JPWO2019003822A1 - Active ester compound and curable composition - Google Patents
Active ester compound and curable composition Download PDFInfo
- Publication number
- JPWO2019003822A1 JPWO2019003822A1 JP2019526746A JP2019526746A JPWO2019003822A1 JP WO2019003822 A1 JPWO2019003822 A1 JP WO2019003822A1 JP 2019526746 A JP2019526746 A JP 2019526746A JP 2019526746 A JP2019526746 A JP 2019526746A JP WO2019003822 A1 JPWO2019003822 A1 JP WO2019003822A1
- Authority
- JP
- Japan
- Prior art keywords
- active ester
- group
- curable composition
- compound
- ester compound
- 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.)
- Granted
Links
- -1 ester compound Chemical class 0.000 title claims abstract description 72
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 150000004820 halides Chemical class 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000004065 semiconductor Substances 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 12
- 125000005843 halogen group Chemical group 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 11
- 239000011889 copper foil Substances 0.000 abstract description 10
- 150000005690 diesters Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- 239000003822 epoxy resin Substances 0.000 description 22
- 229920000647 polyepoxide Polymers 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 150000002148 esters Chemical class 0.000 description 17
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 239000000155 melt Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
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- 239000003960 organic solvent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005538 encapsulation Methods 0.000 description 5
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
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- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 3
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
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- 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 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- XFSBVAOIAHNAPC-WSORPINJSA-N acetylbenzoylaconine Chemical compound O([C@H]1[C@]2(O)C[C@H]3C45[C@@H]6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)C4[C@]([C@@H](C[C@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-WSORPINJSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
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- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
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- 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 2
- 239000003054 catalyst Substances 0.000 description 2
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- 229930003836 cresol Natural products 0.000 description 2
- 150000007973 cyanuric acids Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- BTGKSZSRCPEZLG-UHFFFAOYSA-N dinaphthalen-1-yl benzene-1,3-dicarboxylate Chemical compound C1=CC=C2C(OC(=O)C=3C=CC=C(C=3)C(OC=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 BTGKSZSRCPEZLG-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
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- 229940038032 nitrogen 20 % Drugs 0.000 description 2
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
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- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 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
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- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical class C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
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- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 1
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- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
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- 0 CC(C(C1)*(C2C(C3)C4)C5(C)C2C3C4(C)C2=C(C)CCC2)C5C1=C Chemical compound CC(C(C1)*(C2C(C3)C4)C5(C)C2C3C4(C)C2=C(C)CCC2)C5C1=C 0.000 description 1
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- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 239000004643 cyanate ester Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
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- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
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- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
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- VBQCHPIMZGQLAZ-UHFFFAOYSA-N phosphorane Chemical class [PH5] VBQCHPIMZGQLAZ-UHFFFAOYSA-N 0.000 description 1
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- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 230000000630 rising effect Effects 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
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/78—Benzoic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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Abstract
硬化物における高温条件下での弾性率が低く、銅箔等に対する密着性にも優れる活性エステル化合物、これを含有する硬化性組成物、その硬化物、半導体封止材料及びプリント配線基板を提供する。具体的には、下記構造式（１）（式中Ｒ１はそれぞれ独立して脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基の何れかである。ｍは０又は１〜４の整数であり、ｎは０又は１である。）で表されるジヒドロキシ化合物（ａ１）と芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）とのジエステル化物である活性エステル化合物を提供する。Provided are an active ester compound having a low elastic modulus in a cured product under high temperature conditions and having excellent adhesion to a copper foil, a curable composition containing the same, a cured product thereof, a semiconductor encapsulating material, and a printed wiring board. .. Specifically, the following structural formula (1) (in the formula, each R1 is independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group or an aralkyl group. M is 0 or 1 to 4) And n is 0 or 1.), which is a diester of the dihydroxy compound (a1) represented by the formula (1) and the aromatic monocarboxylic acid or its acid halide (a2).
Description
本発明は硬化物における高温条件下での弾性率が低く、銅箔等に対する密着性にも優れる活性エステル化合物、これを含有する硬化性組成物、その硬化物、半導体封止材料及びプリント配線基板に関する。 The present invention provides an active ester compound having a low elastic modulus under high temperature conditions in a cured product and having excellent adhesion to a copper foil, a curable composition containing the same, a cured product thereof, a semiconductor encapsulating material and a printed wiring board. Regarding
半導体や多層プリント基板等に用いられる絶縁材料の技術分野では、各種電子部材の薄型化や小型化に伴い、これらの市場動向に合わせた新たな樹脂材料の開発が求められている。半導体封止材料に求められる性能としては、リフロー性向上の為に高温条件下での弾性率が低いことが求められる。この他、硬化物における耐熱性や耐吸湿性、銅箔等に対する密着性は勿論のこと、信号の高速化及び高周波数化対策として、硬化物における誘電率及び誘電正接値が低いこと、高温条件下での信頼性としてガラス転移温度（Ｔｇ）等の物性変化がないこと、薄型化に伴う反りや歪み対策として硬化収縮率や線膨張係数が低いこと等も重要である。 In the technical field of insulating materials used for semiconductors, multilayer printed circuit boards, and the like, with the thinning and miniaturization of various electronic members, development of new resin materials that meet these market trends is required. As a performance required of the semiconductor encapsulating material, a low elastic modulus under high temperature conditions is required to improve reflowability. In addition to the heat resistance and moisture absorption resistance of the cured product, the adhesion to copper foil, etc., the low dielectric constant and dielectric loss tangent value of the cured product as a measure for speeding up signals and high frequencies, high temperature conditions It is also important that reliability under the condition that there is no change in physical properties such as glass transition temperature (Tg) and that cure shrinkage and linear expansion coefficient are low as a measure against warpage and distortion due to thinning.
