improve the physical properties of the cured product to a usable level, it is modified with an epoxy resin and used as a curing agent such as dicyandiamide as a common curing agent for the bisimide compound and the epoxy resin. In general, when dicyandiamide is used as a curing agent for an epoxy resin, the above required characteristics are inferior to the cured product obtained by curing the epoxy resin with a phenolic novolac resin in terms of moisture resistance and dielectric properties of the resulting cured product. It is difficult to satisfy.
本発明はかかる状況に鑑みてなされたものであり、Ｎ，Ｎ−ジメチルホルムアミドや、Ｎ−メチルピロリドン等の溶剤を使用しなくても溶剤溶解性に優れ、ワニスの安全性・作業性が良好であり、且つ得られる硬化物の耐熱性、難燃性、耐湿性、誘電特性等に優れ、封止材、積層板等の電気電子材料用、成形材料用等に好適に用いる事が出来る熱硬化性樹脂組成物及びその硬化物を提供することを目的とする。 The present invention has been made in view of such circumstances, and has excellent solvent solubility without using a solvent such as N, N-dimethylformamide or N-methylpyrrolidone, and has good varnish safety and workability. The cured product obtained is excellent in heat resistance, flame retardancy, moisture resistance, dielectric properties, etc., and can be used suitably for electrical and electronic materials such as sealing materials and laminates, and molding materials. It aims at providing curable resin composition and its hardened | cured material.
本発明者等は、上記課題を解決する為に鋭意検討したところ、トリアジン環を有するフェノール樹脂組成物とマレイミド化合物とから得られるフェノール性アミノマレイミドプレポリマー樹脂（Ａ）とアルキレングリコールアルキルエーテル（Ｂ）とを含有することを特徴とする熱硬化性樹脂組成物は溶剤溶解性に優れ、得られる硬化物の耐熱性、難燃性、耐湿性、誘電特性等に優れることを見出し、本発明を完成させた。 The inventors of the present invention diligently studied to solve the above problems, and as a result, a phenolic aminomaleimide prepolymer resin (A) obtained from a phenol resin composition having a triazine ring and a maleimide compound and an alkylene glycol alkyl ether (B And the thermosetting resin composition characterized in that it is excellent in solvent solubility and heat resistance, flame retardancy, moisture resistance, dielectric properties, etc. of the resulting cured product. Completed.
即ち、本発明は、トリアジン環を有するフェノール樹脂組成物（ａ１）と、Ｎ，Ｎ’−（４，４−ジフェニルメタン）ビスマレイミド、ビス（３−エチル−５−メチル−４−マレイミドフェニル）メタン及び２，２−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパンからなる群から選ばれる１種以上のマレイミド化合物（ａ２）とから得られるフェノール性アミノマレイミドプレポリマー樹脂（Ａ）と、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノｎ−プロピルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル及びジプロピレングリコールモノメチルエーテルから成る群から選択されるアルキレングリコールアルキルエーテル（Ｂ）と、エポキシ樹脂（Ｃ）とを含有することを特徴とする熱硬化性樹脂組成物、及びこれを用いて得られる硬化物を提供するものである。 That is, the present invention relates to a phenol resin composition (a1) having a triazine ring , N, N ′-(4,4-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane. And a phenolic aminomaleimide prepolymer resin (A) obtained from one or more maleimide compounds (a2) selected from the group consisting of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane , and ethylene Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, diethylene glycol A thermosetting resin comprising an alkylene glycol alkyl ether (B) selected from the group consisting of monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether and dipropylene glycol monomethyl ether, and an epoxy resin (C) A composition and a cured product obtained by using the composition are provided.
本発明の熱硬化性樹脂組成物は、溶剤溶解性に優れるため、化審法指定化学物質であるＮ，Ｎ−ジメチルホルムアミドや、沸点が２００℃以上あるために硬化物中への溶剤残留が問題となるＮ−メチルピロリドン等の溶剤を使用する必要が無いため、ワニスの安全性や硬化した後の物性に優れる。また、実用レベルの成形性、硬化性を有し、一般のフェノール樹脂組成物やエポキシ樹脂組成物等よりも一層優れた耐熱性、耐湿性、誘電特性、難燃性をその硬化物に付与できる。特にエポキシ樹脂の硬化剤としてジシアンジアミドを用いた際に起こりやすいマイグレーションも、本発明の熱硬化性樹脂組成物を用いて得られる硬化物が耐湿性に優れることから、その抑止効果も有する。このため、本発明の熱硬化性樹脂組成物はプリント基板用樹脂組成物、電子部品用封止材用樹脂組成物、レジストインキ、導電ペースト等の電子材料分野に用いた場合は、高密度実装化や、高周波対応化、高速演算化などに対応する樹脂組成物としてきわめて有用である。また、得られる該成形硬化物は耐熱性、密着性等においても上記用途における要求を満たすものであり、高信頼性が必要な分野にも対応できるものである。 Since the thermosetting resin composition of the present invention is excellent in solvent solubility, N, N-dimethylformamide, which is a chemical substance designated by the Chemical Substances Control Law, and a solvent residue in the cured product because the boiling point is 200 ° C. or higher. Since there is no need to use a problematic solvent such as N-methylpyrrolidone, the safety of the varnish and the physical properties after curing are excellent. In addition, it has a practical level of moldability and curability, and can impart heat resistance, moisture resistance, dielectric properties, and flame retardancy superior to those of general phenol resin compositions and epoxy resin compositions to the cured product. . In particular, migration that is likely to occur when dicyandiamide is used as a curing agent for an epoxy resin has a deterrent effect because the cured product obtained using the thermosetting resin composition of the present invention has excellent moisture resistance. Therefore, when the thermosetting resin composition of the present invention is used in the field of electronic materials such as a resin composition for printed circuit boards, a resin composition for encapsulants for electronic parts, resist inks, conductive pastes, etc. It is extremely useful as a resin composition that is compatible with high-frequency, high-frequency compatibility, and high-speed computation. In addition, the obtained molded cured product satisfies the requirements for the above-mentioned uses in terms of heat resistance, adhesion, and the like, and can also cope with fields requiring high reliability.
以下、本発明を詳細に説明する。
本発明で用いるトリアジン環を有するフェノール樹脂組成物（ａ１）としては、その製造方法として特に限定されるものではないが、例えば、フェノール類（ｘ１）とトリアジン環を有する化合物（ｘ２）とアルデヒド類（ｘ３）とを縮合反応させることによって得る事が出来、フェノール類（ｘ１）とトリアジン環を有する化合物（ｘ２）とアルデヒド類（ｘ３）との縮合物との他に、フェノール類（ｘ１）とアルデヒド類（ｘ３）との縮合物、トリアジン環を有する化合物（ｘ２）とアルデヒド類（ｘ３）との縮合物、未反応のフェノール類（ｘ１）、未反応のトリアジン環を有する化合物（ｘ３）等を含む混合物であっても良い。
Hereinafter, the present invention will be described in detail.
The phenol resin composition (a1) having a triazine ring used in the present invention is not particularly limited as a production method thereof. For example, a phenol (x1), a compound (x2) having a triazine ring, and an aldehyde (X3) can be obtained by condensation reaction, and in addition to the condensation product of phenols (x1), a compound (x2) having a triazine ring and aldehydes (x3), phenols (x1) and Condensates with aldehydes (x3), compounds (x2) having triazine rings and aldehydes (x3), unreacted phenols (x1), compounds having unreacted triazine rings (x3), etc. It may be a mixture containing
トリアジン環を有するフェノール樹脂組成物（ａ１）としては、成型時の揮発分発生を抑え、均一な硬化物を得ることができる点から、フェノール類（ｘ１）とトリアジン環を有する化合物（ｘ２）とアルデヒド類（ｘ３）との縮合物を含有し、該縮合物中に未反応アルデヒド類を含まず、且つメチロール基を含まない樹脂組成物である事が好ましい。 As the phenol resin composition (a1) having a triazine ring, phenols (x1) and a compound (x2) having a triazine ring can be obtained from suppressing generation of volatile components during molding and obtaining a uniform cured product. The resin composition preferably contains a condensate with aldehydes (x3), does not contain unreacted aldehydes, and does not contain a methylol group.
