JP6671958B2 - Phenol resin, epoxy resin, epoxy resin composition, prepreg and cured product thereof - Google Patents
Phenol resin, epoxy resin, epoxy resin composition, prepreg and cured product thereof Download PDFInfo
- Publication number
- JP6671958B2 JP6671958B2 JP2015541604A JP2015541604A JP6671958B2 JP 6671958 B2 JP6671958 B2 JP 6671958B2 JP 2015541604 A JP2015541604 A JP 2015541604A JP 2015541604 A JP2015541604 A JP 2015541604A JP 6671958 B2 JP6671958 B2 JP 6671958B2
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- JP
- Japan
- Prior art keywords
- epoxy resin
- group
- present
- substituted
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000003822 epoxy resin Substances 0.000 title claims description 105
- 229920000647 polyepoxide Polymers 0.000 title claims description 105
- 239000005011 phenolic resin Substances 0.000 title claims description 50
- 239000000203 mixture Substances 0.000 title claims description 44
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 229920001568 phenolic resin Polymers 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 239000004065 semiconductor Substances 0.000 claims description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 6
- 238000005538 encapsulation Methods 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- -1 phenol compound Chemical class 0.000 description 50
- 150000001875 compounds Chemical class 0.000 description 37
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000002904 solvent Substances 0.000 description 22
- 150000002989 phenols Chemical class 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 15
- 229910052698 phosphorus Inorganic materials 0.000 description 15
- 239000011574 phosphorus Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 238000006735 epoxidation reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000011256 inorganic filler Substances 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- 229910003475 inorganic filler Inorganic materials 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920005992 thermoplastic resin Polymers 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
- 239000002966 varnish Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical class C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 3
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000005882 aldol condensation reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical class C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- SULYEHHGGXARJS-UHFFFAOYSA-N 2',4'-dihydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1O SULYEHHGGXARJS-UHFFFAOYSA-N 0.000 description 2
- YNPDFBFVMJNGKZ-UHFFFAOYSA-N 2'-Hydroxy-5'-methylacetophenone Chemical compound CC(=O)C1=CC(C)=CC=C1O YNPDFBFVMJNGKZ-UHFFFAOYSA-N 0.000 description 2
- IXWOUPGDGMCKGT-UHFFFAOYSA-N 2,3-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1O IXWOUPGDGMCKGT-UHFFFAOYSA-N 0.000 description 2
- WNCNWLVQSHZVKV-UHFFFAOYSA-N 2,4,5-trihydroxybenzaldehyde Chemical compound OC1=CC(O)=C(C=O)C=C1O WNCNWLVQSHZVKV-UHFFFAOYSA-N 0.000 description 2
- IUNJCFABHJZSKB-UHFFFAOYSA-N 2,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C(O)=C1 IUNJCFABHJZSKB-UHFFFAOYSA-N 0.000 description 2
- CLFRCXCBWIQVRN-UHFFFAOYSA-N 2,5-dihydroxybenzaldehyde Chemical compound OC1=CC=C(O)C(C=O)=C1 CLFRCXCBWIQVRN-UHFFFAOYSA-N 0.000 description 2
- WZUODJNEIXSNEU-UHFFFAOYSA-N 2-Hydroxy-4-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C(O)=C1 WZUODJNEIXSNEU-UHFFFAOYSA-N 0.000 description 2
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- UCQUAMAQHHEXGD-UHFFFAOYSA-N 3',4'-dihydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C(O)=C1 UCQUAMAQHHEXGD-UHFFFAOYSA-N 0.000 description 2
- RGZHEOWNTDJLAQ-UHFFFAOYSA-N 3,4,5-trihydroxybenzaldehyde Chemical compound OC1=CC(C=O)=CC(O)=C1O RGZHEOWNTDJLAQ-UHFFFAOYSA-N 0.000 description 2
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 description 2
- DOZRDZLFLOODMB-UHFFFAOYSA-N 3,5-di-tert-Butyl-4-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC(C=O)=CC(C(C)(C)C)=C1O DOZRDZLFLOODMB-UHFFFAOYSA-N 0.000 description 2
- LUJMEECXHPYQOF-UHFFFAOYSA-N 3-hydroxyacetophenone Chemical compound CC(=O)C1=CC=CC(O)=C1 LUJMEECXHPYQOF-UHFFFAOYSA-N 0.000 description 2
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- FEUATHOQKVGPEK-UHFFFAOYSA-N 4-hydroxybenzene-1,3-dicarbaldehyde Chemical compound OC1=CC=C(C=O)C=C1C=O FEUATHOQKVGPEK-UHFFFAOYSA-N 0.000 description 2
- FZHSPPYCNDYIKD-UHFFFAOYSA-N 5-methoxysalicylaldehyde Chemical compound COC1=CC=C(O)C(C=O)=C1 FZHSPPYCNDYIKD-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- 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 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- UILPJVPSNHJFIK-UHFFFAOYSA-N Paeonol Chemical compound COC1=CC=C(C(C)=O)C(O)=C1 UILPJVPSNHJFIK-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical class C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-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
- OJOBTAOGJIWAGB-UHFFFAOYSA-N acetosyringone Chemical compound COC1=CC(C(C)=O)=CC(OC)=C1O OJOBTAOGJIWAGB-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- DFYRUELUNQRZTB-UHFFFAOYSA-N apocynin Chemical compound COC1=CC(C(C)=O)=CC=C1O DFYRUELUNQRZTB-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- 150000004074 biphenyls Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical compound CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- JVTZFYYHCGSXJV-UHFFFAOYSA-N isovanillin Chemical compound COC1=CC=C(C=O)C=C1O JVTZFYYHCGSXJV-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 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
- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 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
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 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
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-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
- 150000007522 mineralic acids Chemical class 0.000 description 1
- GVYLCNUFSHDAAW-UHFFFAOYSA-N mirex Chemical compound ClC12C(Cl)(Cl)C3(Cl)C4(Cl)C1(Cl)C1(Cl)C2(Cl)C3(Cl)C4(Cl)C1(Cl)Cl GVYLCNUFSHDAAW-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 150000004002 naphthaldehydes Chemical class 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 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
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- JJVNINGBHGBWJH-UHFFFAOYSA-N ortho-vanillin Chemical compound COC1=CC=CC(C=O)=C1O JJVNINGBHGBWJH-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical class O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical class COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 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
- 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
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KCDXJAYRVLXPFO-UHFFFAOYSA-N syringaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1O KCDXJAYRVLXPFO-UHFFFAOYSA-N 0.000 description 1
- COBXDAOIDYGHGK-UHFFFAOYSA-N syringaldehyde Natural products COC1=CC=C(C=O)C(OC)=C1O COBXDAOIDYGHGK-UHFFFAOYSA-N 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical class CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 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
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 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
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/025—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with heterocyclic organic compounds
- C08G16/0281—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with heterocyclic organic compounds containing phosphorus in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/304—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3272—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- 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
- C08G2190/00—Compositions for sealing or packing joints
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Epoxy Resins (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Reinforced Plastic Materials (AREA)
Description
本発明は、新規なフェノール樹脂、エポキシ樹脂およびエポキシ樹脂組成物に関する。また、かかるエポキシ樹脂組成物により形成されるプリプレグ等の硬化物に関する。 The present invention relates to novel phenolic resins, epoxy resins and epoxy resin compositions. Further, the present invention relates to a cured product such as a prepreg formed of the epoxy resin composition.
エポキシ樹脂組成物は作業性及びその硬化物の優れた電気特性、耐熱性、接着性、耐湿性(耐水性)等により電気・電子部品、構造用材料、接着剤、塗料等の分野で幅広く用いられている。 Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to workability and excellent electrical properties, heat resistance, adhesiveness, moisture resistance (water resistance), etc. of the cured product. Have been.
しかし近年、電気・電子分野においてはその発展に伴い、樹脂組成物の高純度化をはじめ耐湿性、密着性、誘電特性、フィラー(無機または有機充填剤)を高充填させるための低粘度化、成型サイクルを短くするための反応性のアップ等の諸特性の一層の向上が求められている。又、構造材としては航空宇宙材料、レジャー・スポーツ器具用途などにおいて軽量で機械物性の優れた材料が求められている。特に半導体封止分野、基板(基板自体、もしくはその周辺材料)においては、その半導体の変遷に従い、薄層化、スタック化、システム化、三次元化と複雑になっていき、非常に高いレベルの耐熱性や高流動性といった要求特性が求められる。なお、特にプラスチックパッケージの車載用途への拡大に伴い、耐熱性の向上要求がいっそう厳しくなっている。具体的には、半導体の駆動温度の上昇により、150℃以上の耐熱性が求められるようになってきている。一般にエポキシ樹脂は軟化点の高いエポキシ樹脂が高い耐熱性を有する傾向があるが、その反面、粘度が上昇するという傾向で封止材には使用が困難となる。また熱分解温度の低下、難燃性の低下が課題となる。 However, in recent years, in the electric and electronic fields, along with its development, the resin composition has been highly purified, as well as moisture resistance, adhesion, dielectric properties, viscosity reduction for highly filling a filler (inorganic or organic filler), Further improvements in various properties such as increased reactivity for shortening the molding cycle are required. As structural materials, lightweight materials having excellent mechanical properties are required for aerospace materials, leisure and sports equipment applications, and the like. In particular, in the field of semiconductor encapsulation and substrates (substrate itself or its surrounding materials), with the transition of semiconductors, the complexity of thinning, stacking, systematization, and three-dimensionalization has increased, resulting in a very high level. Required characteristics such as heat resistance and high fluidity are required. In particular, with the expansion of plastic packages to in-vehicle applications, the demand for improved heat resistance has become more severe. Specifically, heat resistance of 150 ° C. or higher has been required due to an increase in driving temperature of a semiconductor. In general, an epoxy resin having a high softening point tends to have high heat resistance, but on the other hand, it tends to increase in viscosity, making it difficult to use it as a sealing material. In addition, a reduction in the thermal decomposition temperature and a reduction in the flame retardancy are problems.