硬化物における耐熱性や誘電特性等に優れる樹脂材料として、ジ（１−ナフチル）イソフタレートをエポキシ樹脂の硬化剤として用いる技術が知られている（下記特許文献１参照）。特許文献１に記載されたエポキシ樹脂組成物は、ジ（α−ナフチル）イソフタレートをエポキシ樹脂硬化剤として用いることにより、フェノールノボラック樹脂のような従来型のエポキシ樹脂硬化剤を用いた場合と比較して硬化物における誘電率や誘電正接の値は確かに低いものの、硬化物における高温条件下での弾性率が近年要求されるレベルを満足するものでは無く、銅箔等に対する密着性も低かった。また、溶融粘度が高いことから、半導体封止材料等溶融粘度が低いことが求められる用途においては使用に制限があった。 A technique using di (1-naphthyl) isophthalate as a curing agent for an epoxy resin is known as a resin material having excellent heat resistance and dielectric properties in a cured product (see Patent Document 1 below). The epoxy resin composition described in Patent Document 1 uses di (α-naphthyl) isophthalate as an epoxy resin curing agent to compare with the case of using a conventional epoxy resin curing agent such as phenol novolac resin. Although the values of dielectric constant and dielectric loss tangent of the cured product are certainly low, the elastic modulus of the cured product under high temperature conditions does not satisfy the level required in recent years, and the adhesion to copper foil etc. was also low. . Further, since the melt viscosity is high, there is a limitation in use in applications such as semiconductor encapsulation materials where low melt viscosity is required.
従って、本発明が解決しようとする課題は、硬化物における高温条件下での弾性率が低く、銅箔等に対する密着性にも優れる活性エステル化合物、これを含有する硬化性組成物、その硬化物、半導体封止材料及びプリント配線基板を提供することにある。 Therefore, the problem to be solved by the present invention is that the elastic modulus of the cured product under high temperature conditions is low, and the active ester compound has excellent adhesion to copper foil, etc., a curable composition containing the same, and a cured product thereof. To provide a semiconductor encapsulation material and a printed wiring board.
本発明者らは前記課題を解決すべく鋭意検討した結果、ジシクロペンタジエン付加型フェノール化合物と芳香族モノカルボン酸又はその酸ハロゲン化物とのジエステル化物である活性エステル化合物は、硬化物における高温条件下での弾性率が低い上、銅箔等に対する密着性も高く、溶融粘度も低いことを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an active ester compound which is a diester compound of a dicyclopentadiene addition type phenol compound and an aromatic monocarboxylic acid or an acid halide thereof is at a high temperature in a cured product. The inventors have found that the elastic modulus below is low, the adhesion to copper foil and the like is high, and the melt viscosity is low, and the present invention has been completed.
即ち、本発明は、下記構造式（１） That is, the present invention provides the following structural formula (1)
で表されるジヒドロキシ化合物（ａ１）と芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）とのジエステル化物である活性エステル化合物に関する。
The present invention relates to an active ester compound which is a diester compound of a dihydroxy compound (a1) represented by and an aromatic monocarboxylic acid or its acid halide (a2).
本発明は更に、前記活性エステル化合物と、硬化剤とを含有する硬化性組成物に関する。 The present invention further relates to a curable composition containing the active ester compound and a curing agent.
本発明は更に、前記硬化性組成物の硬化物に関する。 The present invention further relates to a cured product of the curable composition.
本発明は更に、前記硬化性組成物を用いてなる半導体封止材料に関する。 The present invention further relates to a semiconductor encapsulating material using the curable composition.
本発明は更に、前記硬化性組成物を用いてなるプリント配線基板に関する。 The present invention further relates to a printed wiring board using the curable composition.
本発明によれば、硬化物において高温条件下での弾性率が低い活性エステル化合物、これを含有する硬化性組成物、その硬化物、半導体封止材料及びプリント配線基板を提供することができる。 According to the present invention, it is possible to provide an active ester compound having a low elastic modulus in a cured product under high temperature conditions, a curable composition containing the same, a cured product thereof, a semiconductor encapsulating material, and a printed wiring board.
以下、本発明を詳細に説明する。
本発明の活性エステル化合物は、下記構造式（１）Hereinafter, the present invention will be described in detail.
The active ester compound of the present invention has the following structural formula (1)
で表されるジヒドロキシ化合物（ａ１）と芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）とのジエステル化物である。
Is a diester compound of a dihydroxy compound (a1) represented by and an aromatic monocarboxylic acid or an acid halide thereof (a2).
前記ジヒドロキシ化合物（ａ１）について、Ｒ１はそれぞれ独立して脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基の何れかである。前記脂肪族炭化水素基は直鎖型及び分岐型のいずれでもよく、構造中に不飽和結合を有していてもよい。具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、へキシル基等のアルキル基；シクロへキシル基等のシクロアルキル基；ビニル基、アリル基、プロパギル基等の不飽和結合含有基等が挙げられる。前記アルコキシ基は、メトキシ基、エトキシ基、プロピルオキシ基、ブトキシ基等が挙げられる。前記ハロゲン原子は、フッ素原子、塩素原子、臭素原子等が挙げられる。前記アリール基は、フェニル基、ナフチル基、アントリル基、及びこれらの芳香核上に前記脂肪族炭化水素基やアルコキシ基、ハロゲン原子等が置換した構造部位等が挙げられる。前記アラルキル基は、ベンジル基、フェニルエチル基、ナフチルメチル基、ナフチルエチル基、及びこれらの芳香核上に前記アルキル基やアルコキシ基、ハロゲン原子等が置換した構造部位等が挙げられる。前記ジヒドロキシ化合物（ａ１）は一種類を単独で用いても良いし、置換基の種類や置換位置の異なる化合物等を２種類以上併用しても良い。In the dihydroxy compound (a1), R 1 is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group or an aralkyl group. The aliphatic hydrocarbon group may be linear or branched, and may have an unsaturated bond in its structure. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group; cycloalkyl groups such as cyclohexyl group; unsaturated groups such as vinyl group, allyl group, and propargyl group. Examples include a bond-containing group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group and a butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a structural moiety in which the aliphatic hydrocarbon group, the alkoxy group, a halogen atom or the like is substituted on the aromatic nucleus thereof. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and a structural site in which an alkyl group, an alkoxy group, a halogen atom or the like is substituted on the aromatic nucleus thereof. The dihydroxy compound (a1) may be used alone or in combination of two or more compounds having different kinds of substituents or different substitution positions.
前記芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）は、ベンゼンカルボン酸、ナフタレンカルボン酸、これらの芳香核上に脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基等の置換基を一つ乃至複数有する化合物、及びこれらの酸ハロゲン化物等が挙げられる。これらは一種類を単独で用いても良いし、２種類以上を併用しても良い。中でも、硬化物における高温条件下での弾性率が低く、また、硬化性等にも優れる活性エステル化合物となることから、ベンゼンカルボン酸又はそのハロゲン化物が好ましい。したがって、本発明の活性エステル化合物のより好ましい構造としては、下記構造式（２）で表されるものが挙げられる The aromatic monocarboxylic acid or its acid halide (a2) is a benzenecarboxylic acid, a naphthalenecarboxylic acid, or a substituent such as an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group or an aralkyl group on the aromatic nucleus thereof. Examples thereof include compounds having one or more groups and acid halides thereof. These may be used alone or in combination of two or more. Among them, benzenecarboxylic acid or its halide is preferable because it is an active ester compound that has a low elastic modulus in a cured product under high temperature conditions and is excellent in curability and the like. Therefore, as a more preferable structure of the active ester compound of the present invention, a structure represented by the following structural formula (2) can be mentioned.
