CN117043220A - Phenol resin mixture, curable resin composition, and cured product thereof - Google Patents
Phenol resin mixture, curable resin composition, and cured product thereof Download PDFInfo
- Publication number
- CN117043220A CN117043220A CN202280023933.5A CN202280023933A CN117043220A CN 117043220 A CN117043220 A CN 117043220A CN 202280023933 A CN202280023933 A CN 202280023933A CN 117043220 A CN117043220 A CN 117043220A
- Authority
- CN
- China
- Prior art keywords
- group
- phenol resin
- resin composition
- present application
- 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.)
- Pending
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- 239000005011 phenolic resin Substances 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 239000011342 resin composition Substances 0.000 title claims description 41
- -1 bisphenol compound Chemical class 0.000 claims abstract description 40
- 125000001424 substituent group Chemical group 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 9
- 125000003277 amino group Chemical group 0.000 claims abstract description 8
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims abstract description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 8
- 125000002560 nitrile group Chemical group 0.000 claims abstract description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 8
- 239000003822 epoxy resin Substances 0.000 claims description 30
- 229920000647 polyepoxide Polymers 0.000 claims description 30
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- 239000004065 semiconductor Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 13
- 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 13
- 238000002156 mixing Methods 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000011256 inorganic filler Substances 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910003475 inorganic filler Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000004305 biphenyl Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 239000003566 sealing material Substances 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- 239000004848 polyfunctional curative Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 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 5
- 238000007789 sealing Methods 0.000 description 5
- 125000000547 substituted alkyl group Chemical group 0.000 description 5
- 238000001721 transfer moulding Methods 0.000 description 5
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 4
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 4
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 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 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical class C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- QEFMDEFYYCMJPY-UHFFFAOYSA-N 1-(chloromethyl)-2-phenylbenzene Chemical group ClCC1=CC=CC=C1C1=CC=CC=C1 QEFMDEFYYCMJPY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- AORTZIIKTZPIQU-UHFFFAOYSA-N 3-butyl-4-methyloxolane-2,5-dione Chemical compound CCCCC1C(C)C(=O)OC1=O AORTZIIKTZPIQU-UHFFFAOYSA-N 0.000 description 2
- IXCOKTMGCRJMDR-UHFFFAOYSA-N 9h-fluorene;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=C2CC3=CC=CC=C3C2=C1 IXCOKTMGCRJMDR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229960004232 linoleic acid Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011208 reinforced composite material Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- FWHUTKPMCKSUCV-UHFFFAOYSA-N 1,3-dioxo-3a,4,5,6,7,7a-hexahydro-2-benzofuran-5-carboxylic acid Chemical compound C1C(C(=O)O)CCC2C(=O)OC(=O)C12 FWHUTKPMCKSUCV-UHFFFAOYSA-N 0.000 description 1
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 1
- DAJPMKAQEUGECW-UHFFFAOYSA-N 1,4-bis(methoxymethyl)benzene Chemical compound COCC1=CC=C(COC)C=C1 DAJPMKAQEUGECW-UHFFFAOYSA-N 0.000 description 1
- SSPMJQOASMQREI-UHFFFAOYSA-N 1-(methoxymethyl)-2-phenylbenzene Chemical group COCC1=CC=CC=C1C1=CC=CC=C1 SSPMJQOASMQREI-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- ZCFREEKATLZMOJ-UHFFFAOYSA-N 2,2,2-triphenylethylphosphane Chemical class C=1C=CC=CC=1C(C=1C=CC=CC=1)(CP)C1=CC=CC=C1 ZCFREEKATLZMOJ-UHFFFAOYSA-N 0.000 description 1
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 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 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
- MOSSLXZUUKTULI-UHFFFAOYSA-N 3-[3-(2,5-dioxopyrrol-3-yl)-4-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC=C(C=2C(NC(=O)C=2)=O)C=C1C1=CC(=O)NC1=O MOSSLXZUUKTULI-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- AZZWZMUXHALBCQ-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CC=2C=C(C)C(O)=C(C)C=2)=C1 AZZWZMUXHALBCQ-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 1
- RPJFWRZEEKJTGN-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=CC(O)=CC=2)=C1 RPJFWRZEEKJTGN-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 102000016387 Pancreatic elastase Human genes 0.000 description 1
- 108010067372 Pancreatic elastase Proteins 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 101001059734 Thermococcus litoralis (strain ATCC 51850 / DSM 5473 / JCM 8560 / NS-C) Trehalose/maltose-binding protein MalE Proteins 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- BNQRPLGZFADFGA-UHFFFAOYSA-N benzyl(triphenyl)phosphanium Chemical class C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 BNQRPLGZFADFGA-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- RKMJXTWHATWGNX-UHFFFAOYSA-N decyltrimethylammonium ion Chemical class CCCCCCCCCC[N+](C)(C)C RKMJXTWHATWGNX-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- GQKZBCPTCWJTAS-UHFFFAOYSA-N methoxymethylbenzene Chemical compound COCC1=CC=CC=C1 GQKZBCPTCWJTAS-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- VWBWQOUWDOULQN-UHFFFAOYSA-N nmp n-methylpyrrolidone Chemical compound CN1CCCC1=O.CN1CCCC1=O VWBWQOUWDOULQN-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical class CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 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
- 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 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The phenol resin mixture of the present application contains a phenol resin (A) represented by the following formula (1) or (2) and an alkyl-substituted bisphenol compound (B), and the weight ratio of the component (A) to the component (B) is 95/5 to 55/45.(in the formula (1), a plurality of R's are present 1 P are each independently present, R 1 Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, an amine group, or a phenyl group which may have the same substituent as the foregoing, and p is a real number of 0 to 3; n is a repetition number, which is a real number of 1 to 20).In the formula (2), a plurality of R's are present 1 P are each independently present, R 1 Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, an amine group, or a phenyl group which may have the same substituent as the foregoing, and p is a real number of 0 to 3; n is a repetition number, which is a real number of 1 to 20).