また前記トリアジン環を有するフェノール樹脂組成物（ａ１）中に残存する一官能性フェノール類の含有率としては、該フェノール樹脂組成物（ａ１）中で３重量％以下であることが好ましい。一官能性フェノール類を３重量％以下にすることにより、得られる硬化物の耐熱性、耐湿性が良くなるという効果がある。ここでいう一官能性フェノール類とは、１分子中にエポキシ基と反応し得るフェノール性の水酸基を１つだけ含む化合物を意味する。 The content of monofunctional phenols remaining in the phenol resin composition (a1) having a triazine ring is preferably 3% by weight or less in the phenol resin composition (a1). By making monofunctional phenols into 3 weight% or less, there exists an effect that the heat resistance of the hardened | cured material obtained and moisture resistance improve. The monofunctional phenol here means a compound containing only one phenolic hydroxyl group capable of reacting with an epoxy group in one molecule.
前記フェノール類（ｘ１）としては、特に限定されるものではなく、例えば、フェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、ｏ−エチルフェノール、ｍ−エチルフェノール、ｐ−エチルフェノール、ｏ−イソプロピルフェノール、ｍ−プロピルフェノール、ｐ−プロピルフェノール、ｐ−ｓｅｃ−ブチルフェノール、ｐ−ｔｅｒｔ−ブチルフェノール、ｐ−シクロヘキシルフェノール、ｐ−クロロフェノール、ｏ−ブロモフェノール、ｍ−ブロモフェノール、ｐ−ブロモフェノール等のフェノール類、α−ナフトール、β−ナフトール等のナフトール類、２，４−キシレノール、２，５−キシレノール、２，６−キシレノール等のキシレノール類等の一価フェノール類；レゾルシン、カテコール、ハイドロキノン、２，２−ビス（４’−ヒドロキシフェニル）プロパン、１，１’−ビス（ジヒドロキシフェニル）メタン、１，１’−ビス（ジヒドロキシナフチル）メタン、テトラメチルビフェノール、ビフェノール、ヘキサメチルビフェノール、１，２−ジヒドロキシナフタレン、１，３−ジヒドロキシナフタレン、１，４−ジヒドロキシナフタレン、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、１，７−ジヒドロキシナフタレン、１，８−ジヒドロキシナフタレン、２，３−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレン等のナフタレンジオール類等の二価フェノール類；トリスヒドロキシフェニルメタン等の三価フェノール類を挙げることができる。特にフェノール、ｏ−クレゾール、ｍ−クレゾール、ナフトール類、２，２−ビス（４’−ヒドロキシフェニル）プロパン、２，６−キシレノール、レゾルシン、ハイドロキノン、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレン等が経済性及び製造の容易さの点から好ましい。またこれらのフェノール類は、その使用にあたって１種類のみに限定されるものではなく、２種以上の併用も可能である。 The phenols (x1) are not particularly limited, and examples thereof include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o- Isopropylphenol, m-propylphenol, p-propylphenol, p-sec-butylphenol, p-tert-butylphenol, p-cyclohexylphenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, etc. Phenols, naphthols such as α-naphthol and β-naphthol, monohydric phenols such as xylenols such as 2,4-xylenol, 2,5-xylenol and 2,6-xylenol; resorcin, catechol, hydroquinone, 2,2- Bis (4′-hydroxyphenyl) propane, 1,1′-bis (dihydroxyphenyl) methane, 1,1′-bis (dihydroxynaphthyl) methane, tetramethylbiphenol, biphenol, hexamethylbiphenol, 1,2-dihydroxynaphthalene 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, Examples thereof include dihydric phenols such as naphthalenediols such as 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene; and trihydric phenols such as trishydroxyphenylmethane. Especially phenol, o-cresol, m-cresol, naphthols, 2,2-bis (4′-hydroxyphenyl) propane, 2,6-xylenol, resorcin, hydroquinone, 1,5-dihydroxynaphthalene, 1,6-dihydroxy Naphthalene, 2,7-dihydroxynaphthalene and the like are preferable from the viewpoints of economy and ease of production. In addition, these phenols are not limited to one type, and two or more types can be used in combination.
前記トリアジン環を有する化合物（ｘ２）としては、特に限定されるものではないが、下記一般式（１） The compound (x2) having a triazine ring is not particularly limited, but the following general formula (1)
で表わされる化合物であることが好ましい。
It is preferable that it is a compound represented by these.
前記一般式（１）で表わされる化合物としては、具体的にはメラミン、あるいはアセトグアナミン、ベンゾグアナミンなどのグアナミン誘導体、シアヌル酸、あるいはメチルシアヌレート、エチルシアヌレート、アセチルシアヌレート、塩化シアヌルなどのシアヌル酸誘導体等が挙げられる。これらの中でも、Ｒ１、Ｒ２、Ｒ３のうちのいずれか２つ又は３つがアミノ基であるメラミン、アセトグアナミン、ベンゾグアナミンなどのグアナミン誘導体がより好ましい。特に得られる熱硬化性樹脂組成物の成形性、硬化性に優れる点から、メラミンを用いる事が好ましい。 Specific examples of the compound represented by the general formula (1) include melamine, guanamine derivatives such as acetoguanamine and benzoguanamine, cyanuric acid, cyanuric acid such as methyl cyanurate, ethyl cyanurate, acetyl cyanurate, and cyanuric chloride. Examples include acid derivatives. Among these, guanamine derivatives such as melamine, acetoguanamine, and benzoguanamine in which any two or three of R 1 , R 2 , and R 3 are amino groups are more preferable. In particular, melamine is preferably used from the viewpoint of excellent moldability and curability of the resulting thermosetting resin composition.
前記トリアジン環を有する化合物（ｘ２）の使用にあたっては、１種類のみに限定されるものではなく、２種以上を併用することも可能である。 The use of the compound (x2) having a triazine ring is not limited to one type, and two or more types can be used in combination.
前記アルデヒド類（ｘ３）としては、１分子中に１個以上のアルデヒド基をもつ化合物であれば特に限定されるものではなく、例示するならば、ホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、クロトンアルデヒドなどが挙げられ、これらの中でもホルムアルデヒドが得られる熱硬化性樹脂組成物の流動性や硬化性、硬化物の耐熱性に優れる点から好ましい。 The aldehyde (x3) is not particularly limited as long as it is a compound having one or more aldehyde groups in one molecule. Examples thereof include formaldehyde, acetaldehyde, benzaldehyde, crotonaldehyde and the like. Among these, the thermosetting resin composition from which formaldehyde is obtained is preferable from the viewpoint of excellent fluidity and curability and heat resistance of the cured product.
以下に本発明で用いるトリアジン環を有するフェノール樹脂組成物（ａ１）を得るための方法について説明する。まず、前記したフェノール類（ｘ１）とトリアジン環を有する化合物（ｘ２）とアルデヒド類（ｘ３）とを無触媒あるいは触媒存在下で反応させる。この時、系のｐＨは特に限定されるものではないが、ｐＨ３．０〜９．０の範囲であることが好ましい。また、各原料の反応順序も特に制限はなく、フェノール類（ｘ１）、アルデヒド類（ｘ３）をまず反応させてからトリアジン環を有する化合物（ｘ２）を加えても、逆にトリアジン環を有する化合物（ｘ２）とアルデヒド類（ｘ３）とを反応させてからフェノール類（ｘ１）を加えても、同時に全ての原料を加えて反応させても良い。この時、フェノール類（ｘ１）に対するアルデヒド類（ｘ３）のモル比は特に限定されるものではないが、好ましくはアルデヒド類（ｘ３）／フェノール類（ｘ１）＝０．１〜１．１であり、より好ましくは前記比として０．２〜０．８である。 Below, the method for obtaining the phenol resin composition (a1) which has a triazine ring used by this invention is demonstrated. First, the phenols (x1), the compound (x2) having a triazine ring and the aldehydes (x3) are reacted in the absence of a catalyst or in the presence of a catalyst. At this time, the pH of the system is not particularly limited, but is preferably in the range of pH 3.0 to 9.0. In addition, the reaction order of each raw material is not particularly limited, and the compound having a triazine ring is reversed even if the compound (x2) having a triazine ring is added after the phenols (x1) and aldehydes (x3) are first reacted. Phenols (x1) may be added after reacting (x2) and aldehydes (x3), or all raw materials may be added and reacted at the same time. At this time, the molar ratio of the aldehydes (x3) to the phenols (x1) is not particularly limited, but is preferably aldehydes (x3) / phenols (x1) = 0.1 to 1.1. More preferably, the ratio is 0.2 to 0.8.