そのため、従来から耐熱性及び難燃性が高いエポキシ樹脂が要求されていた。そこで、耐熱性が良好なエポキシ樹脂として、様々なエポキシ樹脂が開発されてきた(特許文献1〜5)。しかし、エポキシ樹脂は一般的に高Tg化すると、難燃性が低下する。これは架橋密度が向上することによる影響である。このような特性から、難燃性が求められる半導体周辺材料への高Tg化が要求される中、この相反する特性を有する樹脂の開発が急務であった。 Therefore, an epoxy resin having high heat resistance and high flame retardancy has been conventionally required. Therefore, various epoxy resins have been developed as epoxy resins having good heat resistance (Patent Documents 1 to 5). However, when the Tg of an epoxy resin is generally increased, the flame retardancy is reduced. This is due to the effect of improving the crosslink density. Due to such characteristics, there has been an urgent need to develop a resin having the contradictory characteristics, while a high Tg is required for a semiconductor peripheral material requiring flame retardancy.
本発明はこのような問題を解決すべく検討の結果なされたものであり、その硬化物において、高い耐熱性及び高い難燃性を有するエポキシ樹脂組成物の構成成分であるフェノール樹脂、該フェノール樹脂に由来するエポキシ樹脂、該フェノール樹脂または該エポキシ樹脂を含有するエポキシ樹脂組成物、プリプレグ、およびその硬化物を提供するものである。 The present invention has been made as a result of investigations to solve such problems, and in a cured product thereof, a phenol resin which is a component of an epoxy resin composition having high heat resistance and high flame retardancy, the phenol resin And an epoxy resin composition, a prepreg, and a cured product thereof containing the phenol resin or the epoxy resin.
本発明者らは前記課題を解決するために鋭意研究した結果、本発明を完成させるに到った。
すなわち本発明は、下記(1)〜(7)に関する。The present inventors have conducted intensive studies to solve the above problems, and as a result, have completed the present invention.
That is, the present invention relates to the following (1) to (7).
(1)下記式(1)で表されるフェノール化合物と、下記式(2)で表される化合物との反応によってフェノール化合物(a)を得た後、さらに下記式(3)で表されるリン含有化合物を反応させて得られるフェノール樹脂(b)。 (1) A phenol compound (a) is obtained by reacting a phenol compound represented by the following formula (1) with a compound represented by the following formula (2), and further represented by the following formula (3). A phenolic resin (b) obtained by reacting a phosphorus-containing compound.
(式(1)中、R1はそれぞれ独立に、水素原子、炭素数1〜10の置換若しくは無置換のアルキル基、炭素数6〜10の置換若しくは無置換のアリール基、水酸基、ニトロ基又は炭素数1〜10の置換若しくは無置換のアルコキシ基のいずれかを表す。mはR1の数を表し、0〜4の整数である。)(In the formula (1), R 1 is each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group or Represents either a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms. M represents the number of R 1 and is an integer of 0 to 4.)
(式(2)中、R2はそれぞれ独立に、水素原子、炭素数1〜10の置換若しくは無置換のアルキル基、炭素数6〜10の置換若しくは無置換のアリール基、水酸基、ニトロ基、ホルミル基、アリル基又は炭素数1〜10の置換若しくは無置換のアルコキシ基のいずれかを表す。kはR2の数を表し、0〜4の整数である。)(In the formula (2), each R 2 is independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group, Represents any of a formyl group, an allyl group, and a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms. K represents the number of R 2 and is an integer of 0 to 4.)
(式(3)中、R3はそれぞれ独立に水素原子、アルキル基又は芳香族基を表す。)(In the formula (3), R 3 independently represents a hydrogen atom, an alkyl group, or an aromatic group.)
(2)下記式(4)で表されるフェノール樹脂。 (2) A phenol resin represented by the following formula (4).
(式(4)中、R1はそれぞれ独立に、水素原子、炭素数1〜10の置換若しくは無置換のアルキル基、炭素数6〜10の置換若しくは無置換のアリール基、水酸基、ニトロ基又は炭素数1〜10の置換若しくは無置換のアルコキシ基のいずれかを表し、R2はそれぞれ独立して存在し、水素原子、炭素数1〜10の置換若しくは無置換のアルキル基、炭素数6〜10の置換若しくは無置換のアリール基、水酸基、ニトロ基、ホルミル基、アリル基又は炭素数1〜10の置換若しくは無置換のアルコキシ基のいずれかを表し、kは
R2の数を表し、0〜4の整数であり、mはR1の数を表し、0〜4の整数であり、Zは水素原子又は下記式(5)の構造を表し、複数存在するZのうち少なくとも一つは下記式(5)の構造を表す。)(In the formula (4), R 1 is each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group or Represents any of a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, R 2 is each independently present, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, 10 represents a substituted or unsubstituted aryl group, hydroxyl group, nitro group, formyl group, allyl group or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, k represents the number of R 2 , an to 4 integer, m represents the number of R 1, is an integer of 0 to 4, Z represents a structure of the hydrogen atom or the following formula (5), at least one of the plurality existing Z below Represents the structure of formula (5).)
(式(5)中、R3はそれぞれ独立に水素原子、アルキル基又は芳香族基を表す。)(In the formula (5), R 3 independently represents a hydrogen atom, an alkyl group, or an aromatic group.)
(3)前項(1)又は(2)に記載のフェノール樹脂にエピハロヒドリンを反応させて得られるエポキシ樹脂。
(4)前項(1)又は前項(2)に記載のフェノール樹脂とエポキシ樹脂を含有してなるエポキシ樹脂組成物。
(5)半導体封止用途に用いられる前項(4)に記載のエポキシ樹脂組成物。
(6)前項(4)に記載のエポキシ樹脂組成物及びシート状の繊維基材からなるプリプレグ。
(7)前項(4)若しくは(5)に記載のエポキシ樹脂組成物、または前項(6)に記載のプリプレグを硬化してなる硬化物。(3) An epoxy resin obtained by reacting epihalohydrin with the phenol resin according to the above (1) or (2).
(4) An epoxy resin composition containing the phenolic resin and the epoxy resin according to the above (1) or (2).
(5) The epoxy resin composition according to the above (4), which is used for semiconductor encapsulation.
(6) A prepreg comprising the epoxy resin composition according to the above (4) and a sheet-like fiber base material.
(7) A cured product obtained by curing the epoxy resin composition according to (4) or (5) or the prepreg according to (6).
本発明のフェノール樹脂は、メソゲン基含有エポキシ樹脂を高純度で含むことから、そのフェノール樹脂を構成成分として含むエポキシ樹脂組成物の硬化物が優れた耐熱性、難燃性を示し、半導体封止材料、プリプレグを始めとする各種複合材料、接着剤、塗料等に使用する場合に有用である。 Since the phenolic resin of the present invention contains a mesogen group-containing epoxy resin with high purity, a cured product of the epoxy resin composition containing the phenolic resin as a constituent exhibits excellent heat resistance, flame retardancy, and semiconductor encapsulation. It is useful when used for various composite materials including prepregs, adhesives, paints and the like.
本発明のフェノール樹脂(b)は、下記式(1)で表されるフェノール化合物と、下記式(2)で表される化合物との反応によってフェノール化合物(a)を得た後、さらに下記式(3)で表されるリン含有化合物を反応させて得ることができる。 The phenolic resin (b) of the present invention is obtained by reacting a phenolic compound represented by the following formula (1) with a compound represented by the following formula (2) to obtain a phenolic compound (a). It can be obtained by reacting the phosphorus-containing compound represented by (3).
(式(1)中、R1はそれぞれ独立に、水素原子、炭素数1〜10の置換若しくは無置換のアルキル基、炭素数6〜10の置換若しくは無置換のアリール基、水酸基、ニトロ基又は炭素数1〜10の置換若しくは無置換のアルコキシ基のいずれかを表す。mはR1の数を表し、0〜4の整数である。)(In the formula (1), R 1 is each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group or Represents either a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms. M represents the number of R 1 and is an integer of 0 to 4.)
(式(2)中、R2はそれぞれ独立に、水素原子、炭素数1〜10の置換若しくは無置換のアルキル基、炭素数6〜10の置換若しくは無置換のアリール基、水酸基、ニトロ基、ホルミル基、アリル基又は炭素数1〜10の置換若しくは無置換のアルコキシ基のいずれかを表す。kはR2の数を表し、0〜4の整数である。)(In the formula (2), each R 2 is independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group, Represents any of a formyl group, an allyl group, and a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms. K represents the number of R 2 and is an integer of 0 to 4.)
(式(3)中、R3はそれぞれ独立に水素原子、アルキル基又は芳香族基を表す。)(In the formula (3), R 3 independently represents a hydrogen atom, an alkyl group, or an aromatic group.)