前記ジヒドロキシ化合物（ａ１）と芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）との反応は、例えば、アルカリ触媒の存在下、４０〜６５℃程度の温度条件下で加熱撹拌する方法により行うことができる。反応は必要に応じて有機溶媒中で行っても良い。また、反応終了後は所望に応じて、水洗や再沈殿等により反応生成物を精製しても良い。 The reaction between the dihydroxy compound (a1) and the aromatic monocarboxylic acid or its acid halide (a2) is carried out, for example, by heating and stirring in the presence of an alkali catalyst under a temperature condition of about 40 to 65 ° C. You can The reaction may be carried out in an organic solvent if necessary. Further, after the completion of the reaction, the reaction product may be purified by washing with water or reprecipitation, if desired.
前記アルカリ触媒は、例えば、水酸化ナトリウム、水酸化カリウム、トリエチルアミン、ピリジン等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。また、３．０〜３０％程度の水溶液として用いても良い。中でも、触媒能の高い水酸化ナトリウム又は水酸化カリウムが好ましい。 Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, triethylamine, pyridine and the like. These may be used alone or in combination of two or more. Further, it may be used as an aqueous solution of about 3.0 to 30%. Among them, sodium hydroxide or potassium hydroxide having high catalytic ability is preferable.
前記有機溶媒は、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン溶媒、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル溶媒、セロソルブ、ブチルカルビトール等のカルビトール溶媒、トルエン、キシレン等の芳香族炭化水素溶媒、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上の混合溶媒としても良い。 The organic solvent is, for example, a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetate ester solvent such as carbitol acetate, cellosolve, butyl carbitol. And the like, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. These may be used alone or as a mixed solvent of two or more kinds.
前記ジヒドロキシ化合物（ａ１）と芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）との反応割合は、目的の活性エステル化合物を高収率で得られることから、前記ジヒドロキシ化合物（ａ１）が有する水酸基の合計１モルに対し、前記芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）が０．９５〜１．０５モルとなる割合であることが好ましい。 The reaction ratio between the dihydroxy compound (a1) and the aromatic monocarboxylic acid or its acid halide (a2) is such that the target active ester compound can be obtained in high yield, and therefore the hydroxyl group contained in the dihydroxy compound (a1) is It is preferable that the ratio of the aromatic monocarboxylic acid or its acid halide (a2) is 0.95 to 1.05 mol per 1 mol in total.
本発明では、前記ジヒドロキシ化合物（ａ１）原料として、下記構造式（３）で表され、ｔが１以上の整数であるオリゴマー成分（ａ３）を一部含有するものを用いてもよい。 In the present invention, as the raw material for the dihydroxy compound (a1), those partially containing an oligomer component (a3) represented by the following structural formula (3) and t is an integer of 1 or more may be used.
この場合、前記ジヒドロキシ化合物（ａ１）原料中の前記ジヒドロキシ化合物（ａ１）の含有量は、本発明が奏する効果が十分に発揮されることから、５０％以上であることが好ましく、６５〜９０％の範囲であることが好ましい。また、前記ジヒドロキシ化合物（ａ１）原料中、前記構造式（３）においてｔが１である成分の含有量は５〜３０％の範囲であることが好ましい。更に、前記ジヒドロキシ化合物（ａ１）原料中の前記ジヒドロキシ化合物（ａ１）と前記構造式（３）においてｔが１である成分との合計、即ち、前記構造式（３）においてｔが０又は１である成分の合計は７０％以上であることが好ましく、８５％以上であることがより好ましい。前記ジヒドロキシ化合物（ａ１）原料において構造式（３）中のｔの平均値は０．０５〜０．８の範囲であることが好ましい。なお、ｔの平均値は前記ジヒドロキシ化合物（ａ１）原料の数平均分子量（Ｍｎ）から算出される計算値である。 In this case, the content of the dihydroxy compound (a1) in the raw material of the dihydroxy compound (a1) is preferably 50% or more, and 65 to 90%, since the effect of the present invention is sufficiently exhibited. It is preferably in the range of. In addition, the content of the component in which t is 1 in the structural formula (3) in the dihydroxy compound (a1) raw material is preferably in the range of 5 to 30%. Furthermore, the sum of the dihydroxy compound (a1) in the raw material of the dihydroxy compound (a1) and the component in which t is 1 in the structural formula (3), that is, when t is 0 or 1 in the structural formula (3), The total content of certain components is preferably 70% or more, and more preferably 85% or more. In the dihydroxy compound (a1) raw material, the average value of t in the structural formula (3) is preferably in the range of 0.05 to 0.8. The average value of t is a calculated value calculated from the number average molecular weight (Mn) of the dihydroxy compound (a1) raw material.
本発明において、前記ジヒドロキシ化合物（ａ１）原料中の各成分の含有量や分子量、後述する活性エステル組成物中の各成分の含有量や分子量は下記条件で測定されるＧＰＣチャート図の面積比から算出される値である。 In the present invention, the content and molecular weight of each component in the raw material of the dihydroxy compound (a1), and the content and molecular weight of each component in the active ester composition described later are calculated from the area ratio of the GPC chart diagram measured under the following conditions. It is a calculated value.
測定装置 ：東ソー株式会社製「ＨＬＣ−８３２０ ＧＰＣ」、
カラム：東ソー株式会社製ガードカラム「ＨＸＬ−Ｌ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ４０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ３０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
検出器： ＲＩ（示差屈折計）
データ処理：東ソー株式会社製「ＧＰＣワークステーション ＥｃｏＳＥＣ−ＷｏｒｋＳｔａｔｉｏｎ」
測定条件： カラム温度 ４０℃
展開溶媒 テトラヒドロフラン
流速 １．０ｍｌ／分
標準 ： 前記「ＧＰＣ−８３２０」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
（使用ポリスチレン）
東ソー株式会社製「Ａ−５００」
東ソー株式会社製「Ａ−１０００」
東ソー株式会社製「Ａ−２５００」
東ソー株式会社製「Ａ−５０００」
東ソー株式会社製「Ｆ−１」
東ソー株式会社製「Ｆ−２」
東ソー株式会社製「Ｆ−４」
東ソー株式会社製「Ｆ−１０」
東ソー株式会社製「Ｆ−２０」
東ソー株式会社製「Ｆ−４０」
東ソー株式会社製「Ｆ−８０」
東ソー株式会社製「Ｆ−１２８」
試料 ： 樹脂固形分換算で１．０質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（５０μｌ）Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation,
Column: Tosoh Co., Ltd. guard column "HXL-L"
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: "GPC workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of “GPC-8320”.