またフェノール類（ｘ１）に対するトリアジン環を有する化合物（ｘ２）とのモル比としては、反応系が均一であって、かつ反応物も均一になる点、及び得られる硬化物の架橋密度が適当であり、硬化物物性に優れる点から、トリアジン環を有する化合物（ｘ２）／フェノール類（ｘ１）＝０．０５〜１．５０である事が好ましく、特に好ましくは前記比として０．１０〜０．５０である。 The molar ratio of the compound (x2) having a triazine ring to the phenols (x1) is appropriate in that the reaction system is uniform and the reaction product is uniform, and the crosslinking density of the resulting cured product is appropriate. In view of excellent physical properties of the cured product, the compound having a triazine ring (x2) / phenols (x1) is preferably 0.05 to 1.50, and particularly preferably the ratio is 0.10 to 0.00. 50.
また触媒を使用する場合、触媒種は特に限定されるものではないが、塩基性触媒としては、例えば水酸化ナトリウム、水酸化カリウム、水酸化バリウム等のアルカリ金属およびアルカリ土類金属の水酸化物、およびこれらの酸化物、アンモニア、１〜３級アミン類、ヘキサメチレンテトラミン、炭酸ナトリウム等が挙げられ、酸触媒としては、例えば塩酸、硫酸、スルホン酸等の無機酸、シュウ酸、酢酸等の有機酸、ルイス酸、あるいは酢酸亜鉛などの２価金属塩等が挙げられる。 When a catalyst is used, the type of catalyst is not particularly limited. Examples of the basic catalyst include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide and barium hydroxide. And oxides thereof, ammonia, primary to tertiary amines, hexamethylenetetramine, sodium carbonate, and the like. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and sulfonic acid, oxalic acid, and acetic acid. Examples thereof include divalent metal salts such as organic acids, Lewis acids, and zinc acetate.
本発明の熱硬化性樹脂組成物を電気電子材料用の樹脂として使用する場合には、金属などの無機物が触媒残として残ることは好ましくないことから、塩基性の触媒としてはアミン類、酸性の触媒としては有機酸を使用するのが好ましいが、無触媒系は更に好ましい。 When the thermosetting resin composition of the present invention is used as a resin for electrical and electronic materials, it is not preferable that an inorganic substance such as a metal remains as a catalyst residue. An organic acid is preferably used as the catalyst, but a non-catalytic system is more preferable.
また反応制御の面から反応を各種溶媒の存在下で行ってもよい。必要に応じて中和、水洗して塩類などの不純物の除去を行っても良いが、無触媒あるいは触媒にアミン類を使用した場合は行わなくても良い。 Further, from the viewpoint of reaction control, the reaction may be performed in the presence of various solvents. If necessary, the impurities such as salts may be removed by neutralization and washing with water, but this is not necessary when no amine is used in the catalyst or the catalyst.
反応終了後、未反応のアルデヒド類（ｘ３）、フェノール類（ｘ１）、溶媒等を常圧蒸留、真空蒸留等の常法にしたがって除去する。この時、メチロール基を実質的に含まない樹脂組成物を得るためには１２０℃以上の加熱処理を行うことが好ましい。また１２０℃以上の温度であれば充分時間をかけることによりメチロール基を消滅させることができるが、効率的に消滅させるにはより高い温度、好ましくは１５０℃以上の加熱処理を行うことが好ましい。この時高温においてはノボラック樹脂を得るときの常法にしたがい、加熱とともに蒸留することが好ましい。またこの時前記したように一官能性フェノール類を３重量％以下にすることが好ましい。 After completion of the reaction, unreacted aldehydes (x3), phenols (x1), solvent and the like are removed according to a conventional method such as atmospheric distillation or vacuum distillation. At this time, in order to obtain a resin composition substantially free of methylol groups, it is preferable to perform a heat treatment at 120 ° C. or higher. Further, if the temperature is 120 ° C. or higher, the methylol group can be extinguished by taking a sufficient time, but it is preferable to perform heat treatment at a higher temperature, preferably 150 ° C. or higher, for efficient elimination. At this time, it is preferable to distill together with heating according to a conventional method for obtaining a novolac resin at a high temperature. At this time, as described above, the monofunctional phenols are preferably 3% by weight or less.
トリアジン環を有するフェノール樹脂組成物（ａ１）としては、異なる原料を用いて同様にして得られた複数種の組成物を混合して以下の反応に供しても良い。 As the phenol resin composition (a1) having a triazine ring, plural kinds of compositions obtained in the same manner using different raw materials may be mixed and subjected to the following reaction.
本発明で用いるマレイミド化合物（ａ２）としては、Ｎ，Ｎ’−（４，４−ジフェニルメタン）ビスマレイミド、ビス（３−エチル−５−メチル−４−マレイミドフェニル）メタン、２，２−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパンを使用することが得られる硬化物の耐熱性に優れ、かつ、工業的供給安定性、汎用性などから特に好ましい。 As the maleimide compound (a2) used in the present invention , N, N ′-(4,4-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, 2,2-bis [ Use of 4- (4-maleimidophenoxy) phenyl] propane is particularly preferable from the viewpoint of excellent heat resistance of the cured product, industrial supply stability, versatility, and the like.
本発明で用いるフェノール性アミノマレイミドプレポリマー樹脂（Ａ）の製造方法としては特に限定されるものではないが、前記トリアジン環を有するフェノール樹脂組成物（ａ１）と前記マレイミド化合物（ａ２）とを反応溶媒中において８０℃〜１５０℃、好ましくは１００℃〜１４０℃の温度範囲で加熱反応して得る方法を挙げる事が出来る。このとき、前記フェノール樹脂組成物（Ａ）と前記マレイミド化合物（Ｂ）との重量比［（ａ１）／（ａ２）］が１／３〜３／１である事が、得られる硬化物の難燃性が良好である点から好ましく、特に前記比が１／２．５〜２．５／１の範囲である事が好ましい。また、反応温度としては前記トリアジン環を有するフェノール樹脂組成物（ａ１）と前記マレイミド化合物（ａ２）とのマイケル付加反応が速やかに進行し、経済的である点から８０℃以上であることが好ましく、反応制御しやすい点から１５０℃以下である事が好ましいものである。 Although it does not specifically limit as a manufacturing method of the phenolic amino maleimide prepolymer resin (A) used by this invention, The phenol resin composition (a1) which has the said triazine ring, and the said maleimide compound (a2) are made to react. Examples thereof include a method obtained by heating reaction in a temperature range of 80 ° C. to 150 ° C., preferably 100 ° C. to 140 ° C. in a solvent. At this time, it is difficult for the resulting cured product that the weight ratio [(a1) / (a2)] of the phenol resin composition (A) and the maleimide compound (B) is 1/3 to 3/1. It is preferable from the viewpoint of good flammability, and it is particularly preferable that the ratio is in the range of 1 / 2.5 to 2.5 / 1. The reaction temperature is preferably 80 ° C. or higher from the viewpoint that the Michael addition reaction of the phenol resin composition (a1) having a triazine ring and the maleimide compound (a2) proceeds rapidly and is economical. The temperature is preferably 150 ° C. or lower from the viewpoint of easy reaction control.
このとき反応溶媒としては後述するアルキレングリコールアルキルエーテル（Ｂ）を用いる事が好ましい。アルキレングリコールアルキルエーテル（Ｂ）は、フェノール性アミノマレイミドプレポリマー樹脂（Ａ）を容易に溶解する事が可能であると共に、加熱硬化時に高温としなくても揮発成分としてワニスから除去する事ができ、硬化物に残留溶媒として悪影響を及ぼす事が無い。このため反応溶媒として用いると、反応後に系から取り出す必要がなく、製造工程も簡略化されることになる。 At this time, it is preferable to use an alkylene glycol alkyl ether (B) described later as a reaction solvent. The alkylene glycol alkyl ether (B) can easily dissolve the phenolic aminomaleimide prepolymer resin (A) and can be removed from the varnish as a volatile component even if it is not heated to high temperature. There is no adverse effect on the cured product as a residual solvent. Therefore, when used as a reaction solvent, it is not necessary to remove from the system after the reaction, and the manufacturing process is simplified.