まず、フェノール化合物(a)について説明する。
フェノール化合物(a)は上記式(1)で表される化合物と上記式(2)で表される化合物との反応によって得られる。First, the phenol compound (a) will be described.
The phenol compound (a) is obtained by reacting a compound represented by the above formula (1) with a compound represented by the above formula (2).
式(1)においてR1はそれぞれ独立して存在し、水素原子、炭素数1〜10の無置換のアルキル基、炭素数6〜10の無置換のアリール基、水酸基、ニトロ基、又は炭素数1〜10の無置換のアルコキシ基であることが好ましい。In the formula (1), R 1 is independently present, and represents a hydrogen atom, an unsubstituted alkyl group having 1 to 10 carbon atoms, an unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group, or a carbon number. It is preferably an unsubstituted alkoxy group of 1 to 10.
フェノール化合物(a)を得るために、式(2)で表される化合物との反応に用いられる式(1)で表される化合物の具体例としては、2−ヒドロキシアセトフェノン、3−ヒドロキシアセトフェノン、4−ヒドロキシアセトフェノン、2’,4’−ジヒドロキシアセトフェノン、2’,5’−ジヒドロキシアセトフェノン、3’,4’−ジヒドロキシアセトフェノン、3’,5’−ジヒドロキシアセトフェノン、2’,3’,4’−トリヒドロキシアセトフェノン、2’,4’,6’−トリヒドロキシアセトフェノン一水和物、4’−ヒドロキシ−3’−メチルアセトフェノン、4’−ヒドロキシ−2’−メチルアセトフェノン、2’−ヒドロキシ−5’−メチルアセトフェノン、4’−ヒドロキシ−3’−メトキシアセトフェノン、2’−ヒドロキシ−4’−メトキシアセトフェノン、4’−ヒドロキシ−3’−ニトロアセトフェノン、4’−ヒドロキシ−3’,5’−ジメトキシアセトフェノン、4’,6’−ジメトキシ‐2’−ヒドロキシアセトフェノン、2’−ヒドロキシ−3’,4’−ジメトキシアセトフェノン、2’−ヒドロキシ−4’,5’−ジメトキシアセトフェノン、5−アセチルサリチル酸メチル、2’,3’−ジヒドロキシ−4’−メトキシアセトフェノン水和物、が挙げられる。 Specific examples of the compound represented by the formula (1) used for the reaction with the compound represented by the formula (2) to obtain the phenol compound (a) include 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2 ', 4'-dihydroxyacetophenone, 2', 5'-dihydroxyacetophenone, 3 ', 4'-dihydroxyacetophenone, 3', 5'-dihydroxyacetophenone, 2 ', 3', 4'- Trihydroxyacetophenone, 2 ', 4', 6'-trihydroxyacetophenone monohydrate, 4'-hydroxy-3'-methylacetophenone, 4'-hydroxy-2'-methylacetophenone, 2'-hydroxy-5 ' -Methylacetophenone, 4'-hydroxy-3'-methoxyacetophenone, 2 ' Hydroxy-4'-methoxyacetophenone, 4'-hydroxy-3'-nitroacetophenone, 4'-hydroxy-3 ', 5'-dimethoxyacetophenone, 4', 6'-dimethoxy-2'-hydroxyacetophenone, 2'- Hydroxy-3 ′, 4′-dimethoxyacetophenone, 2′-hydroxy-4 ′, 5′-dimethoxyacetophenone, methyl 5-acetylsalicylate, 2 ′, 3′-dihydroxy-4′-methoxyacetophenone hydrate Can be
フェノール化合物(a)を得るために、式(1)で表される化合物との反応に用いられる式(2)で表される化合物の具体例としては、例えば、2−ヒドロキシベンズアルデヒド、3−ヒドロキシベンズアルデヒド、4−ヒドロキシベンズアルデヒド、2,3‐ジヒドロキシベンズアルデヒド、2,4−ジヒドロキシベンズアルデヒド、2,5−ジヒドロキシベンズアルデヒド、3,4−ジヒドロキシベンズアルデヒド、シリンガアルデヒド、3,5−ジ−tert−ブチル−4−ヒドロキシベンズアルデヒド、イソバニリン、4−ヒドロキシ−3−ニトロベンズアルデヒド、5−ヒドロキシ−2−ニトロベンズアルデヒド、3,4−ジヒドロキシ−5−ニトロベンズアルデヒド、バニリン、o−バニリン、2−ヒドロキシ−1−ナフトアルデヒド、2−ヒドロキシ−5−ニトロ−m−アニスアルデヒド、2−ヒドロキシ−5−メチルイソフタルアルデヒド、2−ヒドロキシ−4−メトキシベンズアルデヒド、1−ヒドロキシ−2−ナフトアルデヒド、2−ヒドロキシ−5−メトキシベンズアルデヒド、5−ニトロバニリン、5−アリル−3−メトキシサリチルアルデヒド、3,5−ジ−tert−ブチルサリチルアルデヒド、3−エトキシサリチルアルデヒド、4−ヒドロキシイソフタルアルデヒド、4−ヒドロキシ−3,5−ジメチルベンズアルデヒド、2,4,6−トリヒドロキシベンズアルデヒド、2,4,5−トリヒドロキシベンズアルデヒド、2,3,4−トリヒドロキシベンズアルデヒド、3,4,5−トリヒドロキシベンズアルデヒド、3−エトキシ−4−ヒドロキシベンズアルデヒド、などが挙げられる。これらは1種のみを使用しても、2種類以上を併用してもよい。 Specific examples of the compound represented by the formula (2) used for the reaction with the compound represented by the formula (1) to obtain the phenol compound (a) include, for example, 2-hydroxybenzaldehyde, 3-hydroxy Benzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, syringaldehyde, 3,5-di-tert-butyl-4 -Hydroxybenzaldehyde, isovanillin, 4-hydroxy-3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 3,4-dihydroxy-5-nitrobenzaldehyde, vanillin, o-vanillin, 2-hydroxy-1-naphthaldehyde , 2-hydroxy-5-nitro-m-anisaldehyde, 2-hydroxy-5-methylisophthalaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 1-hydroxy-2-naphthaldehyde, 2-hydroxy-5-methoxybenzaldehyde , 5-nitrovanillin, 5-allyl-3-methoxysalicylaldehyde, 3,5-di-tert-butylsalicylaldehyde, 3-ethoxysalicylaldehyde, 4-hydroxyisophthalaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde 'S aldehyde, and the like. These may be used alone or in combination of two or more.
フェノール化合物(a)は、酸性条件下もしくは塩基性条件下、式(1)で表される化合物の一種以上と式(2)で表される化合物とのアルドール縮合反応によって得られる。
式(2)で表される化合物は式(1)で表される化合物1モルに対して1.0〜1.05モルを使用する。The phenol compound (a) is obtained by an aldol condensation reaction between one or more compounds represented by the formula (1) and a compound represented by the formula (2) under acidic or basic conditions.
The compound represented by the formula (2) is used in an amount of 1.0 to 1.05 mol per 1 mol of the compound represented by the formula (1).
酸性条件下でアルドール縮合反応を行う場合、用い得る酸性触媒としては、塩酸、硫酸、硝酸のような無機酸、トルエンスルホン酸、キシレンスルホン酸、シュウ酸等の有機酸が挙げられる。これらは単独で使用してもよく、複数の種類を併用してもよい。酸性触媒の使用量は、式(2)で表される化合物1モルに対して0.01〜1.0モル、好ましくは0.2〜0.5モルである。 When the aldol condensation reaction is performed under acidic conditions, examples of the acidic catalyst that can be used include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as toluenesulfonic acid, xylenesulfonic acid, and oxalic acid. These may be used alone or in combination of a plurality of types. The amount of the acidic catalyst to be used is 0.01 to 1.0 mol, preferably 0.2 to 0.5 mol, per 1 mol of the compound represented by the formula (2).
一方、塩基性条件下でアルドール縮合反応を行う場合、用い得る塩基性触媒としては、水酸化ナトリウム及び水酸化カリウム等の金属水酸化物、炭酸カリウム及び炭酸ナトリウム等の炭酸アルカリ金属塩、ジエチルアミン、トリエチルアミン、トリブチルアミン、ジイソブチルアミン、ピリジン及びピペリジン等のアミン誘導体、並びにジメチルアミノエチルアルコール及びジエチルアミノエチルアルコール等のアミノアルコール誘導体が挙げられる。塩基性条件の場合も、先に挙げた塩基性触媒を単独で使用してもよく、複数の種類を併用してもよい。塩基性触媒の使用量は、式(2)で表される化合物1モルに対して0.1〜2.5モル、好ましくは0.2〜2.0モルである。 On the other hand, when the aldol condensation reaction is performed under basic conditions, usable basic catalysts include metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal salts such as potassium carbonate and sodium carbonate, diethylamine, Examples include amine derivatives such as triethylamine, tributylamine, diisobutylamine, pyridine and piperidine, and amino alcohol derivatives such as dimethylaminoethyl alcohol and diethylaminoethyl alcohol. In the case of basic conditions, the above-mentioned basic catalysts may be used alone, or a plurality of types may be used in combination. The amount of the basic catalyst to be used is 0.1 to 2.5 mol, preferably 0.2 to 2.0 mol, per 1 mol of the compound represented by the formula (2).