(Polystyrene used)
Tosoh Corporation "A-500"
Tosoh Corporation "A-1000"
Tosoh Corporation "A-2500"
Tosoh Corporation "A-5000"
Tosoh Corporation "F-1"
Tosoh Corporation "F-2"
Tosoh Corporation "F-4"
Tosoh Corporation "F-10"
Tosoh Corporation "F-20"
Tosoh Corporation "F-40"
Tosoh Corporation “F-80”
Tosoh Corporation "F-128"
Sample: 1.0% by mass of tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (50 μl)
前記ジヒドロキシ化合物（ａ１）原料が前記オリゴマー成分（ａ３）を一部含有する場合、前記ジヒドロキシ化合物（ａ１）原料と芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）との反応割合は、目的の活性エステル化合物を高収率で得られることから、前記ジヒドロキシ化合物（ａ１）原料が有する水酸基の合計１モルに対し、前記芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）が０．９５〜１．０５モルとなる割合であることが好ましい。 When the raw material of the dihydroxy compound (a1) partially contains the oligomer component (a3), the reaction ratio between the raw material of the dihydroxy compound (a1) and the aromatic monocarboxylic acid or the acid halide thereof (a2) is the target. Since the active ester compound can be obtained in a high yield, 0.95 to 1 of the aromatic monocarboxylic acid or the acid halide thereof (a2) is contained with respect to 1 mol of the total of hydroxyl groups contained in the dihydroxy compound (a1) raw material. The ratio is preferably 0.05 mol.
前記ジヒドロキシ化合物（ａ１）原料が前記オリゴマー成分（ａ３）を一部含有する場合、本発明の活性エステル化合物は、下記構造式（４）で表される化合物のうちｔが１以上の整数であるポリエステル化合物を含む活性エステル組成物として得られる。 When the raw material for the dihydroxy compound (a1) partially contains the oligomer component (a3), the active ester compound of the present invention is a compound represented by the following structural formula (4), in which t is an integer of 1 or more. Obtained as an active ester composition containing a polyester compound.
この場合、活性エステル組成物中のジエステル化合物、即ち本発明の活性エステル化合物の含有量は、本発明が奏する効果が十分に発揮されることから、５０％以上であることが好ましく、６５〜９５％の範囲であることが好ましい。また、活性エステル組成物中、前記構造式（４）においてｔが１である成分の含有量が５〜３０％の範囲であることが好ましい。更に、活性エステル組成物中の前記活性エステル化合物と前記構造式（４）においてｔが１である成分との合計、即ち、前記構造式（４）においてｔが０又は１である成分の合計は７０％以上であることが好ましく、８５％以上であることがより好ましい。なお、活性エステル組成物中の各成分の含有量は、前記条件で測定されるＧＰＣチャート図の面積比から算出される値である。活性エステル組成物においてｔの平均値は０．０５〜０．８の範囲であることが好ましい。なお、ｔの平均値は活性エステル組成物の数平均分子量（Ｍｎ）から算出される計算値である。 In this case, the content of the diester compound in the active ester composition, that is, the active ester compound of the present invention is preferably 50% or more, from the viewpoint that the effect of the present invention is sufficiently exhibited, and the content is 65 to 95. It is preferably in the range of%. Further, in the active ester composition, the content of the component in which t is 1 in the structural formula (4) is preferably in the range of 5 to 30%. Further, the total of the active ester compound in the active ester composition and the component in which t is 1 in the structural formula (4), that is, the sum of the components in which t is 0 or 1 in the structural formula (4) is It is preferably 70% or more, and more preferably 85% or more. The content of each component in the active ester composition is a value calculated from the area ratio of the GPC chart diagram measured under the above conditions. In the active ester composition, the average value of t is preferably in the range of 0.05 to 0.8. The average value of t is a calculated value calculated from the number average molecular weight (Mn) of the active ester composition.
本発明の活性エステル化合物或いは前記活性エステル組成物の溶融粘度は、ＡＳＴＭ Ｄ４２８７に準拠し、ＩＣＩ粘度計にて測定した１５０℃における値が０．０１〜５０ｄＰａ・ｓの範囲であることが好ましく、０．０１〜５ｄＰａ・ｓの範囲であることが特に好ましい。 The melt viscosity of the active ester compound of the present invention or the active ester composition is preferably in the range of 0.01 to 50 dPa · s at 150 ° C. measured by an ICI viscometer in accordance with ASTM D4287, The range of 0.01 to 5 dPa · s is particularly preferable.
本発明の硬化性組成物は、前記本発明の活性エステル化合物或いは前記活性エステル組成物と併せて、その他の活性エステル化合物を含有しても良い。前記その他の活性エステル化合物としては、分子構造中にフェノール性水酸基を一つ有する化合物と芳香族ポリカルボン酸又はその酸ハロゲン化物とのエステル化物、前記ジヒドロキシ化合物（ａ１）や前記オリゴマー成分（ａ３）以外のフェノール性水酸基を２つ以上有する化合物と芳香族モノカルボン酸又はその酸ハロゲン化物とのエステル化物、分子構造中にフェノール性水酸基を一つ有する化合物、芳香族ポリカルボン酸又はその酸ハロゲン化物及び分子構造中にフェノール性水酸基を２つ以上有する化合物のエステル化物、芳香族ポリカルボン酸又はその酸ハロゲン化物、分子構造中にフェノール性水酸基を２つ以上有する化合物及び芳香族モノカルボン酸又はその酸ハロゲン化物のエステル化物等が挙げられる。 The curable composition of the present invention may contain other active ester compounds in addition to the active ester compound of the present invention or the active ester composition. Examples of the other active ester compounds include esterified compounds of a compound having one phenolic hydroxyl group in the molecular structure with an aromatic polycarboxylic acid or an acid halide thereof, the dihydroxy compound (a1) and the oligomer component (a3). Ester compound of a compound having two or more phenolic hydroxyl groups other than the above with an aromatic monocarboxylic acid or an acid halide thereof, a compound having one phenolic hydroxyl group in the molecular structure, an aromatic polycarboxylic acid or an acid halide thereof And an esterified product of a compound having two or more phenolic hydroxyl groups in the molecular structure, an aromatic polycarboxylic acid or an acid halide thereof, a compound having two or more phenolic hydroxyl groups in the molecular structure and an aromatic monocarboxylic acid or the same Examples thereof include esterified products of acid halides.