更に、フェノール性アミノマレイミドプレポリマー樹脂（Ａ）のゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定される重量平均分子量としては、未反応のマレイミド化合物（ａ２）含有量が少なく、かつ、高分子量体含有量も少ないため溶剤溶解性に優れる点から１，０００〜６，０００、好ましくは１，５００〜４，５００である。 Furthermore, as a weight average molecular weight measured by gel permeation chromatography (GPC) of the phenolic aminomaleimide prepolymer resin (A), the content of unreacted maleimide compound (a2) is small and high molecular weight is contained. Since the amount is small, it is 1,000 to 6,000, preferably 1,500 to 4,500 from the viewpoint of excellent solvent solubility.
反応後のフェノール性アミノマレイミドプレポリマー樹脂（Ａ）を含有するワニスの粘度調整用として用いても良い溶剤としては、例えば、メタノール、エタノール、イソプロピルアルコール等のアルコール性溶媒、トルエン、キシレン等の芳香族炭化水素性溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、ジメチルホルムアミド等の非アルコール性極性溶媒等の沸点１６０℃以下の溶剤が挙げられる。 Examples of the solvent that may be used for adjusting the viscosity of the varnish containing the phenolic aminomaleimide prepolymer resin (A) after the reaction include alcoholic solvents such as methanol, ethanol and isopropyl alcohol, and aromatics such as toluene and xylene. And a solvent having a boiling point of 160 ° C. or lower, such as a non-alcoholic polar solvent such as an aromatic hydrocarbon solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and dimethylformamide.
本発明で用いるアルキレングリコールアルキルエーテル（Ｂ）としては、特に限定されるものではないが、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノｎ−プロピルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノメチルエーテル等が挙げられる。これらは単独、あるいは２種以上を併用して用いても良い。前述のように、アルキレングリコールアルキルエーテルは、前記フェノール樹脂組成物（ａ１）と前記マレイミド化合物（ａ２）との反応時に用いても良いし、反応後にワニスの粘度調節用として用いても良く、この時、反応時に用いたものと、粘度調節用に用いるものが同一であっても、異なっていても良く、熱硬化性樹脂組成物として用いる際の用途・加熱硬化条件等に応じて適宜選択して用いる事が好ましい。 The alkylene glycol alkyl ether (B) used in the present invention is not particularly limited. For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, Examples include propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, and dipropylene glycol monomethyl ether. These may be used alone or in combination of two or more. As described above, the alkylene glycol alkyl ether may be used during the reaction of the phenol resin composition (a1) and the maleimide compound (a2), or may be used for adjusting the viscosity of the varnish after the reaction. At this time, the one used for the reaction and the one used for viscosity adjustment may be the same or different, and are appropriately selected according to the use, heat curing conditions, etc. when used as a thermosetting resin composition. Are preferably used.
本発明の熱硬化性樹脂組成物には、得られる硬化物の難燃性、耐熱性、耐湿性等の性能を更に付与するために、必要に応じてエポキシ樹脂（Ｃ）を併用する事が出来る。併用しうるエポキシ樹脂（Ｃ）としては、種々のエポキシ樹脂を用いることができるが、例示するならば、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、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、レゾルシン型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、カテコール型エポキシ樹脂、ジヒドロキシナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂等の２価のフェノール類から誘導されるエポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、ジシクロペンタジエン−フェノール変性型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂型エポキシ樹脂、ビフェニル変性ノボラック型エポキシ樹脂等の３価以上のフェノール類から誘導されるエポキシ樹脂、リン原子を構造中に含有する各種変性エポキシ樹脂などが挙げられるがこれらに限定されるものではない。またこれらのエポキシ樹脂は単独で用いてもよく、２種以上を混合してもよい。 The thermosetting resin composition of the present invention may be used in combination with an epoxy resin (C) as necessary in order to further impart performances such as flame retardancy, heat resistance and moisture resistance of the resulting cured product. I can do it. As the epoxy resin (C) that can be used in combination, various epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin , Epoxy resin derived from divalent phenols such as resorcinol type epoxy resin, hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type Epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol modified epoxy resin, phenol alla Kill type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified Examples include, but are not limited to, epoxy resins derived from trihydric or higher phenols such as phenol resin epoxy resins, biphenyl modified novolak epoxy resins, and various modified epoxy resins containing phosphorus atoms in the structure. is not. Moreover, these epoxy resins may be used independently and may mix 2 or more types.
これらの中でも、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、ビスフェノールＳ型エポキシ樹脂、カテコール型エポキシ樹脂、ジヒドロキシナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、ジシクロペンタジエン−フェノール変性型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂、ビフェニル変性ノボラック型エポキシ樹脂を用いることが好ましく、難燃性を向上させるためにはビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ジヒドロキシナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂等の２官能性エポキシ樹脂あるいは、リン原子を構造中に含有する各種変性エポキシ樹脂を用いることが好ましく、耐熱性を向上させるためには、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂等の多官能性エポキシ樹脂を用いることが特に好ましい。 Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin , Cresol novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol modified epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol Aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolak It is preferable to use an epoxy resin or a biphenyl-modified novolac type epoxy resin. In order to improve flame retardancy, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type It is preferable to use a bifunctional epoxy resin such as an epoxy resin or a tetramethylbiphenyl type epoxy resin, or various modified epoxy resins containing phosphorus atoms in the structure. In order to improve the heat resistance, a phenol novolac type epoxy resin It is particularly preferable to use a polyfunctional epoxy resin such as a cresol novolac epoxy resin, a triphenylmethane epoxy resin, a tetraphenylethane epoxy resin, or a naphthol novolac epoxy resin.
さらに硬化促進剤を適宜使用することもでき、その硬化促進剤としては、例えば、リン系化合物、第３級アミン、イミダゾール、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられ、これらは単独のみならず２種以上の併用も可能である。 Further, a curing accelerator can be used as appropriate, and examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. In addition, two or more types can be used in combination.
本発明の熱硬化性樹脂組成物には必要に応じて、無機充填剤、改質剤として使用される熱硬化性および熱可塑性樹脂、難燃付与剤、顔料、シランカップリング剤、離型剤等の種々の配合剤を添加することができる。 If necessary, the thermosetting resin composition of the present invention is an inorganic filler, a thermosetting and thermoplastic resin used as a modifier, a flame retardant, a pigment, a silane coupling agent, a release agent. Various compounding agents such as can be added.
前記無機質充填材としては、例えば、溶融シリカ、結晶シリカ、アルミナ、窒化珪素、水酸化アルミ等が挙げられる。無機充填材の配合量を特に大きくする場合は溶融シリカを用いるのが一般的である。溶融シリカは破砕状、球状のいずれでも使用可能であるが、溶融シリカの配合量を高め且つ成形材料の溶融粘度の上昇を抑制するためには、球状のものを主に用いる方が好ましい。更に球状シリカの配合量を高めるためには、球状シリカの粒度分布を適当に調整することが好ましい。その充填率は適用用途や所望特性によって、望ましい範囲が異なるが、例えば半導体封止材用途に使用する場合は、線膨張係数や難燃性を鑑みれば高い方が好ましく、組成物全体量に対して６５重量％以上が好ましく、特に好ましくは８５重量％以上である。また導電ペーストや導電フィルムなどの用途に使用する場合は、銀粉や銅粉等の導電性充填剤を用いることができる。 Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. In order to increase the blending amount of the inorganic filler, it is common to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The desired range varies depending on the application and desired properties, but for example, when used in semiconductor encapsulant applications, it is preferably higher in view of the coefficient of linear expansion and flame retardancy. It is preferably 65% by weight or more, particularly preferably 85% by weight or more. Moreover, when using for uses, such as an electrically conductive paste and an electrically conductive film, electroconductive fillers, such as silver powder and copper powder, can be used.
前記改質剤として使用される熱硬化性および熱可塑性樹脂としては種々のものが全て使用できるが、例えばフェノキシ樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリエーテルイミド樹脂、ポリエーテルサルホン樹脂、ポリフェニレンエーテル樹脂、ポリフェニレンスルフィド樹脂、ポリエステル樹脂、ポリスチレン樹脂、ポリエチレンテレフタレート樹脂などが例示できる。 Various thermosetting and thermoplastic resins can be used as the modifier. For example, phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene ether resin. And polyphenylene sulfide resin, polyester resin, polystyrene resin, polyethylene terephthalate resin and the like.