Description
Technical Field
The present application relates to a phenol resin mixture, a curable resin composition, and a cured product thereof.
Background
In the field of semiconductor sealing materials, phenol resins are used as hardeners for epoxy resins. In recent years, various properties such as moisture resistance, adhesion, dielectric properties, low viscosity for highly filling a filler (inorganic or organic filler), and reactivity for shortening a molding cycle have been required to be further improved in order to achieve higher purity of the resin composition.
Further, the shape of the semiconductor package has a complexity of thinning, stacking, systemizing, and three-dimensional formation along with the transition, and the Wire wiring is also being made to be narrow-pitch and thin-line, so that if fluidity of the resin composition is not preferable, wire sweep (Wire sweep) is caused. In addition, a burden is imposed on the connection portion of the wire, which causes adverse effects.
In addition, in the flip-chip package, a so-called mold underfill (hereinafter referred to as "MUF") method of sealing at one time without using the underfill has been attracting attention from the viewpoint of a low-cost manufacturing method. In this method, it is necessary to pass the resin through an extremely narrow gap between the chip and the package substrate, and therefore, the miniaturization of the filler is important, and on the other hand, the surface area is increased due to the miniaturization of the filler, which increases the viscosity of the system and causes the occurrence of voids (gaps).
In addition, among sealing resins used in rewiring layers such as wafer level packaging and related insulating films used in build-up layers, the thickness of the layers must be thin, and also, in order to reduce the coefficient of linear expansion, it is necessary to fill with a fine filler, and therefore, there is a similar demand for a resin composition having a low viscosity.
[ Prior Art literature ]
[ non-patent literature ]
[ non-patent document 1] "2008 STRJ report semiconductor blueprint specialty Commission 2008 report", eighth chapter, p1-1, [ online ],2009, 3 th month, JEITA (company) institute of electronic information technology industry semiconductor technology blueprint specialty Commission [ search 5, 30 th day 2012 ], < http:// STRJ-jeita.elastase. Net/STRJ/nenjihoukou-2008 cfm ]
[ non-patent document 2] Gao Cangxin et al, pine electric engineering report vehicle related device technical vehicle high Wen Dongzuo IC, no. 74, japanese, 5/31/2001, pages 35-40
[ patent literature ]
Patent document 1 Japanese patent laid-open No. 2003-41096
[ patent document 2] Japanese patent application laid-open No. 2013-87137.
Disclosure of Invention
[ problem to be solved by the application ]
Various methods for reducing the viscosity have been proposed, but generally, a method for reducing the viscosity by reducing the molecular weight of an epoxy resin or a phenol resin is used. However, when the molecular weight of the epoxy resin or phenol resin is reduced, the resin composition is easy to store and handle because the resin composition is easy to store because the resin composition has a shape at room temperature (20 ℃ C. In the present application) that is easy to flow and difficult to handle at room temperature (liquid to gel to semi-solid, etc.).
Specifically, when a composition manufacturer purchases a material from a resin manufacturer, the material must be transported in frozen form, and thus a large amount of energy is consumed. In addition, the temperature rises during transportation and the caking (lumping) causes it to fail to operate. In addition, even though there is no problem in the transportation step, the composition cannot be used without returning to room temperature when it is used by a manufacturer of the composition, and there are problems such as dew condensation or caking when it returns to room temperature, and blockage of the inlet of the hopper when it is fed. Further, even if the resin composition is pulverized by a ball mill or the like for homogeneous mixing, the resin composition cannot be pulverized, and the resin composition may be agglomerated in a kettle, and the apparatus may be broken. The same problem also occurs with the finished composition.