前記その他の活性エステル化合物を用いる場合、本発明が奏する効果が十分に発揮されることから、全活性エステル化合物の合計に対する本発明の活性エステル化合物又は前記活性エステル組成物の割合が７０質量％以上であることが好ましく、８０質量％以上であることがより好ましい。また、活性エステル化合物全体での溶融粘度が０．０１〜５０ｄＰａ・ｓの範囲であることが好ましく、０．０１〜５ｄＰａ・ｓの範囲であることが特に好ましい。配合物の溶融粘度はＡＳＴＭ Ｄ４２８７に準拠し、ＩＣＩ粘度計にて測定した１５０℃における値である。 When the other active ester compound is used, since the effect of the present invention is sufficiently exhibited, the ratio of the active ester compound of the present invention or the active ester composition to the total of all active ester compounds is 70% by mass or more. Is preferable, and more preferably 80% by mass or more. The melt viscosity of the whole active ester compound is preferably in the range of 0.01 to 50 dPa · s, and particularly preferably in the range of 0.01 to 5 dPa · s. The melt viscosity of the blend is a value at 150 ° C. measured by an ICI viscometer according to ASTM D4287.
本発明の硬化性組成物は、前述の活性エステル化合物と硬化剤とを含有する。前記硬化剤は前記活性エステル化合物と反応し得る化合物であれば良く、特に限定なく様々な化合物が利用できる。硬化剤の一例としては、例えば、エポキシ樹脂が挙げられる。 The curable composition of the present invention contains the above-mentioned active ester compound and a curing agent. The curing agent may be any compound that can react with the active ester compound, and various compounds can be used without particular limitation. An example of the curing agent is an epoxy resin.
前記エポキシ樹脂は、例えば、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、ナフトールノボラック型エポキシ樹脂、ビスフェノールノボラック型エポキシ樹脂、ビフェノールノボラック型エポキシ樹脂、ビスフェノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、テトラフェノールエタン型エポキシ樹脂、ジシクロペンタジエン−フェノール付加反応型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂等が挙げられる。 The epoxy resin is, for example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, bisphenol novolac type epoxy resin, biphenol novolac type epoxy resin, bisphenol type epoxy resin, biphenyl type epoxy resin, triphenol methane. Type epoxy resin, tetraphenolethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin and the like.
本発明の硬化性組成物において、前記活性エステル化合物と硬化剤との配合割合は特に限定なく、所望の硬化物性能等に応じて適宜調整することができる。硬化剤としてエポキシ樹脂を用いる場合の配合の一例としては、硬化性組成物中のエポキシ基の合計１モルに対して、前記活性エステル化合物中の官能基の合計が０．７〜１．５モルとなる割合であることが好ましい。 In the curable composition of the present invention, the mixing ratio of the active ester compound and the curing agent is not particularly limited, and can be appropriately adjusted according to the desired performance of the cured product. As an example of the composition when an epoxy resin is used as a curing agent, the total of the functional groups in the active ester compound is 0.7 to 1.5 mol with respect to the total of 1 mol of the epoxy groups in the curable composition. The following ratio is preferable.
本発明の硬化性組成物は、更にその他の樹脂成分を含有しても良い。その他の樹脂成分は、例えば、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、イミダゾ−ル、ＢＦ３−アミン錯体、グアニジン誘導体等のアミン化合物；ジシアンジアミド、リノレン酸の２量体とエチレンジアミンとより合成されるポリアミド樹脂等のアミド化合物；無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等の酸無水物；シアン酸エステル樹脂；ビスマレイミド樹脂；ベンゾオキサジン樹脂；スチレン−無水マレイン酸樹脂；ジアリルビスフェノールやトリアリルイソシアヌレートに代表されるアリル基含有樹脂；ポリリン酸エステルやリン酸エステル−カーボネート共重合体等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。これらその他の樹脂成分の配合割合は特に限定なく、所望の硬化物性能等に応じて適宜調整することができる。The curable composition of the present invention may further contain other resin components. Other resin components include amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF 3 -amine complex, guanidine derivative; dicyandiamide, dimer of linolenic acid, and the like. Amide compounds such as polyamide resins synthesized with ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride Acids, acid anhydrides such as methylhexahydrophthalic anhydride, cyanate ester resins, bismaleimide resins, benzoxazine resins, styrene-maleic anhydride resins, diallyl bisphenols and triaries Allyl group-containing resin represented by isocyanurate; polyphosphoric acid ester or phosphoric acid ester - carbonate copolymer, and the like. These may be used alone or in combination of two or more. The mixing ratio of these other resin components is not particularly limited, and can be appropriately adjusted according to the desired performance of the cured product and the like.
本発明の硬化性組成物は必要に応じて硬化促進剤、難燃剤、無機質充填材、シランカップリング剤、離型剤、顔料、乳化剤等の各種添加剤を含有しても良い。 The curable composition of the present invention may contain various additives such as a curing accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a release agent, a pigment and an emulsifier, if necessary.
前記硬化促進剤は、例えば、リン系化合物、第３級アミン、イミダゾール化合物、ピリジン化合物、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。中でも、硬化性、耐熱性、電気特性、耐湿信頼性等に優れる点から、リン系化合物ではトリフェニルホスフィン、第３級アミンでは１，８−ジアザビシクロ−［５．４．０］−ウンデセン（ＤＢＵ）、イミダゾール化合物では２−エチル−４−メチルイミダゾール、ピリジン化合物では４−ジメチルアミノピリジンが好ましい。 Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazole compounds, pyridine compounds, organic acid metal salts, Lewis acids, amine complex salts and the like. Of these, triphenylphosphine is a phosphorus compound and 1,8-diazabicyclo- [5.4.0] -undecene (DBU) is a tertiary amine because of its excellent curability, heat resistance, electrical characteristics, and moisture resistance reliability. ), 2-ethyl-4-methylimidazole is preferable for the imidazole compound, and 4-dimethylaminopyridine is preferable for the pyridine compound.