前記難燃付与剤としては種々のものが全て使用できるが、例えば、ハロゲン化合物、燐原子含有化合物や窒素原子含有化合物や無機系難燃化合物などが挙げられる。それらの具体例を挙げるならばテトラブロモビスフェノールＡ型エポキシ樹脂やブロム化フェノールノボラック型エポキシ樹脂などのハロゲン化合物、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリ−２−エチルヘキシルホスフェート、トリブトキシエチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、キシレニルジフェニルホスフェート、２−エチルヘキシルジフェニルホスフェート、トリス（２，６−ジメチルフェニル）ホスフェート、レゾルシンジフェニルホスフェートなどのリン酸エステル、ポリリン酸アンモニウム、ポリリン酸アミド、赤リン、リン酸グアニジン、ジアルキルヒドロキシメチルホスホネートなどの縮合リン酸エステル化合物などの燐原子含有化合物、メラミンなどの窒素原子含有化合物、水酸化アルミニウム、水酸化マグネシウム、硼酸亜鉛、硼酸カルシウムなどの無機系難燃化合物が例示できる。このなかで、ハロゲン化合物は、ハロゲン含有難燃剤及びアンチモン化合物を使用しない地球環境にやさしい新規の難燃化方法の開発要求とは合致しないことを付記する。 Various flame retardants can be used as the flame retardant, and examples thereof include halogen compounds, phosphorus atom-containing compounds, nitrogen atom-containing compounds, and inorganic flame retardant compounds. Specific examples thereof include halogen compounds such as tetrabromobisphenol A type epoxy resin and brominated phenol novolac type epoxy resin, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, tri Phosphate esters such as phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2,6-dimethylphenyl) phosphate, resorcin diphenyl phosphate, Ammonium polyphosphate, polyphosphate amide, red phosphorus, guanidine phosphate, dialkylhydroxymethylphosphine Phosphorus atom-containing compounds such as condensed phosphoric acid ester compounds such as sulfonates, nitrogen atom-containing compound such as melamine, aluminum hydroxide, magnesium hydroxide, zinc borate, inorganic flame retardant compounds such as calcium borate may be exemplified. Among these, it is added that the halogen compound does not meet the development requirements of a new flame retardant method friendly to the global environment that does not use halogen-containing flame retardants and antimony compounds.
本発明の熱硬化性樹脂組成物の使用用途としては、特に制限されるものではなく、例えば、プリント基板用、電子部品の封止材用、導電ペースト、樹脂注型材料、接着剤、絶縁塗料等のコーティング材料等が挙げられ、これらの中でも、得られる硬化物の誘電特性に優れる点から、プリント基板用樹脂組成物、電子部品の封止材用樹脂組成物、導電ペーストに好適に用いることができ、耐湿性に優れる点から接着剤に好適に用いることができ、更に高機能性である点から複合材料に好適に用いることができる。 The use of the thermosetting resin composition of the present invention is not particularly limited, and for example, for printed circuit boards, electronic component sealing materials, conductive pastes, resin casting materials, adhesives, and insulating paints. Among these, among these, it is suitable for use as a resin composition for printed circuit boards, a resin composition for encapsulants for electronic parts, and a conductive paste because of the excellent dielectric properties of the resulting cured product. It can be suitably used for an adhesive because it has excellent moisture resistance, and can be suitably used for a composite material because of its high functionality.
前記プリント基板用としては、特にプリプレグ用、銅張り積層板用、ビルドアッププリント基板の層間絶縁材料用に好適に用いることができる。 As the printed circuit board, it can be suitably used particularly for prepregs, copper-clad laminates, and interlayer insulation materials for build-up printed circuit boards.
本発明の熱硬化性樹脂組成物をプリント基板用プリプレグ用樹脂組成物とするには、有機溶剤を用いてワニス化することでプリプレグ用樹脂組成物とすることが好ましい。前記有機溶剤としては、前記アルキレングリコールアルキルエーテル（Ｂ）は勿論のこと、その他の溶剤としては、例えば、メタノール、エタノール、イソプロピルアルコール、メチルセロソルブ、エチルセロソルブ等のアルコール性溶媒、トルエン、キシレン等の芳香族炭化水素性溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、ジメチルホルムアミド等の非アルコール性極性溶媒等沸点１６０℃以下の溶剤が挙げられ、適宜に２種または、それ以上の混合溶剤として使用することができる。得られた該ワニスを、紙、ガラス布、ガラス不織布、アラミド紙、アラミド布、ガラスマット、ガラスロービング布などの各種補強基材に含浸し、用いた溶剤種に応じた加熱温度、好ましくは５０〜１７０℃で加熱することによって、硬化物であるプリプレグを得ることができる。この時用いる樹脂組成物と補強基材の重量割合としては、特に限定されないが、通常、プリプレグ中の樹脂分が２０〜６０重量％となるように調整することが好ましい。 In order to make the thermosetting resin composition of the present invention into a resin composition for a prepreg for a printed circuit board, it is preferable to form a resin composition for a prepreg by varnishing using an organic solvent. Examples of the organic solvent include the alkylene glycol alkyl ether (B), and other solvents include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, and ethyl cellosolve, toluene, xylene, and the like. Non-alcoholic polar solvents such as aromatic hydrocarbon solvents, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, and the like. Solvents with a boiling point of 160 ° C. or lower are used, and two or more mixed solvents are used as appropriate can do. The obtained varnish is impregnated into various reinforcing substrates such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth, and the heating temperature according to the solvent type used, preferably 50 By heating at ˜170 ° C., a prepreg that is a cured product can be obtained. The weight ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is adjusted to 20 to 60% by weight.
本発明の熱硬化性樹脂組成物から銅張り積層板用樹脂組成物を得るには、上記プリプレグ用樹脂組成物とする方法と同じであり、得られたプリプレグを、例えば特開平７−４１５４３号公報に記載されているように積層し、適宜銅箔を重ねて、１〜１０ＭＰａの加圧下に１７０〜２５０℃で１０分〜３時間、加熱圧着させることにより、銅張り積層板を得ることができる。 In order to obtain a resin composition for a copper-clad laminate from the thermosetting resin composition of the present invention, it is the same as the above method for preparing a resin composition for a prepreg, and the obtained prepreg is, for example, JP-A-7-41543. It is possible to obtain a copper-clad laminate by laminating as described in the official gazette, stacking copper foils as appropriate, and thermocompression bonding at 170 to 250 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa. it can.
本発明の熱硬化性樹脂組成物からビルドアップ基板用層間絶縁材料を得る方法としては特に限定されないが、例えば特公平４−６１１６号公報、特開平７−３０４９３１号公報、特開平８−６４９６０号公報、特開平９−７１７６２号公報、特開平９−２９８３６９号公報などに記載の各種方法を採用できる。より具体的には、ゴム、フィラーなどを適宜配合した当該樹脂組成物を、回路を形成した配線基板にスプレーコーティング法、カーテンコーティング法等を用いて塗布した後、硬化させる。その後、必要に応じて所定のスルーホール部等の穴あけを行った後、粗化剤により処理し、その表面を湯洗することによって、凹凸を形成させ、銅などの金属をめっき処理する。前記めっき方法としては、無電解めっき、電解めっき処理が好ましく、また前記粗化剤としては酸化剤、アルカリ、有機溶剤等が挙げられる。このような操作を所望に応じて順次繰り返し、樹脂絶縁層及び所定の回路パターンの導体層を交互にビルドアップして形成することにより、ビルドアップ基盤を得ることができる。但し、スルーホール部の穴あけは、最外層の樹脂絶縁層の形成後に行う。また、銅箔上で当該樹脂組成物を半硬化させた樹脂付き銅箔を、回路を形成した配線基板上に、１７０〜２５０℃で加熱圧着することで、粗化面を形成、メッキ処理の工程を省き、ビルドアップ基板を作製することも可能である。 A method for obtaining an interlayer insulating material for a build-up substrate from the thermosetting resin composition of the present invention is not particularly limited. For example, JP-B-4-6116, JP-A-7-304931, JP-A-8-64960 Various methods described in Japanese Patent Laid-Open No. 9-71762, Japanese Patent Laid-Open No. 9-298369, and the like can be employed. More specifically, the resin composition appropriately blended with rubber, filler, and the like is applied to a wiring board on which a circuit is formed using a spray coating method, a curtain coating method, or the like, and then cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.