For the above problems, the use of crystalline epoxy resins has been studied (patent document 1). However, the following problems remain: the fluidity is limited in the course of molding, and it is difficult to maintain the handling characteristics after the composition is formed because the crystallinity is destroyed by mixing with the phenol resin. In general, when a crystalline epoxy resin is used, if the crystalline epoxy resin is not kneaded at a temperature equal to or higher than the melting point of the crystalline epoxy resin during melt kneading by a kneader, the epoxy resin is not sufficiently melted and is not uniformly dispersed, and thus a molded article of an epoxy resin molding material obtained by using the melted mixture becomes uneven, and the strength of the molded article varies from part to part, resulting in a decrease in the characteristics of a semiconductor device. However, when the temperature of the molten mixture is high during melt kneading, hardening reaction proceeds in the kneader, and fluidity is lowered, which may cause generation of gel or the like, which may cause unfilling during molding. Or recrystallization is caused by the high crystallinity, and even if crystallinity remains after heating and kneading, the remaining crystals are first melted during molding, and there is a concern that the hardenability is low, burrs or holes are generated, and the formability of the obtained semiconductor device is deteriorated such as wrinkles easily formed on the surface.
On the other hand, although attempts have been made to introduce crystallinity into a phenol resin, there is a problem that it is difficult to obtain a homogeneous resin composition because of local crystallization due to a high degree of crystallinity. In order to solve the problem of incomplete dissolution when using a crystalline phenol compound, patent document 2 discloses that a quaternary phosphonium compound in a molten state is used as a solvent, and the crystalline phenol compound is completely dissolved in the solvent, thereby obtaining a molten mixture excellent in storage stability without incomplete dissolution. However, since the hardening accelerator must be dissolved by heating, a sufficient amount of the crystalline phenol compound cannot be added.
The present inventors have studied in detail in view of the above-described actual conditions, and have found a phenol resin mixture which is free from tackiness at 20 ℃ and has both fluidity and handleability, and have further completed the present application.
[ means for solving the problems ]
That is, the present application relates to the following [1] to [5].
[1]
A phenol resin mixture comprising a phenol resin (A) represented by the following formula (1) or (2) and an alkyl-substituted bisphenol compound (B) in a weight ratio of 95/5 to 55/45.
(in the formula (1), a plurality of R's are present 1 P are each independently present, R 1 Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, an amine group, or a phenyl group which may have the same substituent as the foregoing, and p is a real number of 0 to 3; n is a repetition number, which is a real number of 1 to 20).
(in the formula (2), a plurality of R's are present 1 P are each independently present, R 1 Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, an amine group, or a phenyl group which may have the same substituent as the foregoing, and p is a real number of 0 to 3; n is a repetition number, which is a real number of 1 to 20).
[2]
The phenol resin mixture as described in the preceding item [1], wherein the melting point of the aforementioned alkyl-substituted bisphenol compound (B) is 70 to 180 ℃.
[3]
The phenol resin mixture as described in the preceding item [1] or [2], which has ICI melt viscosity (cone-plate method) of 0.001 to 0.20 Pa.s at 150 ℃.
[4]
A curable resin composition comprising the phenol resin mixture of any one of the preceding items [1] to [3] and an epoxy resin.
[5]
A cured product obtained by curing the curable resin composition according to item [4 ].
[ Effect of the application ]
The phenol resin mixture of the present application is useful for various composite materials, adhesives, paints, etc. including insulating materials for electric and electronic parts, laminated boards (printed wiring boards, build-up boards, etc.), and carbon fiber reinforced composite materials (hereinafter also referred to as "CFRP"), because of extremely high flowability and excellent handling characteristics, and contributes to productivity. Particularly useful as a semiconductor sealing material for protecting semiconductor elements.
Detailed Description
The phenol resin mixture of the present application contains a phenol resin represented by the following formula (1) or (2) (hereinafter also referred to as component (a)) and an alkyl-substituted bisphenol compound (B) (hereinafter also referred to as component (B)).
(in the formula (1), a plurality of R's are present 1 P are each independently present, R 1 Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, an amine group, or a phenyl group which may have the same substituent as the foregoing, and p is a real number of 0 to 3; n is a repetition number, which is a real number of 1 to 20).
(in the formula (2), a plurality of R's are present 1 P are each independently present, R 1 Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, an amine group, or a phenyl group which may have the same substituent as the foregoing, and p is a real number of 0 to 3; n is a repetition number, which is a real number of 1 to 20).
R in the above formula (1) and formula (2) 1 More preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, still more preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, particularlyPreferably a hydrogen atom. p is more preferably a real number of 0 or 1, and particularly preferably 0.
The value of n in the above formulae (1) and (2) is a number average molecular weight obtained by measurement by gel permeation chromatography (GPC, detector: RI) of phenol resin, or can be calculated from the area ratio of the separated peaks.
The value of n in the above formulas (1) and (2) is usually 1 to 20, more preferably 1.1 to 20, and still more preferably 1.1 to 10. When n is less than 1, the crystallinity is strong, and even if mechanical kneading is performed, a homogeneous resin mixture cannot be obtained. On the other hand, when n is more than 20, the melt viscosity is high, and the use thereof is not easy from the viewpoints of fluidity and high filler content.