フェノール化合物(a)を得る反応では、必要に応じて溶剤を使用してもよい。用い得る溶剤としては、例えばケトン類のように式(2)で表される化合物との反応性を有するものでなければ特に制限はないが、原料の式(2)で表される化合物を容易に溶解させる点ではアルコール類を溶剤として用いるのが好ましい。 In the reaction for obtaining the phenol compound (a), a solvent may be used as necessary. The solvent that can be used is not particularly limited as long as it does not have reactivity with the compound represented by the formula (2), for example, ketones. It is preferable to use alcohols as a solvent from the viewpoint of dissolving in water.
反応温度は通常10〜90℃であり、好ましくは35〜70℃である。反応時間は通常0.5〜10時間であるが、原料化合物の種類によって反応性に差があるため、この限りではない。反応終了後、樹脂として取り出す場合には、反応物を水洗後または水洗無しに、加熱減圧下で反応液から未反応物や溶媒等を除去する。結晶で取り出す場合、大量の水中に反応液を滴下することにより結晶を析出させる。塩基性条件で反応を行った場合は生成したフェノール化合物が水中に溶け込むこともありうるので、塩酸を加えるなどして中性〜酸性条件にして結晶として析出させる。 The reaction temperature is usually from 10 to 90 ° C, preferably from 35 to 70 ° C. The reaction time is generally 0.5 to 10 hours, but is not limited to this, since there is a difference in reactivity depending on the type of the starting compound. When the reaction product is taken out as a resin after completion of the reaction, unreacted substances, solvent, and the like are removed from the reaction solution under heating and reduced pressure after or without washing the reaction product with water. When taking out as a crystal, the reaction liquid is dropped into a large amount of water to precipitate a crystal. When the reaction is carried out under basic conditions, the generated phenol compound may be dissolved in water. Therefore, crystals are precipitated under neutral to acidic conditions by adding hydrochloric acid or the like.
本発明のフェノール樹脂(b)は、上記フェノール化合物(a)に上記式(3)で表されるリン含有化合物を付加反応させることにより得ることができる。
上記式(3)で表される化合物は、例えば、HCA(三光株式会社製)として入手することができる。The phenol resin (b) of the present invention can be obtained by subjecting the phenol compound (a) to an addition reaction with the phosphorus-containing compound represented by the above formula (3).
The compound represented by the above formula (3) can be obtained, for example, as HCA (manufactured by Sanko Corporation).
更に本発明のフェノール樹脂(b)の製造方法を具体的に述べると、リン含有化合物中に、フェノール化合物(a)を、発熱に注意しながら、滴下または分割添加することが好ましい。この際、反応溶媒として有機溶剤を用いてもよい。 More specifically, the method for producing the phenolic resin (b) of the present invention is specifically described. It is preferable that the phenolic compound (a) is added dropwise or dividedly to the phosphorus-containing compound while paying attention to heat generation. At this time, an organic solvent may be used as a reaction solvent.
上記フェノール化合物(a)を、リン含有化合物中に滴下する際の温度は、20℃〜200℃が好ましく、反応性の制御、及び反応熱の除去の容易さから、50℃〜160℃が特に好ましい。 The temperature at which the phenol compound (a) is dropped into the phosphorus-containing compound is preferably from 20 ° C to 200 ° C, and particularly preferably from 50 ° C to 160 ° C from the viewpoint of controlling the reactivity and removing the reaction heat easily. preferable.
上記のリン含有化合物と、フェノール化合物(a)を付加反応するときの割合には、特に制限がないが、例えば、得られる生成物が加水分解性に優れる点から、リン含有化合物をフェノール化合物(a)のオレフィン基1当量に対し、1当量ないしはそれ以上過剰(例えば1〜5当量)に用いることが好ましい。また、得られた化合物をエポキシ樹脂用の硬化剤として用いる場合は、過剰に存在するリン含有化合物を存在させたまま使用しても除去してから用いてもよいが、最終的に得られる硬化物が耐熱性、耐湿性に優れる点から、本発明のリン原子含有フェノール化合物とリン含有化合物の合計100重量部中に、本発明のリン原子含有フェノール化合物を少なくとも50重量部以上含有していることが好ましく、更に、80重量部以上含有していることが、とくに好ましい。 The ratio when the above-mentioned phosphorus-containing compound and the phenol compound (a) are subjected to the addition reaction is not particularly limited, but, for example, the phosphorus-containing compound is converted into a phenol compound ( It is preferable to use 1 equivalent or more excess (for example, 1 to 5 equivalents) to 1 equivalent of the olefin group of a). When the obtained compound is used as a curing agent for an epoxy resin, the compound may be used in the presence or removal of the phosphorus-containing compound in excess, but may be used after removal. Since the product is excellent in heat resistance and moisture resistance, the phosphorus-containing phenol compound of the present invention contains at least 50 parts by weight or more of the phosphorus-containing phenol compound of the present invention in a total of 100 parts by weight of the phosphorus-containing phenol compound and the phosphorus-containing compound of the present invention. It is particularly preferable that the content be 80 parts by weight or more.
上記の反応において、反応溶媒として有機溶剤を用いる場合、特に限定されないが、例えば、リン含有化合物、フェノール化合物(a)に不活性であるものが好ましく、例えば、脂肪族アルコール、芳香族炭化水素又はこれらの混合溶剤が用いられる。脂肪族アルコールとしては、用いる反応原料、得られる生成物の溶解度、反応条件、反応の経済性等を考慮して、メタノール、エタノール、イソプロピルアルコール、n−プロピルアルコール、t−ブチルアルコール、イソブチルアルコール、n−ブチルアルコール、エチレングリコール低級アルキルエーテル類、又は、プロピレングリコール低級アルキルエーテル等を挙げることができる。また、芳香族炭化水素溶剤としては、例えば、トルエン、キシレン、クメン等を挙げることができる。このような溶剤は、通常、用いるリン含有化合物の合計100重量部に対して、20〜500重量部の範囲で用いられるが、これに限定されるものではない。 In the above reaction, when an organic solvent is used as a reaction solvent, it is not particularly limited. For example, a phosphorus-containing compound or a phenol compound (a) that is inert to the phenol compound (a) is preferable, for example, an aliphatic alcohol, an aromatic hydrocarbon or These mixed solvents are used. As the aliphatic alcohol, in consideration of the reaction raw material used, the solubility of the obtained product, the reaction conditions, the economics of the reaction, and the like, methanol, ethanol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol, isobutyl alcohol, Examples thereof include n-butyl alcohol, ethylene glycol lower alkyl ethers, and propylene glycol lower alkyl ether. Examples of the aromatic hydrocarbon solvent include toluene, xylene, cumene and the like. Such a solvent is usually used in a range of 20 to 500 parts by weight based on a total of 100 parts by weight of the phosphorus-containing compound used, but is not limited thereto.
このようにして得られた本発明のフェノール樹脂(b)は、下記式(4)で表される構造を有する。 The phenolic resin (b) of the present invention thus obtained has a structure represented by the following formula (4).
(式(4)中、R1、R2、k、mは式(1)〜(2)と同様であり、Zは水素原子又は下記式(5)の構造を表し、複数存在するZのうち少なくとも一つは下記式(5)の構造を表す。)(In the formula (4), R 1 , R 2 , k, and m are the same as those in the formulas (1) and (2), and Z represents a hydrogen atom or a structure of the following formula (5). At least one of them represents the structure of the following formula (5).)
(式(5)中、R3は式(3)と同じ。)(In the formula (5), R 3 is the same as the formula (3).)
本発明のフェノール樹脂(b)の水酸基当量は200〜800g/eq.が好ましく、220〜750g/eq.がより好ましい。一方、軟化点は100〜150℃が好ましい。 The phenolic resin (b) of the present invention has a hydroxyl equivalent of 200 to 800 g / eq. Is preferred, and 220 to 750 g / eq. Is more preferred. On the other hand, the softening point is preferably from 100 to 150C.
次に、本発明のエポキシ樹脂について説明する。
本発明のエポキシ樹脂は、上記手法によって得られた本発明のフェノール樹脂(b)とアルコール溶剤中、エピハロヒドリンとを反応させ、エポキシ化することにより得られる。なお、エポキシ化の際には、本発明のフェノール樹脂(b)の1種類のみを使用しても、2種以上を併用してもよい。また、本発明のフェノール樹脂(b)に、フェノール樹脂(b)以外のフェノール化合物を併用しても良い。
併用できるフェノール樹脂(b)以外のフェノール化合物としては、エポキシ樹脂の原料として通常用いられるフェノール化合物であれば特に制限なく用いることができる。
本発明のエポキシ樹脂としては、特に優れた溶剤溶解性を示し、なおかつ高い難燃性を有する硬化物が得られることから、式(2)で表される化合物と式(1)で表される化合物との反応によって得られたフェノール化合物(a)と、式(3)で表されるリン含有化合物と反応により得られた本発明のフェノール樹脂(b)のエポキシ化物が好ましい。Next, the epoxy resin of the present invention will be described.
The epoxy resin of the present invention can be obtained by reacting the phenolic resin (b) of the present invention obtained by the above method with epihalohydrin in an alcohol solvent, followed by epoxidation. In the epoxidation, only one type of the phenolic resin (b) of the present invention may be used, or two or more types may be used in combination. Further, a phenol compound other than the phenol resin (b) may be used in combination with the phenol resin (b) of the present invention.