前記電子部品の封止材用としては、半導体チップのテープ状封止材用、ポッティング型液状封止剤、アンダーフィル用樹脂、半導体の層間絶縁膜用に好適に用いることができる。 As a sealing material for the electronic component, it can be suitably used for a tape-shaped sealing material for a semiconductor chip, a potting type liquid sealing agent, an underfill resin, and a semiconductor interlayer insulating film.
本発明の熱硬化性樹脂組成物を半導体封止材料用に調整するためには、前記フェノール性アミノマレイミドプレポリマー樹脂（Ａ）、アルキレングリコールアルキルエーテル（Ｂ）、エポキシ樹脂（Ｃ）、その他のカップリング剤、離型剤などの添加剤や無機充填材などを予備混合した後、押出機、ニ−ダ、ロ−ル等を用いて均一になるまで充分に混合する手法が挙げられる。テープ状封止剤として使用する場合には、前述の手法によって得られた樹脂組成物を加熱して半硬化シートを作製し、封止剤テープとした後、この封止剤テープを半導体チップ上に置き、１００〜１５０℃に加熱して軟化させ成形し、１７０〜２５０℃で完全に硬化させる方法を挙げることができる。 In order to prepare the thermosetting resin composition of the present invention for a semiconductor sealing material, the phenolic aminomaleimide prepolymer resin (A), alkylene glycol alkyl ether (B) , epoxy resin (C), other An example is a method in which an additive such as a coupling agent and a release agent and an inorganic filler are premixed and then sufficiently mixed until uniform using an extruder, kneader, roll or the like. When used as a tape-like sealant, the resin composition obtained by the above-described method is heated to produce a semi-cured sheet, which is used as a sealant tape, and then this sealant tape is applied to a semiconductor chip. And a method of softening by heating to 100 to 150 ° C. and completely curing at 170 to 250 ° C. can be mentioned.
更にポッティング型液状封止剤として使用する場合には、前述の手法によって得られた樹脂組成物を必要に応じて溶剤に溶解した後、半導体チップや電子部品上に塗布し、直接、硬化させればよい。 Further, when used as a potting type liquid sealant, the resin composition obtained by the above-mentioned method is dissolved in a solvent as necessary, and then applied onto a semiconductor chip or an electronic component and directly cured. That's fine.
本発明の熱硬化性樹脂組成物をアンダーフィル用樹脂として使用する方法についても特に限定されないが、予め基板ないし半導体素子上に本発明の熱硬化性樹脂組成物を半硬化させてから、加熱して半導体素子と基板を密着させ、完全硬化させるコンプレッションフロー法等が挙げられる。 The method of using the thermosetting resin composition of the present invention as an underfill resin is not particularly limited. However, the thermosetting resin composition of the present invention is semi-cured on a substrate or a semiconductor element in advance and then heated. A compression flow method in which the semiconductor element and the substrate are brought into close contact with each other and completely cured.
本発明の熱硬化性樹脂組成物を半導体の層間絶縁材料として使用する場合は、例えば特開平６−８５０９１号公報の記載の方法が採用できる。層間絶縁膜に用いる場合は半導体に直接することになるため、高温環境下において線膨張率の差によるクラックが生じないよう、絶縁材の線膨張率を半導体の線膨張率に近づけることが要求される。また、半導体の微細化、多層化、高密度化による信号遅延の問題に対応するため、絶縁材の低容量化技術が求められており、絶縁材を低誘電化することによってこの問題を解決することができる。当該樹脂組成物は、これらの要求を満たす特性を有するため好ましい。 When the thermosetting resin composition of the present invention is used as a semiconductor interlayer insulating material, for example, a method described in JP-A-6-85091 can be employed. When used for an interlayer insulating film, it is directly applied to the semiconductor, so it is required that the linear expansion coefficient of the insulating material be close to that of the semiconductor so that cracks due to the difference in linear expansion coefficient do not occur in a high temperature environment. The In addition, in order to deal with the problem of signal delay due to miniaturization, multilayering, and high density of semiconductors, there is a demand for technology for reducing the capacity of insulating materials, and this problem can be solved by reducing the dielectric of insulating materials. be able to. The resin composition is preferable because it has characteristics satisfying these requirements.
本発明の熱硬化性樹脂組成物を導電ペーストとして使用する場合には、例えば、特開平３−４６７０７号公報に記載の微細導電性粒子を該樹脂組成物中に分散させ異方性導電膜用組成物とする方法、特開昭６２−４０１８３号公報、特開昭６２−７６２１５号公報、特開昭６２−１７６１３９号公報などに開示されているような室温で液状である回路接続用ペースト樹脂組成物や異方性導電接着剤とする方法が挙げられる。 When the thermosetting resin composition of the present invention is used as a conductive paste, for example, fine conductive particles described in JP-A-3-46707 are dispersed in the resin composition for use in an anisotropic conductive film. A paste resin for circuit connection which is liquid at room temperature as disclosed in a method for forming a composition, such as JP 62-40183, JP 62-76215, JP 62-176139, etc. Examples thereof include a method of using a composition or an anisotropic conductive adhesive.
本発明の熱硬化性樹脂組成物を接着剤用樹脂組成物として使用する場合には、例えば前記フェノール性アミノマレイミドプレポリマー樹脂（Ａ）、アルキレングリコールアルキルエーテル（Ｂ）、必要に応じて配合されるエポキシ樹脂（Ｃ）、硬化促進剤、溶剤、添加剤等を室温または加熱下で混合ミキサー等を用いて均一に混合することによって得ることができ、各種の基材に塗布した後、室温又は加熱下に放置することによって基材の接着を行うことができる。 When the thermosetting resin composition of the present invention is used as a resin composition for an adhesive, for example, the phenolic aminomaleimide prepolymer resin (A), alkylene glycol alkyl ether (B), and blended as necessary. Epoxy resin (C), curing accelerator, solvent, additive, etc. can be obtained by uniformly mixing with a mixing mixer or the like at room temperature or under heating. The substrate can be adhered by leaving it to stand under heating.
本発明の熱硬化性樹脂組成物から複合材料を得るには、用途に応じた粘度に調製するために有機溶剤を用いてワニス化し、該当ワニスを補強基材に含浸し、加熱してプリプレグを得た後、それを繊維の方向を少しずつ変えて、擬似的に等方性を持たせるように積層し、その後加熱することにより硬化成形する方法が挙げられる。前記有機溶剤としては、例えば、前記アルキレングリコールアルキルエーテル（Ｂ）、メタノール、エタノール、イソプロピルアルコール、メチルセロソルブ、エチルセロソルブ等のアルコール性溶媒、トルエン、キシレン等の芳香族炭化水素性溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、ジメチルホルムアミド等の非アルコール性極性溶媒等沸点１６０℃以下の溶剤が挙げられ、適宜に２種または、それ以上の混合溶剤として使用することができる。加熱温度としては、用いる溶剤の種類を考慮して決定され、好ましくは５０〜１５０℃とされる。補強基材の種類は特に限定されず、例えば炭素繊維、ポリエステル繊維、ポリアミド繊維、アルミナ繊維、紙、ガラス布、ガラス不織布、アラミド紙、アラミド布、ガラスマット、ガラスロービング布などが挙げられる。樹脂分と補強基材の割合も特に限定されないが、通常、プリプレグ中の樹脂分が２０〜６０重量％となるように調整するのが好ましい。 In order to obtain a composite material from the thermosetting resin composition of the present invention, it is varnished with an organic solvent in order to adjust the viscosity according to the use, the varnish is impregnated into a reinforcing substrate, and heated to heat the prepreg. There is a method in which, after being obtained, the direction of the fiber is changed little by little, the layers are laminated so as to have pseudo-isotropic properties, and then heated to be cured and molded. Examples of the organic solvent include alcoholic solvents such as the alkylene glycol alkyl ether (B), methanol, ethanol, isopropyl alcohol, methyl cellosolve, and ethyl cellosolve, aromatic hydrocarbon solvents such as toluene and xylene, acetone, and methyl ethyl ketone. Non-alcoholic polar solvents such as methyl isobutyl ketone, cyclohexanone, dimethylformamide and the like, and solvents having a boiling point of 160 ° C. or lower can be used, and two or more mixed solvents can be used as appropriate. The heating temperature is determined in consideration of the type of solvent used, and is preferably 50 to 150 ° C. The type of the reinforcing substrate is not particularly limited, and examples thereof include carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. The ratio of the resin component and the reinforcing substrate is not particularly limited, but it is usually preferable that the resin component in the prepreg is adjusted to 20 to 60% by weight.