The phenol resins represented by the above formula (1) and formula (2) can be synthesized by a known synthesis method, and are also easily available on the market. For example, KAYAHARD GPH-65 (softening point 65 ℃ C. Manufactured by Japanese chemical Co., ltd.) can be obtained as the phenol resin represented by the above formula (1), and MEHC-7840-4S (softening point 58-65 ℃ C. Manufactured by Ming' S chemical Co., ltd.) can be obtained as the phenol resin represented by the above formula (2).
In the phenol resin mixture of the present application, the method of mixing the component (a) and the component (B) is not particularly limited, and the phenol resin mixture can be obtained by melt-mixing at a temperature of about 150 ℃ or higher than the melting point of both, kneading/mixing at a temperature of not higher than the melting point by using an extruder, a kneader, a roll or the like, and the like.
The weight ratio of the component (A) to the component (B) is usually 95/5 to 55/45, more preferably 92/8 to 55/45, still more preferably 90/10 to 60/40. If the weight ratio of the component (A) is more than 95, fluidity becomes poor. On the other hand, if the weight ratio of the component (a) is less than 55, a part of the phenol resin mixture is unevenly crystallized at 20 ℃, resulting in difficulty in producing a homogeneous cured product of the molding material. That is, by making the weight ratio of the component (A) to the component (B) 95/5 to 55/45, there is no tackiness at 20℃and fluidity at high temperature, and thus fluidity and handleability can be achieved.
From the viewpoint of fluidity at high temperature, the ICI melt viscosity (cone-plate method) of the phenol resin mixture of the present application at 150 ℃ is more preferably 0.001 to 0.20pa·s, still more preferably 0.005 to 0.15pa·s, particularly preferably 0.01 to 0.10pa·s.
The melting point of the component (B) is usually 70 to 180 ℃, more preferably 100 to 180 ℃, still more preferably 120 to 180 ℃. Below 70 c, sticking is generated at room temperature and is difficult to handle. Above 300 c, crystals are not easily melted during mixing.
The melting point can be obtained from the endothermic peak temperature using a commercially available Differential Scanning Calorimeter (DSC), for example.
In order to improve fluidity, the molecular weight of the component (B) is preferably small, more preferably 200 to 400, and even more preferably 214 to 400.
In addition, the hydroxyl equivalent of the component (B) is more preferably 100 to 200g/eq., still more preferably 110 to 175g/eq., particularly preferably 120 to 150g/eq.
The component (B) is not particularly limited as long as it is a bisphenol compound having an alkyl substituent. Specific examples may include: resins such as bisphenol a type resins, bisphenol F type resins, bisphenol E type resins, bisphenol Z type resins having an alkyl substituent are applicable to alkyl-substituted bisphenol a type resins and bisphenol F type resins.
In addition, in the component (B), the number of substituted alkyl groups is more preferably 2 to 6. From the viewpoint of crystallinity, the number of substituted alkyl groups is more preferably an even number of 2, 4, 6. The substituted alkyl group is more preferably an alkyl group having 1 to 6 carbon atoms, and methyl, ethyl, phenyl, or allyl groups are exemplified.
Specific examples thereof include: dimethyl bisphenol a, tetramethyl bisphenol a, diallyl bisphenol a, diethyl bisphenol a, tetraethyl bisphenol a, diphenyl bisphenol a, dimethyl bisphenol F, tetramethyl bisphenol F, diallyl bisphenol F, diethyl bisphenol F, tetraethyl bisphenol F, diphenyl bisphenol F, and the like.
In the present application, when the substituted alkyl group is a methyl group or an ethyl group, a bisphenol compound having a 4 to 6 substitution pattern is more preferable, and when the substituted alkyl group is a phenyl group or an allyl group, a bisphenol compound having a 2 substitution pattern is more preferable. In the case of the 2-substituted form of methyl or ethyl having a small alkyl group, the reactivity is high, and even when the molecular weight is small and the initial viscosity is low, the reactivity is high, and as a result, the fluidity may be lowered.
On the other hand, if the substituent is a large phenyl group or allyl group, the effect is large, and if a 4-substitution is formed, the reaction may be difficult. The total carbon number of the substituents is more preferably 2 to 12, particularly preferably 4 to 10.
The component (B) used in the present application may be a commercially available product, or may be a component (B) produced by a known method. Specific examples of commercially available products include: 3,3 '-dimethyl-4, 4' -bisphenol A (total carbon number 2 of the hydroxyl equivalent 128 substituent having a melting point of 136 ℃ C. And a molecular weight of 256.34, manufactured by Tokyo chemical industry Co., ltd.), 3 '-dimethyl-4, 4' -bisphenol F (total carbon number 2 of the hydroxyl equivalent 114 substituent having a molecular weight of 228.29, a melting point of 126 ℃ C. And a molecular weight of 3,3', 5' -tetramethyl-4, 4 '-bisphenol A (total carbon number 4 of the hydroxyl equivalent 142 substituent having a melting point of 165 ℃ C. And a molecular weight of 284.40, manufactured by DEEPAK), 3',5 '-tetramethyl-4, 4' -bisphenol F (total carbon number 4 of the hydroxyl equivalent 128 substituent having a melting point of 284.40, manufactured by DEEPAK), and the like, but are not limited thereto.