As the phenol compound other than the phenol resin (b) that can be used in combination, any phenol compound that is generally used as a raw material for an epoxy resin can be used without any particular limitation.
As the epoxy resin of the present invention, a cured product having particularly excellent solvent solubility and high flame retardancy can be obtained. Therefore, the epoxy resin is represented by the compound represented by the formula (2) and the compound represented by the formula (1). An epoxidized product of the phenolic resin (b) of the present invention obtained by reacting the phenolic compound (a) obtained by the reaction with the compound and the phosphorus-containing compound represented by the formula (3) is preferable.
本発明のエポキシ樹脂を得る反応において、エピハロヒドリンとしてはエピクロルヒドリン、α−メチルエピクロルヒドリン、β−メチルエピクロルヒドリン、エピブロモヒドリン等が使用できるが、工業的に入手が容易なエピクロルヒドリンが好ましい。エピハロヒドリンの使用量は、フェノール樹脂(b)の水酸基1モルに対し通常2〜20モル、好ましくは2〜15モル、特に好ましくは2〜4.5モルである。エポキシ樹脂は、アルカリ金属酸化物の存在下でフェノール樹脂(b)とエピハロヒドリンとを付加させ、次いで生成した1,2−ハロヒドリンエーテル基を開環させてエポキシ化する反応により得られる。この際、エピハロヒドリンを上記のように通常より顕著に少ない量で使用することで、エポキシ樹脂の分子量を延ばすとともに分子量分布を広げることができる。この結果、得られるエポキシ樹脂は、比較的低い軟化点を有する樹脂状物として系中から取り出せ、優れた溶剤溶解性を示す。 In the reaction for obtaining the epoxy resin of the present invention, epichlorohydrin, α-methylepichlorohydrin, β-methylepichlorohydrin, epibromohydrin and the like can be used as epihalohydrin, but epichlorohydrin which is easily available industrially is preferable. The amount of epihalohydrin to be used is generally 2 to 20 mol, preferably 2 to 15 mol, particularly preferably 2 to 4.5 mol, per 1 mol of the hydroxyl group of the phenol resin (b). The epoxy resin is obtained by a reaction in which phenol resin (b) is added to epihalohydrin in the presence of an alkali metal oxide, and the resulting 1,2-halohydrin ether group is ring-opened to undergo epoxidation. At this time, by using epihalohydrin in a significantly smaller amount than usual as described above, the molecular weight distribution and the molecular weight distribution of the epoxy resin can be extended. As a result, the obtained epoxy resin can be taken out of the system as a resin having a relatively low softening point, and exhibits excellent solvent solubility.
また、エポキシ化の際に、メタノール、エタノール、イソプロピルアルコールなどのアルコール類、ジメチルスルホン、ジメチルスルホキシド、テトラヒドロフラン、ジオキサン等の非プロトン性極性溶媒などを添加して反応を行うことが反応進行上好ましい。中でも、アルコール類が好ましく、アルコール溶剤の極性により、エポキシ化時のイオン反応を効率良く進行させることができ、高純度でエポキシ樹脂を得ることができる。さらに、本発明のメソゲン基含有エポキシ樹脂において、α,β−不飽和カルボニル部位が高い反応性を示し、分解しやすい傾向に有るが、アルコール溶剤を用いることにより、溶媒和されるため、分解反応を受けにくくなる。用い得るアルコール溶剤としては、メタノール、エタノール、イソプロピルアルコールが好ましい。中でも、エポキシ樹脂との相溶性の観点から、メタノールを用いることが特に好ましい。 In addition, at the time of epoxidation, it is preferable from the viewpoint of the progress of the reaction that the reaction is performed by adding an alcohol such as methanol, ethanol, or isopropyl alcohol, or an aprotic polar solvent such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, or dioxane. Among them, alcohols are preferable, and the ionic reaction during epoxidation can efficiently proceed according to the polarity of the alcohol solvent, and an epoxy resin can be obtained with high purity. Further, in the mesogen group-containing epoxy resin of the present invention, the α, β-unsaturated carbonyl moiety exhibits high reactivity and tends to be decomposed. Hard to receive. As the alcohol solvent that can be used, methanol, ethanol, and isopropyl alcohol are preferable. Among them, it is particularly preferable to use methanol from the viewpoint of compatibility with the epoxy resin.
上記アルコール類を使用する場合、その使用量はエピハロヒドリンの使用量に対し通常2〜50質量%、好ましくは4〜35質量%である。また非プロトン性極性溶媒を用いる場合はエピハロヒドリンの使用量に対し通常5〜100質量%、好ましくは10〜80質量%である。 When the alcohols are used, they are used in an amount of usually 2 to 50% by mass, preferably 4 to 35% by mass, based on the amount of epihalohydrin used. When an aprotic polar solvent is used, it is usually 5 to 100% by mass, preferably 10 to 80% by mass, based on the amount of epihalohydrin used.
上記エポキシ化反応においてはアルカリ金属水酸化物が使用できる。
エポキシ化反応に使用できるアルカリ金属水酸化物としては、水酸化ナトリウム、水酸化カリウム等が挙げられ、これらは固形物をそのまま使用しても、あるいはその水溶液を使用してもよい。水溶液を使用する場合は、該アルカリ金属水酸化物の水溶液を連続的に反応系内に添加すると共に、減圧下または常圧下で連続的に留出させた水及びエピハロヒドリンの混合液から分液により水を除去し、エピハロヒドリンのみを反応系内に連続的に戻す方法でもよい。アルカリ金属水酸化物の使用量は、本発明のフェノール樹脂(b)の水酸基1モルに対して通常0.9〜3.0モル、好ましくは1.0〜2.5モル、より好ましくは1.0〜2.0モル、特に好ましくは1.0〜1.3モルである。
また、本発明者等は、エポキシ化反応において、特にフレーク状の水酸化ナトリウムを用いることで、水溶液とした水酸化ナトリウムを使用するよりも得られるエポキシ樹脂に含まれるハロゲン量を顕著に低減させることが可能となることを知見するに至った。更にこのフレーク状の水酸化ナトリウムは、反応系内に分割添加されることが好ましい。分割添加を行なうことで、反応温度の急激な減少を防ぐことができ、これにより不純物である1,3−ハロヒドリン体やハロメチレン体の生成を防止することができる。In the epoxidation reaction, an alkali metal hydroxide can be used.
Examples of the alkali metal hydroxide that can be used in the epoxidation reaction include sodium hydroxide, potassium hydroxide, and the like. These may be used as a solid or as an aqueous solution thereof. When an aqueous solution is used, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and separated from a mixed solution of water and epihalohydrin continuously distilled under reduced pressure or normal pressure. A method in which water is removed and only epihalohydrin is continuously returned into the reaction system may be used. The amount of the alkali metal hydroxide used is usually 0.9 to 3.0 mol, preferably 1.0 to 2.5 mol, more preferably 1 to 1 mol of the hydroxyl group of the phenolic resin (b) of the present invention. 0.0 to 2.0 mol, particularly preferably 1.0 to 1.3 mol.
Further, the present inventors have found that in the epoxidation reaction, particularly by using flake-like sodium hydroxide, the amount of halogen contained in the obtained epoxy resin is significantly reduced as compared with the use of aqueous solution of sodium hydroxide. It has been found that it becomes possible to do so. Further, it is preferable that the flake-form sodium hydroxide is added in portions in the reaction system. By performing the divisional addition, it is possible to prevent a rapid decrease in the reaction temperature, thereby preventing the generation of impurities such as 1,3-halohydrin and halomethylene.
エポキシ化反応を促進するために、テトラメチルアンモニウムクロライド、テトラメチルアンモニウムブロマイド、トリメチルベンジルアンモニウムクロライド等の4級アンモニウム塩を触媒として添加することが好ましい。4級アンモニウム塩の使用量としては、本発明のフェノール樹脂の水酸基1モルに対し通常0.1〜15gであり、好ましくは0.2〜10gである。 In order to accelerate the epoxidation reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride as a catalyst. The amount of the quaternary ammonium salt to be used is generally 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol resin of the present invention.
反応温度は通常30〜90℃であり、好ましくは35〜80℃である。反応時間は通常0.5〜10時間であり、好ましくは1〜8時間である。中でも、アルコール溶剤を用いた場合、50℃〜90℃が好ましく、60〜85℃がより好ましく、70〜80℃が特に好ましい。
反応終了後、反応物を水洗後、または水洗無しに加熱減圧下で反応液からエピハロヒドリンや溶媒等を除去する。また得られたエポキシ樹脂中に含まれるハロゲン量をさらに低減させるために、回収した本発明のエポキシ樹脂をトルエン、メチルイソブチルケトンなどの溶剤に溶解し、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物の水溶液を加えて反応を行ない、閉環を確実なものにすることも出来る。この場合、アルカリ金属水酸化物の使用量は、本発明のフェノール樹脂の水酸基1モルに対して通常0.01〜0.3モル、好ましくは0.05〜0.2モルである。反応温度は通常50〜120℃、反応時間は通常0.5〜2時間である。The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is generally 0.5 to 10 hours, preferably 1 to 8 hours. Among them, when an alcohol solvent is used, the temperature is preferably from 50C to 90C, more preferably from 60C to 85C, and particularly preferably from 70C to 80C.