前記難燃剤は、例えば、赤リン、リン酸一アンモニウム、リン酸二アンモニウム、リン酸三アンモニウム、ポリリン酸アンモニウム等のリン酸アンモニウム、リン酸アミド等の無機リン化合物；リン酸エステル化合物、ホスホン酸化合物、ホスフィン酸化合物、ホスフィンオキシド化合物、ホスホラン化合物、有機系含窒素リン化合物、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド、１０−（２，５―ジヒドロオキシフェニル）―１０Ｈ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド、１０―（２，７−ジヒドロオキシナフチル）−１０Ｈ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド等の環状有機リン化合物、及びそれをエポキシ樹脂やフェノール樹脂等の化合物と反応させた誘導体等の有機リン化合物；トリアジン化合物、シアヌル酸化合物、イソシアヌル酸化合物、フェノチアジン等の窒素系難燃剤；シリコーンオイル、シリコーンゴム、シリコーン樹脂等のシリコーン系難燃剤；金属水酸化物、金属酸化物、金属炭酸塩化合物、金属粉、ホウ素化合物、低融点ガラス等の無機難燃剤等が挙げられる。これら難燃剤を用いる場合は、硬化性組成物中０．１〜２０質量％の範囲であることが好ましい。 Examples of the flame retardant include red phosphorous, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, inorganic phosphorus compounds such as phosphoric acid amides; phosphate ester compounds and phosphonic acids. Compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl ) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic organic phosphorus Compounds and compounds such as epoxy resins and phenolic resins Organic phosphorus compounds such as reacted derivatives; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds and phenothiazines; silicone-based flame retardants such as silicone oils, silicone rubbers and silicone resins; metal hydroxides, metals Inorganic flame retardants such as oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass are included. When using these flame retardants, it is preferably in the range of 0.1 to 20 mass% in the curable composition.
前記無機質充填材は、例えば、本発明の硬化性組成物を半導体封止材料用途に用いる場合などに配合される。前記無機質充填材は、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。中でも、無機質充填材をより多く配合することが可能となることから、前記溶融シリカが好ましい。前記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、硬化性組成物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ことが好ましい。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。その充填率は硬化性組成物１００質量部中、０．５〜９５質量部の範囲で配合することが好ましい。 The inorganic filler is blended, for example, when the curable composition of the present invention is used for semiconductor encapsulation material. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among them, the fused silica is preferable because it is possible to add a larger amount of the inorganic filler. The fused silica may be used in the crushed form or in the spherical form, but in order to increase the blending amount of the fused silica and suppress the increase in the melt viscosity of the curable composition, the spherical form is mainly used. It is preferable. Further, in order to increase the compounding amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably 0.5 to 95 parts by mass in 100 parts by mass of the curable composition.
この他、本発明の硬化性組成物を導電ペースト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。 In addition, when the curable composition of the present invention is used for applications such as a conductive paste, a conductive filler such as silver powder or copper powder can be used.
以上詳述した通り、本発明の活性エステル化合物及びこれを含有する硬化性組成物は、硬化物における高温条件下での弾性率が低く、銅箔等に対する密着性にも優れる特徴を有する。この他、汎用有機溶剤への溶解性や、耐熱性、耐吸水性、低硬化収縮性、誘電特性にも優れ、また、溶融粘度が低い等、樹脂材料に求められる他の一般的な要求性能も十分に高いものである。このため、プリント配線基板や半導体封止材料、レジスト材料等の電子材料用途の他、塗料や接着剤、成型品等の用途にも広く利用することができる。 As described in detail above, the active ester compound of the present invention and the curable composition containing the same have the characteristics that the elastic modulus of the cured product under high temperature conditions is low and the adhesion to copper foil and the like is excellent. In addition, other general required performance required for resin materials such as solubility in general-purpose organic solvents, heat resistance, water absorption resistance, low curing shrinkage, excellent dielectric properties, low melt viscosity, etc. Is also high enough. Therefore, it can be widely used not only for electronic materials such as printed wiring boards, semiconductor encapsulation materials, resist materials and the like, but also for applications such as paints, adhesives and molded products.
本発明の硬化性組成物をプリント配線基板用途やビルドアップ接着フィルム用途に用いる場合、一般には有機溶剤を配合して希釈して用いることが好ましい。前記有機溶剤は、メチルエチルケトン、アセトン、ジメチルホルムアミド、メチルイソブチルケトン、メトキシプロパノール、シクロヘキサノン、メチルセロソルブ、エチルジグリコールアセテート、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。有機溶剤の種類や配合量は硬化性組成物の使用環境に応じて適宜調整できるが、例えば、プリント配線板用途では、メチルエチルケトン、アセトン、ジメチルホルムアミド等の沸点が１６０℃以下の極性溶剤であることが好ましく、不揮発分が４０〜８０質量％となる割合で使用することが好ましい。ビルドアップ接着フィルム用途では、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン溶剤、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル溶剤、セロソルブ、ブチルカルビトール等のカルビトール溶剤、トルエン、キシレン等の芳香族炭化水素溶剤、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等を用いることが好ましく、不揮発分が３０〜６０質量％となる割合で使用することが好ましい。 When the curable composition of the present invention is used for printed wiring board applications and build-up adhesive film applications, it is generally preferable to use an organic solvent after diluting it. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. The type and blending amount of the organic solvent can be appropriately adjusted according to the environment in which the curable composition is used. For example, in printed wiring board applications, methyl ethyl ketone, acetone, dimethylformamide, etc. must be a polar solvent with a boiling point of 160 ° C. or less. Is preferable, and it is preferable to use it in a ratio such that the nonvolatile content is 40 to 80 mass%. For build-up adhesive film applications, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, acetic acid ester solvents such as cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, carbitol such as cellosolve, butyl carbitol, etc. It is preferable to use a solvent, an aromatic hydrocarbon solvent such as toluene or xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone or the like, and it is preferable to use a nonvolatile content of 30 to 60% by mass.