The curable resin composition of the present application contains an epoxy resin.
Specific examples of the epoxy resin that can be used include: novolac type epoxy resins, bisphenol a type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins, and the like. Specific examples thereof include: bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4 '-biphenol, 2' -biphenol, 3',5,5' -tetramethyl- [1,1 '-biphenyl ] -4,4' -diol, hydroquinone, resorcinol, naphthalene diol, ginseng- (4-hydroxyphenyl) methane, halogenated bisphenols such as 1, 2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.), and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furan aldehyde, 4 '-bis (chloromethyl) -1,1' -biphenyl, 4 '-bis (methoxymethyl) -1,1' -biphenyl, 1, 4-bis (chloromethyl) benzene, polycondensates of 1, 4-bis (methoxymethyl) benzene, etc., halogenated bisphenols such as tetrabromobisphenol A, epoxypropyl etherified compounds derived from alcohols, alicyclic epoxy resins, epoxypropyl-series epoxy resins, liquid epoxy resins such as silsesquioxane resins (epoxypropyl-series epoxy resins having a solid or epoxypropyl-and/or epoxysiloxane structure in chain, cyclic, ladder-like, or at least 2-series epoxy resins, but are not limited to these.
However, the softening point at the time of melt-mixing all of the epoxy resins to be used is more preferably 40 to 180 ℃. Particularly preferably from 40 to 150 ℃.
The curable resin composition of the present application may contain an inorganic filler. Examples of the inorganic filler include: crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, magnesium silicate, steatite, spinel, titanium dioxide, talc, or other powders or these spheroidized beads, etc., but are not limited thereto. These may be used alone or in combination of 2 or more. In the present application, in the case of being preset for a semiconductor sealing material, crystalline silica, fused silica, and alumina are more preferable from the viewpoint of balance of characteristics.
The content of these inorganic fillers is more preferably 70 to 96 mass% based on 100 mass% of the curable resin composition of the present application. Particularly preferably 70 to 93 mass%. In the present application, since the fluidity is extremely high, if the amount of the inorganic filler is too small, the inorganic filler and the resin lose balance, and a large amount of the inorganic filler, a small amount of the inorganic filler, and the like appear in the molded article of the resin composition, which is not preferable in terms of characteristics.
In addition, if the content of the inorganic filler exceeds 96%, fluidity cannot be exhibited, which is not preferable.
In the curable resin composition of the present application, a phenol resin mixture is used as a curing agent for an epoxy resin. In the present application, as the hardener, not only the phenol resin mixture of the present application but also other hardeners may be used in combination.
Other hardeners that may be used are listed: the phenolic compounds other than the phenolic resin, amine compounds, acid anhydride compounds, amide compounds, carboxylic acid compounds, and the like of the present application. Examples of the phenol resin and phenol compound include: bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4 '-biphenol, 2' -biphenol, 4 '-dihydroxy-3, 3',5,5 '-tetramethylbiphenyl, 3' -dimethyl-4, 4 '-biphenol, 4' -dihydroxy-3, 3 '-diphenyldiphenyl, 3' -diallyl-4, 4 '-diphenyl, hydroquinone, resorcinol, naphthalene diol, ginseng- (4-hydroxyphenyl) methane, 1, 2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.), formaldehyde, acetaldehyde, benzaldehyde polycondensates of p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furan aldehyde, 4' -bis (chloromethyl) -1,1 '-biphenyl, 4' -bis (methoxymethyl) -1,1 '-bis (chloromethyl) benzene, 1,4' -bis (methoxymethyl) benzene and the like, modified products of these, halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes with phenols and the like, but are not limited to these. These may be used alone or in combination of 2 or more.
The phenol resin is preferably a phenol aralkyl resin (a resin having an aromatic alkylene structure), and particularly preferably a resin having the following constitution: the alkylene group which is a linking group of the alkylene group having at least one structure selected from phenol, naphthol and cresol is at least one structure selected from benzene, biphenyl and naphthalene (specifically, zylock, naphthol-Zylock, phenol-biphenylene novolac, cresol-biphenylene novolac, phenol-naphthol novolac, etc.).
Examples of the amine-based compound and the amide-based compound include: and nitrogen-containing compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and polyamide resins synthesized from dimers of linoleic acid (linolic acid) and ethylenediamine.