After completion of the reaction, epihalohydrin, a solvent, and the like are removed from the reaction solution after heating or under reduced pressure after washing with or without washing with water. Further, in order to further reduce the amount of halogen contained in the obtained epoxy resin, the recovered epoxy resin of the present invention is dissolved in a solvent such as toluene, methyl isobutyl ketone, and an alkali metal such as sodium hydroxide or potassium hydroxide. The reaction can be carried out by adding an aqueous solution of a hydroxide to ensure ring closure. In this case, the amount of the alkali metal hydroxide to be used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per 1 mol of the hydroxyl group of the phenol resin of the present invention. The reaction temperature is usually 50 to 120 ° C, and the reaction time is usually 0.5 to 2 hours.
反応終了後、生成した塩を濾過、水洗などにより除去し、更に加熱減圧下で溶剤を留去することにより本発明のエポキシ樹脂が得られる。また、本発明のエポキシ樹脂が結晶として析出する場合は、大量の水に生成した塩を溶解した後に、本発明のエポキシ樹脂の結晶を濾取してもよい。 After completion of the reaction, the formed salt is removed by filtration, washing with water, or the like, and the solvent is distilled off under reduced pressure while heating to obtain the epoxy resin of the present invention. When the epoxy resin of the present invention precipitates as crystals, the crystals of the epoxy resin of the present invention may be collected by filtration after dissolving the generated salt in a large amount of water.
上記の通りフレーク状の水酸化ナトリウムを使用して得られる本発明のエポキシ樹脂の全ハロゲン量は1800ppm以下が通常であり、1600ppm以下であることが好ましく、さらに好ましくは1300ppm以下である。全ハロゲン量が多すぎるものは硬化物の電気信頼性に悪影響を及ぼすことがある。 As described above, the total halogen content of the epoxy resin of the present invention obtained by using flaky sodium hydroxide is usually 1800 ppm or less, preferably 1600 ppm or less, more preferably 1300 ppm or less. If the total halogen content is too large, the electrical reliability of the cured product may be adversely affected.
以下、本発明のエポキシ樹脂組成物について記載する。本発明のエポキシ樹脂組成物は、本発明のエポキシ樹脂及び本発明のフェノール樹脂の少なくともどちらか1つを必須成分として含有する。 Hereinafter, the epoxy resin composition of the present invention will be described. The epoxy resin composition of the present invention contains at least one of the epoxy resin of the present invention and the phenol resin of the present invention as essential components.
本発明のエポキシ樹脂組成物において、本発明のエポキシ樹脂を必須成分として含有する場合には、本発明のエポキシ樹脂は単独でまたは他のエポキシ樹脂と併用して使用することが出来る。 When the epoxy resin of the present invention contains the epoxy resin of the present invention as an essential component, the epoxy resin of the present invention can be used alone or in combination with another epoxy resin.
他のエポキシ樹脂の具体例としては、ビスフェノール類(ビスフェノールA、ビスフェノールF、ビスフェノールS、ビフェノール、ビスフェノールAD及びビスフェノールI等)やフェノール類(フェノール、アルキル置換フェノール、芳香族置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、アルキル置換ジヒドロキシベンゼン及びジヒドロキシナフタレン等)と各種アルデヒド(ホルムアルデヒド、アセトアルデヒド、アルキルアルデヒド、ベンズアルデヒド、アルキル置換ベンズアルデヒド、ヒドロキシベンズアルデヒド、ナフトアルデヒド、グルタルアルデヒド、フタルアルデヒド、クロトンアルデヒド及びシンナムアルデヒド等)との重縮合物、キシレン等の芳香族化合物とホルムアルデヒドの重縮合物とフェノール類との重縮合物、フェノール類と各種ジエン化合物(ジシクロペンタジエン、テルペン類、ビニルシクロヘキセン、ノルボルナジエン、ビニルノルボルネン、テトラヒドロインデン、ジビニルベンゼン、ジビニルビフェニル、ジイソプロペニルビフェニル、ブタジエン及びイソプレン等)との重合物、フェノール類とケトン類(アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン及びベンゾフェノン等)との重縮合物、フェノール類と芳香族ジメタノール類(ベンゼンジメタノール及びビフェニルジメタノール等)との重縮合物、フェノール類と芳香族ジクロロメチル類(α,α’−ジクロロキシレン及びビスクロロメチルビフェニル等)との重縮合物、フェノール類と芳香族ビスアルコキシメチル類(ビスメトキシメチルベンゼン、ビスメトキシメチルビフェニル及びビスフェノキシメチルビフェニル等)との重縮合物、ビスフェノール類と各種アルデヒドの重縮合物、並びにアルコール類等をグリシジル化したグリシジルエーテル系エポキシ樹脂、脂環式エポキシ樹脂、グリシジルアミン系エポキシ樹脂、グリシジルエステル系エポキシ樹脂等が挙げられるが、通常用いられるエポキシ樹脂であればこれらに限定されるものではない。これらは、1種類のみ使用しても、2種以上を併用してもよい。
他のエポキシ樹脂を併用する場合、本発明のエポキシ樹脂組成物中の全エポキシ樹脂成分に占める本発明のエポキシ樹脂の割合は30質量%以上が好ましく、40質量%以上がより好ましく、70質量%以上が更に好ましく、特に好ましくは100質量%(他のエポキシ樹脂を併用しない場合)である。ただし、本発明のエポキシ樹脂をエポキシ樹脂組成物の改質剤として使用する場合は、全エポキシ樹脂中で1〜30質量%となる割合で添加する。Specific examples of other epoxy resins include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD and bisphenol I) and phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted). Naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Of polycondensation with an aromatic compound such as xylene and formaldehyde Polycondensates of compounds and phenols, phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene and isoprene And polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzene dimethanol, biphenyl dimethanol, etc.) With phenols and aromatic dichloromethyls (such as α, α'-dichloroxylene and bischloromethylbiphenyl), phenols and aromatic bisalkoxymethyls (Bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylation of alcohols, etc., alicyclic Examples include an epoxy resin, a glycidylamine-based epoxy resin, and a glycidyl ester-based epoxy resin. However, the epoxy resin is not limited to these as long as it is a commonly used epoxy resin. These may be used alone or in combination of two or more.
When another epoxy resin is used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin component in the epoxy resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, and 70% by mass. The above is more preferably, and particularly preferably 100% by mass (when no other epoxy resin is used in combination). However, when the epoxy resin of the present invention is used as a modifier for an epoxy resin composition, it is added at a ratio of 1 to 30% by mass in all epoxy resins.
本発明のエポキシ樹脂組成物において、本発明のエポキシ樹脂を必須成分として含有する場合には、硬化剤を用いることが好ましい。この場合、用い得る硬化剤としては、前述の本発明のフェノール樹脂であっても良く、その他の硬化剤であっても良い。その他の硬化剤としては、例えばアミン系化合物、酸無水物系化合物、アミド系化合物及びフェノール系化合物等が挙げられる。これら他の硬化剤の具体例を下記(a)〜(e)に示す。
(a)アミン系化合物 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及びナフタレンジアミン等
(b)酸無水物系化合物 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及びメチルヘキサヒドロ無水フタル酸等
(c)アミド系化合物 ジシアンジアミド、若しくはリノレン酸の2量体とエチレンジアミンより合成されるポリアミド樹脂等、When the epoxy resin composition of the present invention contains the epoxy resin of the present invention as an essential component, it is preferable to use a curing agent. In this case, the curing agent that can be used may be the phenol resin of the present invention described above, or may be another curing agent. Examples of other curing agents include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds. Specific examples of these other curing agents are shown in (a) to (e) below.
(A) amine compounds diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, etc. (b) acid anhydride compounds phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride , Tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. (c) Amide compounds Dicyandiamide or dimer of linolenic acid and ethylene diamine Polyamide resin, etc.