また、本発明の硬化性組成物を用いてプリント配線基板を製造する方法は、例えば、硬化性組成物を補強基材に含浸し硬化させてプリプレグを得、これと銅箔とを重ねて加熱圧着させる方法が挙げられる。前記補強基材は、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。硬化性組成物の含浸量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質量％となるように調製することが好ましい。 Further, the method for producing a printed wiring board using the curable composition of the present invention is, for example, impregnating a curable composition into a reinforcing base material and curing it to obtain a prepreg. A method of pressure bonding may be mentioned. Examples of the reinforcing substrate include paper, glass cloth, glass non-woven cloth, aramid paper, aramid cloth, glass mat, and glass roving cloth. The impregnated amount of the curable composition is not particularly limited, but it is usually preferable to prepare it so that the resin content in the prepreg is 20 to 60% by mass.
本発明の硬化性組成物を半導体封止材料用途に用いる場合、一般には無機質充填材を配合することが好ましい。半導体封止材料は、例えば、押出機、ニーダー、ロール等を用いて配合物を混合して調製することができる。得られた半導体封止材料を用いて半導体パッケージを成型する方法は、例えば、該半導体封止材料を注型或いはトランスファー成形機、射出成型機などを用いて成形し、更に５０〜２００℃の温度条件下で２〜１０時間加熱する方法が挙げられ、このような方法により、成形物である半導体装置を得ることが出来る。 When the curable composition of the present invention is used for semiconductor encapsulation materials, it is generally preferable to add an inorganic filler. The semiconductor encapsulating material can be prepared by mixing the compound using an extruder, a kneader, a roll, or the like. The method of molding a semiconductor package using the obtained semiconductor encapsulating material is, for example, molding the semiconductor encapsulating material using a casting or transfer molding machine, an injection molding machine or the like, and further, at a temperature of 50 to 200 ° C. There is a method of heating for 2 to 10 hours under the conditions, and a semiconductor device which is a molded product can be obtained by such a method.
次に本発明を実施例、比較例により具体的に説明する。実施例中の「部」及び「％」の記載は、特に断わりのない限り質量基準である。 Next, the present invention will be specifically described with reference to Examples and Comparative Examples. Descriptions of "part" and "%" in Examples are based on mass unless otherwise specified.
ＧＰＣの測定条件
測定装置 ：東ソー株式会社製「ＨＬＣ−８３２０ ＧＰＣ」、
カラム：東ソー株式会社製ガードカラム「ＨＸＬ−Ｌ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ４０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ３０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
検出器： ＲＩ（示差屈折計）
データ処理：東ソー株式会社製「ＧＰＣワークステーション ＥｃｏＳＥＣ−ＷｏｒｋＳｔａｔｉｏｎ」
測定条件： カラム温度 ４０℃
展開溶媒 テトラヒドロフラン
流速 １．０ｍｌ／分
標準 ： 前記「ＧＰＣ−８３２０」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
（使用ポリスチレン）
東ソー株式会社製「Ａ−５００」
東ソー株式会社製「Ａ−１０００」
東ソー株式会社製「Ａ−２５００」
東ソー株式会社製「Ａ−５０００」
東ソー株式会社製「Ｆ−１」
東ソー株式会社製「Ｆ−２」
東ソー株式会社製「Ｆ−４」
東ソー株式会社製「Ｆ−１０」
東ソー株式会社製「Ｆ−２０」
東ソー株式会社製「Ｆ−４０」
東ソー株式会社製「Ｆ−８０」
東ソー株式会社製「Ｆ−１２８」
試料 ： 樹脂固形分換算で１．０質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（５０μｌ）GPC measurement conditions Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation,
Column: Tosoh Co., Ltd. guard column "HXL-L"
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: "GPC workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of “GPC-8320”.
(Polystyrene used)
Tosoh Corporation "A-500"
Tosoh Corporation "A-1000"
Tosoh Corporation "A-2500"
Tosoh Corporation "A-5000"
Tosoh Corporation "F-1"
Tosoh Corporation "F-2"
Tosoh Corporation "F-4"
Tosoh Corporation "F-10"
Tosoh Corporation "F-20"
Tosoh Corporation "F-40"
Tosoh Corporation “F-80”
Tosoh Corporation "F-128"
Sample: 1.0% by mass of tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (50 μl)
溶融粘度測定法
本願実施例において活性エステル化合物或いは組成物の溶融粘度は、ＡＳＴＭ Ｄ４２８７に準拠し、１５０℃における溶融粘度をＩＣＩ粘度計にて測定した。Melt Viscosity Measurement Method In the examples of the present application, the melt viscosity of the active ester compound or composition was measured according to ASTM D4287, and the melt viscosity at 150 ° C. was measured with an ICI viscometer.
実施例１ 活性エステル組成物（１）の製造
温度計、滴下ロート、冷却管、分留管、攪拌器を取り付けたフラスコにジシクロペンタジエン付加型フェノール化合物（前記構造式（３）においてｍが０であり、数平均分子量（Ｍｎ）から算出されるｔの平均値が０．２であるもの、水酸基当量１６６．６ｇ/当量）３３３ｇとトルエン１６００ｇを仕込み、系内を減圧窒素置換しながら溶解させた。次いで、塩化ベンゾイル２１８ｇを仕込み、系内を減圧窒素置換しながら溶解させた。テトラブチルアンモニウムブロマイド０．８ｇを加え、窒素ガスパージを施しながら、系内を６０℃以下に制御して、２０％水酸化ナトリウム水溶液４２０ｇを３時間かけて滴下した。滴下終了後、そのまま１時間撹拌を続けて反応させた。反応終了後、反応混合物を静置して分液し、水層を取り除いた。残った有機層に水を加えて約１５分間攪拌混合した後、混合物を静置して分液し、水層を取り除いた。水層のｐＨが７になるまでこの操作を繰り返した後、デカンタ脱水で水分とトルエンを除去し、活性エステル組成物（１）を得た。活性エステル組成物（１）のＧＰＣチャート図を図１に示す。ＧＰＣチャート図の面積比から算出される活性エステル組成物（１）中のジエステル化合物の含有量は７７％、前記構造式（４）においてｔが１である化合物に相当する成分の含有量は１５％であった。また、活性エステル組成物（１）の溶融粘度は１．４８ｄＰａ・ｓであった。Example 1 Production of Active Ester Composition (1) A dicyclopentadiene-added phenol compound was added to a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer (m is 0 in the above structural formula (3). And the average value of t calculated from the number average molecular weight (Mn) is 0.2, 333 g of hydroxyl group equivalent (166.6 g / equivalent) and 1600 g of toluene are charged, and the system is dissolved under reduced pressure nitrogen substitution. It was Next, 218 g of benzoyl chloride was charged, and the system was dissolved while substituting nitrogen under reduced pressure. Tetrabutylammonium bromide (0.8 g) was added, the system was controlled at 60 ° C. or lower while purging with nitrogen gas, and 20% aqueous sodium hydroxide solution (420 g) was added dropwise over 3 hours. After completion of the dropping, stirring was continued for 1 hour to carry out the reaction. After completion of the reaction, the reaction mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Water was added to the remaining organic layer, and the mixture was stirred and mixed for about 15 minutes, and then the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. After repeating this operation until the pH of the aqueous layer reached 7, water and toluene were removed by decanter dehydration to obtain an active ester composition (1). A GPC chart diagram of the active ester composition (1) is shown in FIG. The content of the diester compound in the active ester composition (1) calculated from the area ratio in the GPC chart is 77%, and the content of the component corresponding to the compound in which t is 1 in the structural formula (4) is 15%. %Met. The melt viscosity of the active ester composition (1) was 1.48 dPa · s.