本発明の硬化物は、前述の本発明の熱硬化性樹脂組成物を成形硬化させて得られるものであり、積層物、注型物、接着剤、塗膜、フィルム等として使用できる。その硬化方法としては特に制限されるものではなく、例えば、フェノール性アミノマレイミドプレポリマー樹脂（Ａ）、アルキレングリコールアルキルエーテル（Ｂ）、エポキシ樹脂（Ｃ）、その他の樹脂、各種配合剤等を均一に混合した後、室温または８０〜２００℃で加熱硬化する方法を挙げることができる。また、前述の各種用途に応じて調製された熱硬化性樹脂組成物は、適応する用途に応じた硬化方法を適宜採用することが好ましい。 The cured product of the present invention is obtained by molding and curing the above-described thermosetting resin composition of the present invention, and can be used as a laminate, a cast product, an adhesive, a coating film, a film, and the like. The curing method is not particularly limited, and for example, phenolic aminomaleimide prepolymer resin (A), alkylene glycol alkyl ether (B) , epoxy resin (C), other resins, various compounding agents, etc. And a method of heat curing at room temperature or 80 to 200 ° C. Moreover, it is preferable to employ | adopt suitably the hardening method according to the use to which the thermosetting resin composition prepared according to the above-mentioned various uses.
次に本発明を合成例、実施例、比較例により具体的に説明するが、以下において「部」「％」は特に断わりのない限り重量基準である。 Next, the present invention will be specifically described with reference to synthesis examples, examples and comparative examples. In the following, “parts” and “%” are based on weight unless otherwise specified.
以下の合成例、合成比較例で得られたフェノール樹脂組成物（ａ１）のメチロール基の存在の有無、および一官能性フェノール類は次のように求めた。 Presence / absence of methylol groups in the phenol resin compositions (a1) obtained in the following synthesis examples and synthesis comparative examples, and monofunctional phenols were determined as follows.
＜メチロール基の存在の有無＞
１３Ｃ−ＮＭＲを用いて樹脂組成物中に存在するメチロール基を測定した。
装置：日本電子株式会社製 ＧＳＸ２７０プロトン：２７０ＭＨｚ、測定溶媒：重メタノールあるいは重アセトン、重ジメチルスルホキシド、基準物質：テトラメチルシラン。得られたチャートの６０〜７０ｐｐｍに現れ、ノイズと明確に区別され得るピークを用いて判定した。ピークが認められた場合を「有」、認められない場合を「無」とした。
<Presence or absence of methylol group>
The methylol group present in the resin composition was measured using 13 C-NMR.
Apparatus: GSX270 proton made by JEOL Ltd .: 270 MHz, measurement solvent: heavy methanol or heavy acetone, heavy dimethyl sulfoxide, reference material: tetramethylsilane. Judgment was made using a peak appearing at 60 to 70 ppm of the obtained chart and clearly distinguishable from noise. The case where a peak was observed was “present”, and the case where a peak was not observed was “not present”.
＜一官能性フェノール類量＞
カラム：３０％セライト５４５カルナバワックス２ｍ×３ｍｍφ、カラム温度：１７０℃、注入口温度：２３０℃、検出器：ＦＩＤ、キャリアガス：Ｎ２ガス １．０ｋｇ／ｃｍ２、測定法：内部標準法の測定条件において、フェノール樹脂組成物（ａ１）中の一官能性フェノール量を測定した。
<Amount of monofunctional phenols>
Column: 30% Celite 545 carnauba wax 2 m × 3 mmφ, column temperature: 170 ° C., inlet temperature: 230 ° C., detector: FID, carrier gas: N 2 gas 1.0 kg / cm 2 , measurement method: internal standard method Under the measurement conditions, the amount of monofunctional phenol in the phenol resin composition (a1) was measured.
＜重量平均分子量＞
装置：東ソー株式会社製 ＨＬＣ−８２２０、カラム：ＴＳＫ−ＧＥＬ Ｇ４０００ＨＸＬ１本、Ｇ３０００ＨＸＬ １本、Ｇ２０００ＨＸＬ ２本 ＨＬＣ−８２２０、キャリア溶媒：ＴＨＦ、測定温度：４０℃、測定流速：１ｍＬ／ｍｉｎ、検出器：ＲＩ、測定濃度：０．５ｗｔ％（樹脂分）
<Weight average molecular weight>
Apparatus: HLC-8220 manufactured by Tosoh Corporation, column: TSK-GEL G4000HXL 1, G3000HXL 1, G2000HXL 2 HLC-8220, carrier solvent: THF, measurement temperature: 40 ° C., measurement flow rate: 1 mL / min, detector: RI, measured concentration: 0.5 wt% (resin content)
合成例１
コンデンサーと常圧および減圧蒸留装置とを備えた反応器に、フェノール９４部、メラミン１８．８部、および４１．５％ホルマリン３６．１部を仕込み、１００℃に昇温して２時間リフラックス反応させた。次いで、常圧蒸留しながら１３５℃に昇温し、そのまま２時間リフラックス反応させ、再度常圧蒸留しながら１８０℃に昇温し、１８０℃で減圧蒸留を行って未反応モノマーや水等の低沸点成分を除去し、軟化点１３６℃のトリアジン環を有するフェノール樹脂組成物６７部を得た。この樹脂組成物を（ａ１−１）とする。尚、得られたフェノール樹脂組成物中の固形分にはメチロール基は存在せず、一官能性フェノール類は０．９重量％、水酸基当量は１４６ｇ／ｅｑ．であった。
Synthesis example 1
A reactor equipped with a condenser and an atmospheric and vacuum distillation apparatus was charged with 94 parts of phenol, 18.8 parts of melamine, and 36.1 parts of 41.5% formalin, heated to 100 ° C. and refluxed for 2 hours. Reacted. Next, the temperature was raised to 135 ° C. during atmospheric distillation, and the reflux reaction was continued for 2 hours, and the temperature was raised to 180 ° C. again under atmospheric distillation, followed by distillation under reduced pressure at 180 ° C. to remove unreacted monomers, water, etc. Low-boiling components were removed, and 67 parts of a phenol resin composition having a triazine ring with a softening point of 136 ° C. was obtained. Let this resin composition be (a1-1). In the solid content of the obtained phenol resin composition, no methylol group was present, the monofunctional phenols were 0.9% by weight, and the hydroxyl group equivalent was 146 g / eq. Met.
合成例２
コンデンサーを備えた反応器に、合成例１で得られた樹脂組成物（ａ１−１）を１３５部、ビス（３−エチル−５−メチル−４−マレイミドフェニル）メタン１６５部、エチレングリコールモノメチルエーテル２００部を仕込み、１２５℃で３０分加熱攪拌を行い、室温に冷却した後、フェノール性アミノマレイミドプレポリマー樹脂（Ａ−１）の溶液５００部を得た。固形分（フェノール性アミノマレイミドプレポリマー樹脂）のＧＰＣで測定した重量平均分子量は２，９０５であった。
Synthesis example 2
In a reactor equipped with a condenser, 135 parts of the resin composition (a1-1) obtained in Synthesis Example 1, 165 parts of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, ethylene glycol monomethyl ether After 200 parts were charged and heated and stirred at 125 ° C. for 30 minutes and cooled to room temperature, 500 parts of a phenolic aminomaleimide prepolymer resin (A-1) solution was obtained. The weight average molecular weight measured by GPC of the solid content (phenolic aminomaleimide prepolymer resin) was 2,905.
合成例３
コンデンサーを備えた反応器に、合成例１で得られた樹脂組成物（ａ１−１）を１３５部、Ｎ，Ｎ’−（４，４−ジフェニルメタン）ビスマレイミド１３４部、エチレングリコールモノメチルエーテル１７９部を仕込み、１０５℃で１０分加熱攪拌を行い、室温に冷却した後、フェノール性アミノマレイミドプレポリマー樹脂（Ａ−２）の溶液４４８部を得た。固形分（フェノール性アミノマレイミドプレポリマー樹脂）のＧＰＣで測定した重量平均分子量は３，９２３であった。
Synthesis example 3
In a reactor equipped with a condenser, 135 parts of the resin composition (a1-1) obtained in Synthesis Example 1, 134 parts of N, N ′-(4,4-diphenylmethane) bismaleimide, 179 parts of ethylene glycol monomethyl ether Was heated and stirred at 105 ° C. for 10 minutes and cooled to room temperature to obtain 448 parts of a phenolic aminomaleimide prepolymer resin (A-2) solution. The weight average molecular weight measured by GPC of the solid content (phenolic aminomaleimide prepolymer resin) was 3,923.