Examples of the acid anhydride-based compound and carboxylic acid-based compound include: anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2, 1] heptane-2, 3-dicarboxylic anhydride, methylbicyclo [2, 1] heptane-2, 3-dicarboxylic anhydride, cyclohexane-1, 3, 4-tricarboxylic acid-3, 4-anhydride, and the like; carboxylic acid resins obtained by addition reaction of various alcohol-and methanol-modified polysilicones with the aforementioned acid anhydrides.
Other examples are: imidazole, boron trifluoride-amine complex, guanidine derivative compound, and the like.
The other hardening agents are not limited to these, and these may be used alone or 2 or more kinds thereof may be used. In the present application, the use of a phenol compound is more preferable in terms of reliability in particular.
In the curable resin composition of the present application, the amount of the epoxy resin and the hardener used is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy groups of all the epoxy resins. When the amount of the epoxy group is less than 0.7 equivalent or exceeds 1.2 equivalent, the curing is not complete, and good curing properties cannot be obtained.
The curable resin composition of the present application may further contain a curing accelerator.
Specific examples of the hardening accelerator that can be used include: imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, tertiary amines such as 2- (dimethylaminomethyl) phenol and 1, 8-diaza-bicyclo (5, 4, 0) undecene-7, phosphines such as triphenylphosphine, quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethyl ammonium salt, trimethyldecyl ammonium salt and cetyltrimethylammonium salt, quaternary phosphonium salts such as triphenylbenzyl phosphonium salt, triphenylethyl phosphonium salt and tetrabutylphosphonium salt. The counter ion of the quaternary salt is halogen, organic acid ion, hydroxide ion, or the like, and although not particularly specified, organic acid ion or hydroxide ion is particularly preferable. Examples thereof include metal compounds such as tin octoate. The amount of the hardening accelerator to be used is 0.01 to 5.0 parts by mass based on 100 parts by mass of the epoxy resin.
In addition, various blending agents such as silane coupling agents, stearic acid, palmitic acid, zinc stearate, calcium stearate and the like, surfactants, dyes, pigments, ultraviolet absorbers and various thermosetting resins can be added to the curable resin composition of the present application.
The curable resin composition of the present application may be formulated with a binder resin as required. The binder resin may be exemplified by: the butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, polyamide resin, polyimide resin, silicone resin, and the like, but are not limited thereto. The amount of the binder resin to be blended is preferably in the range of not impairing the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by mass, more preferably 0.05 to 20 parts by mass, based on 100 parts by mass of the resin component, as required.
The curable resin composition of the present application can be formulated into a known maleimide compound according to the need. Specific examples of the maleimide compound that can be used include: 4,4' -diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2' -bis [4- (4-maleimide phenoxy) phenyl ] propane, 3' -dimethyl-5, 5' -diethyl-4, 4' -diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 4' -diphenyl ether bismaleimide, 4' -diphenyl sulfone bismaleimide, 1, 3-bis (3-maleimide phenoxy) benzene, 1, 3-bis (4-maleimide phenoxy) benzene, biphenyl aralkyl maleimide and the like, but are not limited thereto. These may be used alone or in combination of 2 or more. In the preparation of the maleimide compound, a hardening accelerator may be optionally prepared, and the radical polymerization initiator such as the hardening accelerator, the organic oxide, and the azo compound may be used.
The curable resin composition of the present application can be obtained by uniformly mixing the above components at a predetermined ratio, and is usually obtained by pre-curing at 130 to 180℃for 30 to 500 seconds, then post-curing at 150 to 200℃for 2 to 15 hours, and then performing a sufficient curing reaction to obtain the cured product of the present application. In addition, the components of the curable resin composition may be uniformly dispersed or dissolved in a solvent or the like, and then post-curing may be performed by removing the solvent.
The curable resin composition of the present application thus obtained has moisture resistance, heat resistance, high adhesion, low dielectric constant, and low dielectric loss tangent. Therefore, the curable resin composition of the present application is useful in a wide range of fields where moisture resistance, heat resistance, high adhesion, low dielectric constant, and low dielectric loss tangent are required. Specifically, the material can be used as a material for all electric/electronic parts such as insulating materials, laminated boards (printed wiring boards, BGA substrates, build-up substrates, etc.), sealing materials, and photoresists. In addition, the material can be used in the fields of coating materials, adhesives, 3D printing and the like besides forming materials and composite materials. In particular, reflow resistance is an advantageous property in semiconductor sealing.
The semiconductor device has a structure in which the curable resin composition of the present application is sealed. The semiconductor device may be exemplified by: DIP (Dual Inline Package), quad flat Package (QFP, quad Flat Package), ball Grid Array (BGA), chip scale Package (CSP, chip Size Package), small Out-Line Package (SOP), thin Small outline Package (TSOP, thin Small Outline Package), thin quad flat Package (TQFP, thin Quad Flat Package), and the like.