(d)フェノール系化合物 多価フェノール類(ビスフェノールA、ビスフェノールF、ビスフェノールS、フルオレンビスフェノール、テルペンジフェノール、4,4’−ジヒドロキシビフェニル、2,2’−ジヒドロキシビフェニル、3,3’,5,5’−テトラメチル−(1,1’−ビフェニル)−4,4’−ジオール、ハイドロキノン、レゾルシン、ナフタレンジオール、トリス−(4−ヒドロキシフェニル)メタン及び1,1,2,2−テトラキス(4−ヒドロキシフェニル)エタン等);フェノール類(例えば、フェノール、アルキル置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン及びジヒドロキシナフタレン等)と、アルデヒド類(ホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、p−ヒドロキシベンズアルデヒド、o−ヒドロキシベンズアルデヒド及びフルフラール等)、ケトン類(p−ヒドロキシアセトフェノン及びo−ヒドロキシアセトフェノン等)、若しくはジエン類(ジシクロペンタジエン及びトリシクロペンタジエン等)との縮合により得られるフェノール樹脂;前記フェノール類と、置換ビフェニル類(4,4’−ビス(クロルメチル)−1,1’−ビフェニル及び4,4’−ビス(メトキシメチル)−1,1’−ビフェニル等)、若しくは置換フェニル類(1,4−ビス(クロロメチル)ベンゼン、1,4−ビス(メトキシメチル)ベンゼン及び1,4−ビス(ヒドロキシメチル)ベンゼン等)等との重縮合により得られるフェノール樹脂;前記フェノール類及び/又は前記フェノール樹脂の変性物;テトラブロモビスフェノールA及び臭素化フェノール樹脂等のハロゲン化フェノール類
(e)その他 イミダゾール類、BF3 −アミン錯体、グアニジン誘導体(D) Phenol compound Polyhydric phenols (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 3,3 ′, 5 5'-tetramethyl- (1,1'-biphenyl) -4,4'-diol, hydroquinone, resorcinol, naphthalene diol, tris- (4-hydroxyphenyl) methane and 1,1,2,2-tetrakis (4 Phenols (eg, phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and aldehydes (formaldehyde, acetaldehyde, benzaldehyde, p-hydro A phenolic resin obtained by condensation with xybenzaldehyde, o-hydroxybenzaldehyde, furfural, etc.), ketones (p-hydroxyacetophenone, o-hydroxyacetophenone, etc.), or dienes (dicyclopentadiene, tricyclopentadiene, etc.); Phenols and substituted biphenyls (such as 4,4'-bis (chloromethyl) -1,1'-biphenyl and 4,4'-bis (methoxymethyl) -1,1'-biphenyl) or substituted phenyls ( A phenol resin obtained by polycondensation with 1,4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, 1,4-bis (hydroxymethyl) benzene, etc .; Or a modified product of the phenolic resin; Lumpur A and halogenated phenols such as brominated phenol resin (e) Other imidazoles, BF 3 - amine complex, guanidine derivatives
これら他の硬化剤の中ではジアミノジフェニルメタン、ジアミノジフェニルスルホン及びナフタレンジアミンなどのアミン系化合物、並びにカテコールとアルデヒド類、ケトン類、ジエン類、置換ビフェニル類又は置換フェニル類との縮合物などの活性水素基が隣接している構造を有する硬化剤がエポキシ樹脂の配列に寄与するため好ましい。
他の硬化剤は単独で用いてもよく、複数を併用してもよい。Among these other curing agents, amine compounds such as diaminodiphenylmethane, diaminodiphenylsulfone and naphthalenediamine, and active hydrogen such as condensates of catechol with aldehydes, ketones, dienes, substituted biphenyls or substituted phenyls A curing agent having a structure in which groups are adjacent to each other is preferable because it contributes to the arrangement of the epoxy resin.
Other curing agents may be used alone or in combination.
なお、本発明のエポキシ樹脂組成物において、本発明のフェノール樹脂を硬化剤として用いる場合には、本発明のフェノール樹脂以外に、その他の硬化剤を併用して用いてもよい。併用して用いられる硬化剤としては、例えば、前述と同様の、アミン系化合物、酸無水物系化合物、アミド系化合物及びフェノール系化合物等が挙げられる。 When the phenolic resin of the present invention is used as a curing agent in the epoxy resin composition of the present invention, other curing agents may be used in combination with the phenolic resin of the present invention. Examples of the curing agent used in combination include an amine compound, an acid anhydride compound, an amide compound, and a phenol compound as described above.
他の硬化剤を併用する場合、本発明のエポキシ樹脂組成物中の全硬化剤成分に占める本発明のフェノール樹脂の割合は5質量%以上が好ましく、10質量%以上がより好ましく、30質量%以上が更に好ましい。本発明のエポキシ樹脂組成物において、本発明のフェノール化合物を含む全硬化剤の使用量は、全エポキシ樹脂のエポキシ基1当量に対して0.5〜2.0当量が好ましく、0.6〜1.5当量が特に好ましい。 When another curing agent is used in combination, the proportion of the phenolic resin of the present invention in all the curing agent components in the epoxy resin composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and 30% by mass. The above is more preferred. In the epoxy resin composition of the present invention, the amount of the total curing agent containing the phenolic compound of the present invention is preferably 0.5 to 2.0 equivalents, more preferably 0.6 to 2.0 equivalents to 1 equivalent of the epoxy group of all epoxy resins. 1.5 equivalents are particularly preferred.
本発明のエポキシ樹脂組成物には、必要により硬化促進剤を添加しても良い。硬化促進剤の具体例としては、トリフェニルフォスフィン、ビス( メトキシフェニル) フェニルフォスフィン等のフォスフィン類、2―メチルイミダゾール、2−エチルイミダゾール、2―エチル,4―メチルイミダゾール等のイミダゾール類、2−(ジメチルアミノメチル)フェノール、トリスジメチルアミノメチルフェノール、ジアザビシクロウンデセン等の3級アミン類、テトラブチルアンモニウム塩、トリイソプロピルメチルアンモニウム塩、トリメチルデカニルアンモニウム塩、セチルトリメチルアンモニウム塩などの4級アンモニウム塩、トリフェニルベンジルフォスフォニウム塩、トリフェニルエチルフォスフォニウム塩、テトラブチルフォスフォニウム塩などの4級フォスフォニウム塩(4級塩のカウンターイオンはハロゲン、有機酸イオン、水酸化物イオンなど、特に指定は無いが、特に有機酸イオン、水酸化物イオンが好ましい。)、オクチル酸スズ等の金属化合物等が例示される。
硬化促進剤の使用量は、エポキシ樹脂100重量部当たり、通常0.2〜5.0重量部、好ましくは、0.2〜4.0重量部である。If necessary, a curing accelerator may be added to the epoxy resin composition of the present invention. Specific examples of the curing accelerator include phosphines such as triphenylphosphine and bis (methoxyphenyl) phenylphosphine; imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethylimidazole, and the like; Tertiary amines such as 2- (dimethylaminomethyl) phenol, trisdimethylaminomethylphenol, diazabicycloundecene, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, etc. Quaternary phosphonium salts such as quaternary ammonium salts, triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, and tetrabutylphosphonium salts (the counter ion of the quaternary salt is halogen , Organic acid ions, hydroxide ions, etc. are not particularly specified, but organic acid ions and hydroxide ions are particularly preferred.), And metal compounds such as tin octylate.
The amount of the curing accelerator to be used is generally 0.2 to 5.0 parts by weight, preferably 0.2 to 4.0 parts by weight, per 100 parts by weight of the epoxy resin.
本発明のエポキシ樹脂組成物(以下、硬化性樹脂組成物とも称する)には、必要に応じて無機充填剤を添加することができる。無機充填剤としては、結晶シリカ、溶融シリカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、炭化ケイ素、窒化ケイ素、窒化ホウ素、ジルコニア、フォステライト、ステアタイト、スピネル、チタニア、タルク等の粉体またはこれらを球形化したビーズ等が挙げられるが、これらに限定されるものではない。これらは単独で用いてもよく、2種以上を用いてもよい。これら無機充填剤の含有量は、本発明の硬化性樹脂組成物中において0〜95重量%を占める量が用いられる。更に本発明の硬化性樹脂組成物には、シランカップリング剤、ステアリン酸、パルミチン酸、ステアリン酸亜鉛、ステアリン酸カルシウム等の離型剤、界面活性剤、染料、顔料、紫外線吸収剤等の種々の配合剤、各種熱硬化性樹脂を添加することができる。 An inorganic filler can be added to the epoxy resin composition of the present invention (hereinafter also referred to as a curable resin composition) as needed. Examples of the inorganic filler include powders of crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc and the like. And the like, but are not limited to these. These may be used alone or in combination of two or more. As the content of these inorganic fillers, an amount occupying 0 to 95% by weight in the curable resin composition of the present invention is used. Further, the curable resin composition of the present invention includes a silane coupling agent, a releasing agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, a surfactant, a dye, a pigment, and various kinds of ultraviolet absorbers. A compounding agent and various thermosetting resins can be added.
本発明のエポキシ樹脂組成物には、必要に応じてシランカップリング剤、離型剤及び顔料等種々の配合剤、各種熱硬化性樹脂並びに各種熱可塑性樹脂等を添加することができる。熱硬化性樹脂及び熱可塑性樹脂の具体例としては、ビニルエステル樹脂、不飽和ポリエステル樹脂、マレイミド樹脂、シアナート樹脂、イソシアナート化合物、ベンゾオキサジン化合物、ビニルベンジルエーテル化合物、ポリブタジエンおよびこの変性物、アクリロニトリル共重合体の変性物、インデン樹脂、フッ素樹脂、シリコーン樹脂、ポリエーテルイミド、ポリエーテルスルホン、ポリフェニレンエーテル、ポリアセタール、ポリスチレン、ポリエチレン、ジシクロペンタジエン樹脂等が挙げられる。熱硬化性樹脂、または熱可塑性樹脂は本発明のエポキシ樹脂組成物中において60質量%以下を占める量が用いられる。 Various compounding agents such as a silane coupling agent, a release agent and a pigment, various thermosetting resins, various thermoplastic resins, and the like can be added to the epoxy resin composition of the present invention as needed. Specific examples of the thermosetting resin and the thermoplastic resin include a vinyl ester resin, an unsaturated polyester resin, a maleimide resin, a cyanate resin, an isocyanate compound, a benzoxazine compound, a vinylbenzyl ether compound, polybutadiene and a modified product thereof, and acrylonitrile. Modified polymer, indene resin, fluororesin, silicone resin, polyetherimide, polyethersulfone, polyphenylene ether, polyacetal, polystyrene, polyethylene, dicyclopentadiene resin and the like can be mentioned. The thermosetting resin or the thermoplastic resin is used in an amount occupying 60% by mass or less in the epoxy resin composition of the present invention.