比較製造例１ 活性エステル化合物（１’）の製造
温度計、滴下ロート、冷却管、分留管、攪拌器を取り付けたフラスコにイソフタル酸クロリド２０２ｇとトルエン１２５０ｇを仕込み、系内を減圧窒素置換しながら溶解させた。次いで、１−ナフトール２８８ｇを仕込み、系内を減圧窒素置換しながら溶解させた。テトラブチルアンモニウムブロマイド０．６ｇを加え、窒素ガスパージを施しながら、系内を６０℃以下に制御して、２０％水酸化ナトリウム水溶液４２０ｇを３時間かけて滴下した。滴下終了後、そのまま１時間撹拌を続けて反応させた。反応終了後、反応混合物を静置して分液し、水層を取り除いた。残った有機層に水を加えて約１５分間攪拌混合した後、混合物を静置して分液し、水層を取り除いた。水層のｐＨが７になるまでこの操作を繰り返した後、デカンタ脱水で水分とトルエンを除去し、活性エステル化合物（１’）を得た。活性エステル化合物（１’）の溶融粘度は０．６５ｄＰａ・ｓであった。Comparative Production Example 1 Production of Active Ester Compound (1 ′) 202 g of isophthalic chloride and 1250 g of toluene were charged into a flask equipped with a thermometer, a dropping funnel, a cooling pipe, a fractionating pipe, and a stirrer, and the system was replaced with nitrogen under reduced pressure. While dissolving. Next, 288 g of 1-naphthol was charged, and the system was dissolved while substituting nitrogen under reduced pressure. Tetrabutylammonium bromide (0.6 g) was added, and the inside of the system was controlled at 60 ° C or lower while purging with nitrogen gas, and 20% aqueous sodium hydroxide solution (420 g) was added dropwise over 3 hours. After completion of the dropping, stirring was continued for 1 hour to carry out the reaction. After completion of the reaction, the reaction mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Water was added to the remaining organic layer, and the mixture was stirred and mixed for about 15 minutes, and then the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. After repeating this operation until the pH of the aqueous layer reached 7, water and toluene were removed by decanter dehydration to obtain an active ester compound (1 ′). The melt viscosity of the active ester compound (1 ′) was 0.65 dPa · s.
実施例２及び比較例１
下記表１に示す割合で各成分を配合して硬化性組成物を製造し、下記要領で評価試験を行った。結果を表１に示す。Example 2 and Comparative Example 1
A curable composition was produced by mixing the components in the proportions shown in Table 1 below, and an evaluation test was conducted according to the following procedure. The results are shown in Table 1.
高温条件下での貯蔵弾性率の測定
硬化性組成物を型枠へ流し込み、プレス機を用いて１７５℃の温度で１０分間成型した。型枠から成型物を取り出し、１７５℃の温度で５時間硬化させて硬化物を得た。
前記硬化物から５ｍｍ×５４ｍｍ×２．４ｍｍサイズの試験片を切り出した。試験片について、粘弾性測定装置（レオメトリック社製「固体粘弾性測定装置ＲＳＡＩＩ」）を用い、レクタンギュラーテンション法、周波数１Ｈｚ、昇温温度３℃／分の条件で、２６０℃における貯蔵弾性率を測定した。Measurement of storage elastic modulus under high temperature conditions The curable composition was poured into a mold and molded at a temperature of 175 ° C for 10 minutes using a press machine. The molded product was taken out of the mold and cured at 175 ° C. for 5 hours to obtain a cured product.
A test piece having a size of 5 mm × 54 mm × 2.4 mm was cut out from the cured product. For the test piece, using a viscoelasticity measuring device (“solid viscoelasticity measuring device RSAII” manufactured by Rheometric Co., Ltd.), the storage elastic modulus at 260 ° C. was measured under the conditions of rectangular tension method, frequency 1 Hz, temperature rising temperature 3 ° C./min. It was measured.
銅箔密着性の評価
真空成型機（株式会社名機製作所製「ＭＨＰＣ−ＶＦ」）を用いて、金型温度１７５℃、成形圧力０．４ＭＰａ、硬化時間９０分の条件で、銅箔と硬化物の積層体を製造した。
先で得た積層体から幅７ｍｍ、長さ２００ｍｍサイズの試験片を切り出し、ＪＩＳ Ｋ ６８５４に準拠して、剥離速度５０ｍｍ/分条件にて銅箔のピール強度を測定した。Evaluation of Copper Foil Adhesion Using a vacuum forming machine (“MHPC-VF” manufactured by Meiki Seisakusho Co., Ltd.), it was cured with a copper foil under conditions of a mold temperature of 175 ° C., a molding pressure of 0.4 MPa and a curing time of 90 minutes. A laminate of products was manufactured.
A test piece with a width of 7 mm and a length of 200 mm was cut out from the laminate obtained above, and the peel strength of the copper foil was measured under a peeling speed of 50 mm / min according to JIS K 6854.
エポキシ樹脂（＊１）：クレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製「Ｎ−６５５−ＥＸＰ−Ｓ」、エポキシ当量２０２ｇ/当量） Epoxy resin (* 1): Cresol novolac type epoxy resin ("N-655 EXP-S" manufactured by DIC Corporation, epoxy equivalent 202 g / equivalent)
Claims (5)
で表されるジヒドロキシ化合物（ａ１）と芳香族モノカルボン酸又はその酸ハロゲン化物（ａ２）とのジエステル化物である活性エステル化合物。The following structural formula (1)
An active ester compound which is a diester compound of a dihydroxy compound (a1) represented by and an aromatic monocarboxylic acid or an acid halide thereof (a2).
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