The method for preparing the curable resin composition of the present application is not particularly limited, and the components may be dispersed or dissolved in a solvent or the like, and the solvent may be distilled off as needed to prepare the composition by uniformly mixing the components, or may be prepolymerized. For example, the phenol resin mixture of the present application is heated in the presence or absence of a solvent, and a hardener such as an epoxy resin, an amine compound, a maleimide compound, a cyanate ester compound, a phenol resin, an acid anhydride compound, and other additives are added thereto to perform prepolymerization. The mixing or prepolymerization of the components is carried out in the absence of a solvent, for example, by using an extruder, kneader, roll or the like, or by using a reaction vessel equipped with a stirring device in the presence of a solvent.
As a method of uniformly mixing without using a solvent or the like, a kneading machine, a roll, a planetary mixer or the like is used to knead and mix at a temperature in the range of 50 to 100 ℃ to obtain a uniform curable resin composition. The obtained curable resin composition may be molded into a cylindrical ingot shape by a molding machine such as a tablet press after pulverization, or into a pellet-like powder or powder-like molded body, or into a sheet-like shape having a thickness of 0.05mm to 10mm by melting the composition on a surface support. The obtained molded article is tack-free at 0 to 20 ℃ and hardly has reduced fluidity and hardening properties even when stored at-25 to 0 ℃ for 1 week or more.
The molded article thus obtained can be molded into a cured product by a transfer molding machine or a compression molding machine.
The curable resin composition of the present application may be a varnish-like composition (hereinafter also simply referred to as varnish) by adding an organic solvent thereto. The curable resin composition of the present application may be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone (Methyl pyrrolidone) as a varnish, impregnated into a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and dried by heating to obtain a prepreg, and the prepreg is subjected to hot press molding, thereby forming a cured product of the curable resin composition of the present application. In this case, the amount of the solvent is usually 10 to 70% by weight, and more preferably 15 to 70% by weight, based on the mixture of the curable resin composition of the present application and the solvent. If the amount of the solvent is less than this range, the varnish viscosity becomes high, the workability becomes poor, and if the amount of the solvent is large, voids are generated in the cured product. In addition, in the case of a liquid composition, a curable resin cured product containing carbon fibers can be obtained in this state, for example, by resin transfer molding (RTM, resin Transfer Molding).
The cured product of the present application can be used for various purposes.
For example, examples of the adhesive, paint, coating agent, molding material (including sheet, film, FRP, etc.), insulating material (including printed board, wire coating, etc.), and sealant include: other additives to resins and the like. Examples of the adhesive include adhesives for electronic materials, in addition to adhesives for civil engineering, construction, automobiles, general business and medical use. Among these, the adhesive for electronic materials includes: interlayer adhesives for multilayer substrates such as build-up substrates, die attach adhesives for semiconductors such as underfills, underfills for BGA reinforcement, mounting adhesives such as Anisotropic Conductive Films (ACF) and Anisotropic Conductive Pastes (ACP), and the like.
In particular, in the present application, the composition is mainly used as a sealing material for semiconductors, but the composition may be used as a substrate or as a Mold Underfill (MUF).
Specifically, the main uses of the sealant currently used include: for example, potting (dipping) for capacitors, transistors, diodes, light emitting diodes, ICs, LSI, etc., dipping, transfer molding sealing, sealing at the time of mounting IC packages such as QFP, BGA, CSP (including underfill for reinforcement), etc.
Examples (example)
The present application will be described more specifically by way of examples, and the following "parts" are mass parts unless otherwise specified. Furthermore, the present application is not limited to these examples.
Various analysis methods used in examples are described below.
ICI melt viscosity: according to JIS K7117-2 (ISO 3219)
Examples 1 to 6 and comparative examples 1 to 4
KAYAHARD GPH-65 (phenol resin represented by the above formula (1), manufactured by Japanese chemical Co., ltd., melting point 65 ℃ C.), MEHC-7840-4S (phenol resin represented by the above formula (2), manufactured by Ming Hei chemical Co., ltd., melting point 58-65 ℃ C.), 3', 5' -tetramethyl-4, 4' -bisphenol A (abbreviation: TMBPA, DEEPAK having a melting point of 165 ℃ and a total carbon number of the substituent having a molecular weight of 284.40 hydroxyl equivalent 142), 3', 5' -tetramethyl-4, 4' -bisphenol F (abbreviated as TMBPF, DEEPAK having a melting point of 175 ℃ and a total carbon number of the substituent having a molecular weight of 284.40 hydroxyl equivalent 128), and 4,4' -dihydroxy-3, 3', 5' -tetramethylbiphenyl (abbreviated as TMBP, manufactured by Tokyo chemical industry Co., ltd.) were melt-mixed at 150 ℃ for 30 minutes to prepare a phenol resin mixture.
[ appearance observation ]
The appearance of the resulting phenol resin mixture at room temperature (20 ℃) was visually observed.
The phenol resin mixture having no crystal block and having a uniform appearance was evaluated as "o", and the phenol resin mixture having a crystal block was evaluated as "x".