合成例４
コンデンサーを備えた反応器に、合成例１で得られた樹脂組成物（ａ１−１）を１３５部、２，２−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパン２１３部、エチレングリコールモノメチルエーテル２３２部を仕込み、１１０℃で１０分加熱攪拌を行い、室温に冷却した後、フェノール性アミノマレイミドプレポリマー樹脂（Ａ−３）の溶液５８０部を得た。固形分（フェノール性アミノマレイミドプレポリマー樹脂）のＧＰＣで測定した重量平均分子量は３，４５２であった。
Synthesis example 4
In a reactor equipped with a condenser, 135 parts of the resin composition (a1-1) obtained in Synthesis Example 1, 213 parts of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, ethylene glycol monomethyl After charging 232 parts of ether and heating and stirring at 110 ° C. for 10 minutes and cooling to room temperature, 580 parts of a phenolic aminomaleimide prepolymer resin (A-3) solution was obtained. The weight average molecular weight measured by GPC of the solid content (phenolic aminomaleimide prepolymer resin) was 3,452.
比較合成例１
特開平５−２３０２４２号公報の実施例１を参考にして合成を行った。コンデンサーを備えた反応器に、Ｎ，Ｎ’−（４，４−ジフェニルメタン）ビスマレイミド１５０部、４，４−ジアミノジフェニルメタン３０部、エチレングリコールモノメチルエーテル１８０部を仕込み、１２５℃で３０分加熱攪拌を行った後、大日本インキ化学工業株式会社製ビスフェノールＦ型エポキシ樹脂（商品名［ＥＰＩＣＬＯＮ ８３０−Ｓ］、エポキシ当量１７１ｇ／ｅｑ．）１２０部加え、さらに９０℃で３０分反応させた後、室温まで冷却し、ジシアンジアミド７．４部とメチルエチルケトン１２０部を加え、組成物の不揮発分（Ｎ．Ｖ．）が５０％となるように調整した。この樹脂溶液をＡ’１とする。
Comparative Synthesis Example 1
The synthesis was carried out with reference to Example 1 of JP-A-5-230242. A reactor equipped with a condenser was charged with 150 parts of N, N ′-(4,4-diphenylmethane) bismaleimide, 30 parts of 4,4-diaminodiphenylmethane, and 180 parts of ethylene glycol monomethyl ether, and heated and stirred at 125 ° C. for 30 minutes. Then, 120 parts of a bisphenol F type epoxy resin (trade name [EPICLON 830-S], epoxy equivalent 171 g / eq.) Manufactured by Dainippon Ink & Chemicals, Inc. was added, and further reacted at 90 ° C. for 30 minutes. After cooling to room temperature, 7.4 parts of dicyandiamide and 120 parts of methyl ethyl ketone were added to adjust the nonvolatile content (NV) of the composition to 50%. This resin solution is designated as A′1.
実施例
実施例１〜３、比較例１
第１表の配合で下記の方法でワニスを調整し、下記の如き条件で硬化させて両面銅張積層板を試作し、各種の評価を行った。結果を第１表に示す。
Examples Examples 1 to 3 and Comparative Example 1
A varnish was prepared by the following method according to the formulation shown in Table 1 and cured under the following conditions to produce a double-sided copper-clad laminate, and various evaluations were performed. The results are shown in Table 1.
［積層板作製条件］
基材 ：１８０μｍ； 日東紡績株式会社製 ガラスクロス「ＷＥＡ ７６２８ Ｈ２５８」
プライ数 ：８ プリプレグ化条件：１６０℃／４分 銅 箔 ：３５μｍ； 古河サ−キットホイ−ル株式会社製 硬化条件 ：２００℃、４０ｋｇ／ｃｍ２で１．５時間 成型後板厚 ：１．６ｍｍ 樹脂含有量 ：４０％
[Laminate production conditions]
Substrate: 180 μm; glass cloth “WEA 7628 H258” manufactured by Nitto Boseki Co., Ltd.
Number of plies: 8 Pre-pregation conditions: 160 ° C./4 minutes Copper foil: 35 μm; Furukawa Sark Wheel Co., Ltd. Curing conditions: 1.5 hours at 200 ° C. and 40 kg / cm 2 Thickness after molding: 1.6 mm Resin Content: 40%
［物性試験条件］
成形状態： エッチング処理を施し銅箔除去した後、目視で外観検査を行い、欠損、カスレ、ミーズリング等が無く、均一に成形されているものを○とした。
ガラス転移温度： エッチング処理を施し銅箔除去した後、ＤＭＡ法にて測定。昇温スピード３℃／ｍｉｎ。
吸湿率： プレッシャークッカー試験機を使用し、１２１℃、２．１気圧、１００％ＲＨの条件において試験片（２５ｍｍ×５０ｍｍ）を２時間保持後、その前後の重量変化を測定した。
誘電特性： 誘電特性評価器を用いて１００ＭＨｚ、１ＧＨｚの周波数における誘電率と誘電正接を測定した（試験片のサイズ７５×２５×２ｍｍ）。
燃焼試験： ＵＬ−９４垂直試験に準拠。
[Physical property test conditions]
Molded state: After removing the copper foil by etching, visual inspection was performed, and a product that was uniformly molded without defects, scraping, and mising was marked as ◯.
Glass transition temperature: Measured by DMA method after removing copper foil by etching. Temperature rising speed 3 ° C / min.
Moisture absorption: Using a pressure cooker tester, a test piece (25 mm × 50 mm) was held for 2 hours under the conditions of 121 ° C., 2.1 atm and 100% RH, and the weight change before and after the test piece was measured.
Dielectric characteristics: Dielectric constant and dielectric loss tangent at frequencies of 100 MHz and 1 GHz were measured using a dielectric characteristic evaluator (test piece size 75 × 25 × 2 mm).
Combustion test: Conforms to UL-94 vertical test.
尚、第１表中の各原料及び略号は以下の通りである。
「８３０−Ｓ」 ：ビスフェノールＦ型エポキシ樹脂（大日本インキ化学工業株式会社製、商品名［ＥＰＩＣＬＯＮ ８３０−Ｓ］、エポキシ当量１７１ｇ／ｅｑ．）
「ＭＥＫ」 ：メチルエチルケトン
The raw materials and abbreviations in Table 1 are as follows.
"830-S": Bisphenol F type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name [EPICLON 830-S], epoxy equivalent 171 g / eq.)
"MEK": Methyl ethyl ketone
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| JPS59136324A (en) * | 1983-01-13 | 1984-08-04 | チバ−ガイギ−・アクチエンゲゼルシヤフト | Curable epoxy resin mixture containing imide compound, phenol amine and aldehyde or ketone condensate |
| JPH08311142A (en) * | 1995-03-15 | 1996-11-26 | Dainippon Ink & Chem Inc | Phenolic resin composition and curing agent for epoxy resin |
| JPH09110954A (en) * | 1995-10-23 | 1997-04-28 | Dainippon Ink & Chem Inc | Phenolic resin composition and hardener for epoxy resin |
| JPH09124897A (en) * | 1995-11-06 | 1997-05-13 | Dainippon Ink & Chem Inc | Thermosetting resin composition |
| JPH09183814A (en) * | 1995-12-28 | 1997-07-15 | Menicon Co Ltd | Lens material for eye |
| JP2003119247A (en) * | 2001-08-07 | 2003-04-23 | Nippon Kayaku Co Ltd | Resin composition, soldering resist composition and their cured product |
| JP2003113221A (en) * | 2001-10-05 | 2003-04-18 | Nippon Kayaku Co Ltd | Resin composition, solder resist resin composition and their cured products |
| JP2004169004A (en) * | 2002-11-06 | 2004-06-17 | Nippon Shokubai Co Ltd | Flame-retardant resin composition |
| JP2005314656A (en) * | 2004-03-08 | 2005-11-10 | Dainippon Ink & Chem Inc | Thermosetting composition and cured product thereof |
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| JP2006022179A (en) | 2006-01-26 |
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