[ sticky feeling ]
The resultant ingot was evaluated for the sticking feeling on the surface. The evaluation method was to press the obtained ingot with a finger for 10 seconds, and the degree of adhesion of the coating film was evaluated based on this.
A dry, tack-free surface of o ….
Delta … is tacky but does not adhere to the finger.
X … is very sticky and adheres to the finger.
TABLE 1
Examples 7 and 8 and comparative example 5
[ cyclone test ]
The epoxy resin, the phenol resin mixture (examples 5, 6 and comparative example 2), the silica filler and the hardening accelerator were kneaded at 80℃for 25 minutes at the ratios shown in Table 2 using a mixing roll to mix. Then, a swirl test was performed under the following conditions using an archimedes screw die and a transfer molding machine.
And (3) a mold: obtained from EMMI-1-66
Mold temperature: 175 DEG C
Transfer pressure: 70kgf/cm 2
Pressure: 5t press, pan diameter: 30mm
Injection time: 1 second
Forming time: 120 seconds
[ gel time ]
The curable resin composition described in Table 2 was placed on a hot plate at 175℃with a metal spatula, and stirred with the metal spatula, and the time required for peeling off the sample from the hot plate or for the adhesion to disappear was measured.
In the swirl test, a larger value indicates better flowability. The gel time is a time from when the sealing material is heated at a fixed temperature to when fluidity is lost, and can be appropriately selected with respect to hardening characteristics.
TABLE 2
NC-3000: biphenyl aralkyl epoxy resin (manufactured by Japanese chemical Co., ltd., epoxy equivalent 277 g/eq)
MSR-2102: high purity spherical silica filler (Dragon Co., ltd.)
TPP: triphenylphosphine (pure chemical Co., ltd.)
From tables 1 and 2, it was confirmed that the phenol resin mixtures of the present application were excellent in handleability and fluidity.
Although the application has been described in detail with reference to particular aspects, those skilled in the art will appreciate that various changes and modifications can be made without departing from the spirit and scope of the application.
The present application is based on Japanese patent application (Japanese patent application No. 2021-048213) filed on 3/23 of 2021, the entire content of which is incorporated by reference. In addition, all references cited herein are the entire contents of the access references.
[ Industrial applicability ]
From the above, the phenol resin mixture of the present application has high fluidity and handleability, and is excellent in productivity and moldability. Therefore, the curable resin composition of the present application can be used as various composite materials, adhesives, paints, and the like, including insulating materials for electric and electronic parts, laminated boards (printed wiring boards, build-up boards, and the like), and carbon fiber reinforced composite materials (hereinafter also referred to as "CFRP"). Particularly useful as a semiconductor sealing material for protecting semiconductor elements.
Claims (5)
1. A phenol resin mixture comprising a phenol resin (A) represented by the following formula (1) or (2) and an alkyl-substituted bisphenol compound (B), the weight ratio of the component (A) to the component (B) being 95/5 to 55/45;
in the formula (1), a plurality of R's are present 1 P are each independently present, R 1 Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, an amine group, or a phenyl group which may have the same substituent as the foregoing, and p is a real number of 0 to 3; n is a repetition number, which is a real number of 1 to 20;
in the formula (2), a plurality of R's are present 1 P are each independently present, R 1 Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, an amine group, or a phenyl group which may have the same substituent as the foregoing, and p is a real number of 0 to 3; n is a repetition number, which is a real number from 1 to 20.
2. The phenol resin mixture according to claim 1, wherein the melting point of the aforementioned alkyl-substituted bisphenol compound (B) is 70 to 180 ℃.
3. The phenol resin mixture according to claim 1 or 2, wherein ICI melt viscosity (cone-plate method) at 150 ℃ is 0.001 to 0.20 Pa-s.
4. A curable resin composition comprising the phenol resin mixture according to any one of claims 1 to 3 and an epoxy resin.
5. A cured product obtained by curing the curable resin composition according to claim 4.
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JP2021048213 | 2021-03-23 | ||
JP2021-048213 | 2021-03-23 | ||
PCT/JP2022/010370 WO2022202335A1 (en) | 2021-03-23 | 2022-03-09 | Phenolic resin mixture, curable resin composition, and cured product thereof |
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KR (1) | KR20230158502A (en) |
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JP2003041096A (en) | 2001-07-31 | 2003-02-13 | Sumitomo Bakelite Co Ltd | Method for manufacturing epoxy resin molding material and semiconductor device |
JP2013006328A (en) * | 2011-06-23 | 2013-01-10 | Sumitomo Bakelite Co Ltd | Laminate, circuit board, and semiconductor package |
JP5899498B2 (en) | 2011-10-13 | 2016-04-06 | パナソニックIpマネジメント株式会社 | Epoxy resin composition for semiconductor encapsulation, method for producing the same, and semiconductor device |
JP6120363B2 (en) * | 2013-04-19 | 2017-04-26 | 日本化薬株式会社 | Epoxy resin, epoxy resin composition and cured product thereof |
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