本発明のエポキシ樹脂組成物は、上記各成分を均一に混合することにより得られ、その好ましい用途としては半導体封止材やプリント配線板等が挙げられる。
本発明のエポキシ樹脂組成物は従来知られているのと同様の方法で容易にその硬化物とすることが出来る。例えば、本発明のエポキシ樹脂組成物の必須成分であるエポキシ樹脂、硬化剤及び無機充填材、並びに必要により硬化促進剤、配合剤、各種熱硬化性樹脂や各種熱可塑性樹脂等を、必要に応じて押出機、ニーダ又はロール等を用いて均一になるまで充分に混合して得られた本発明のエポキシ樹脂組成物を、溶融注型法あるいはトランスファー成型法やインジェクション成型法、圧縮成型法などによって成型し、更にその融点以上で2〜10時間加熱することにより本発明のエポキシ樹脂組成物の硬化物を得ることが出来る。前述の方法でリードフレーム等に搭載された半導体素子を封止することにより、本発明のエポキシ樹脂組成物を半導体封止用途に用いることができる。The epoxy resin composition of the present invention is obtained by uniformly mixing the above-mentioned components, and preferable applications thereof include a semiconductor sealing material and a printed wiring board.
The epoxy resin composition of the present invention can be easily made into a cured product by the same method as conventionally known. For example, an epoxy resin, a curing agent and an inorganic filler, which are essential components of the epoxy resin composition of the present invention, and, if necessary, a curing accelerator, a compounding agent, various thermosetting resins and various thermoplastic resins, if necessary, The epoxy resin composition of the present invention obtained by thoroughly mixing until uniform using an extruder, kneader or roll, etc., by a melt casting method or a transfer molding method, an injection molding method, a compression molding method, etc. The cured product of the epoxy resin composition of the present invention can be obtained by molding and heating at a temperature higher than the melting point for 2 to 10 hours. The epoxy resin composition of the present invention can be used for semiconductor encapsulation by encapsulating a semiconductor element mounted on a lead frame or the like by the method described above.
また、本発明のエポキシ樹脂組成物は溶剤を含むワニスとすることもできる。該ワニスは、例えば、エポキシ樹脂、硬化剤のうち、少なくとも一方に本発明のエポキシ樹脂、もしくは本発明のフェノール樹脂を含み、必要に応じて無機充填材などのその他の成分を含む混合物を、トルエン、キシレン、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、シクロペンタノン、N,N’−ジメチルホルムアミド、N,N’−ジメチルアセトアミド、ジメチルスルホキシド、N−メチルピロリドン、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールジエチルエーテル等のグリコールエーテル類、酢酸エチル、酢酸ブチル、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート、グルタル酸ジアルキル、コハク酸ジアルキル、アジピン酸ジアルキル等のエステル類、γ−ブチロラクトン等の環状エステル類、石油エーテル、石油ナフサ、水添石油ナフサ及びソルベントナフサ等の石油系溶剤等の有機溶剤と混合することにより得ることが出来る。溶剤の量はワニス全体に対し通常10〜95質量%、好ましくは15〜85質量%である。
上記のようにして得られるワニスをガラス繊維、カーボン繊維、ポリエステル繊維、ポリアミド繊維、アルミナ繊維及び紙などの繊維基材に含浸させた後に加熱によって溶剤を除去すると共に、本発明のエポキシ樹脂組成物を半硬化状態とすることにより、本発明のプリプレグを得ることが出来る。尚、ここで言う「半硬化状態」とは、反応性の官能基であるエポキシ基が一部未反応で残っている状態を意味する。該プリプレグを熱プレス成型して硬化物を得ることが出来る。Further, the epoxy resin composition of the present invention may be a varnish containing a solvent. The varnish includes, for example, a mixture containing an epoxy resin of the present invention in at least one of an epoxy resin and a curing agent, or a phenolic resin of the present invention, and, if necessary, other components such as an inorganic filler. , Xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, N, N'-dimethylformamide, N, N'-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Glycol ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, vinegar Esters such as butyl, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate, cyclic esters such as γ-butyrolactone, petroleum ether , Petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, and other organic solvents such as petroleum solvents. The amount of the solvent is usually 10 to 95% by mass, preferably 15 to 85% by mass based on the whole varnish.
The varnish obtained as described above is impregnated into a fiber base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber and paper, and then the solvent is removed by heating and the epoxy resin composition of the present invention. In a semi-cured state, the prepreg of the present invention can be obtained. Here, the “semi-cured state” means a state in which an epoxy group, which is a reactive functional group, partially remains unreacted. The prepreg can be subjected to hot press molding to obtain a cured product.
以下、本発明を実施例で更に詳細に説明するが、本発明はこれら実施例に限定されるものではない。合成例、実施例、比較例において部は質量部を意味する。
なお、水酸基当量、軟化点、は以下の条件で測定した。
・水酸基当量
JIS K−7236に記載された方法で測定し、単位はg/eq.である。
・軟化点
JIS K−7234に準拠した方法で測定し、単位は℃である。Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the synthesis examples, examples, and comparative examples, “parts” means “parts by mass”.
In addition, the hydroxyl equivalent and the softening point were measured under the following conditions.
-Hydroxy group equivalent Measured according to the method described in JIS K-7236, and the unit is g / eq. It is.
-Softening point Measured by a method according to JIS K-7234, and the unit is ° C.
(合成例1)
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、4’−ヒドロキシアセトフェノン150部、バニリン167部およびエタノール221部を仕込み、溶解した。これに97質量%硫酸22部を添加後60℃ まで昇温し、この温度で10時間反応後、反応液を水1324部に注入し、晶析させた。結晶を濾別後、水662部で2回水洗し、その後真空乾燥し、黄色結晶のフェノール化合物(a)を282部得た。得られた結晶のDSC測定による吸熱ピーク温度は233℃であった。(Synthesis example 1)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 150 parts of 4'-hydroxyacetophenone, 167 parts of vanillin, and 221 parts of ethanol, and dissolved therein. After adding 22 parts of 97% by mass sulfuric acid, the temperature was raised to 60 ° C., and after reacting at this temperature for 10 hours, the reaction solution was poured into 1324 parts of water to be crystallized. After the crystals were separated by filtration, the crystals were washed twice with 662 parts of water and then dried under vacuum to obtain 282 parts of phenol compound (a) as yellow crystals. The endothermic peak temperature of the obtained crystal measured by DSC was 233 ° C.
(実施例1)
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながらHCA(三光株式会社製)178部、キシレン360部を加え、100℃に加熱した。そこにフェノール化合物(a)200部を1時間かけて分割添加し、その後130℃に昇温し、10時間加熱還流した。反応物にエタノール180部を加えた後、エバポレーターで溶媒を減圧留去し、本発明のフェノール樹脂(b)(P1)を320g得た。得られたフェノール樹脂(b)の水酸基当量は243g/eqであり、軟化点は135.8℃であった。(Example 1)
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 178 parts of HCA (manufactured by Sanko Co., Ltd.) and 360 parts of xylene were added while heating with nitrogen, and heated to 100 ° C. Thereto was added 200 parts of the phenol compound (a) in portions over 1 hour, then the temperature was raised to 130 ° C., and the mixture was heated under reflux for 10 hours. After 180 parts of ethanol was added to the reaction product, the solvent was distilled off under reduced pressure using an evaporator to obtain 320 g of the phenol resin (b) (P1) of the present invention. The hydroxyl equivalent of the obtained phenol resin (b) was 243 g / eq, and the softening point was 135.8 ° C.
(実施例2)
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながら本発明のフェノール樹脂(P1 水酸基当量243g/eq.)163部、エピクロロヒドリン433部(7モル当量 対 フェノール樹脂)、メタノール130部を加え、撹拌下で溶解し、70〜75℃にまで昇温した。次いでフレーク状の水酸化ナトリウム30部を90分かけて分割添加した後、更に75℃で75分反応を行った。反応終了後、水90部で水洗を行い、油層からロータリーエバポレーターを用いて減圧下、過剰のエピクロルヒドリン等の溶剤類を留去した。残留物にメチルイソブチルケトン380部を加え溶解し、75℃にまで昇温した。撹拌下で30重量%の水酸化ナトリウム水溶液11部を加え、1時間反応を行った後、油層の洗浄水が中性になるまで水洗を行った。得られた溶液をロータリーエバポレーターを用いて減圧下、メチルイソブチルケトン等を留去することで本発明のエポキシ樹脂(EP1)183部を得た。得られたエポキシ樹脂のエポキシ当量は304g/eq.であった。(Example 2)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen while 163 parts of the phenol resin of the present invention (P1 hydroxyl equivalent: 243 g / eq.) And 433 parts of epichlorohydrin (7 mole equivalent to phenol resin). ) And 130 parts of methanol were added, dissolved under stirring, and heated to 70 to 75 ° C. Next, 30 parts of sodium hydroxide in the form of flakes were added in portions over 90 minutes, and the reaction was further performed at 75 ° C. for 75 minutes. After the completion of the reaction, the mixture was washed with 90 parts of water, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure using a rotary evaporator. 380 parts of methyl isobutyl ketone was added to and dissolved in the residue, and the temperature was raised to 75 ° C. After stirring, 11 parts of a 30% by weight aqueous sodium hydroxide solution was added thereto, and the mixture was reacted for 1 hour. Thereafter, the oil layer was washed with water until the washing water became neutral. Methyl isobutyl ketone and the like were distilled off from the obtained solution under reduced pressure using a rotary evaporator to obtain 183 parts of an epoxy resin (EP1) of the present invention. The epoxy equivalent of the obtained epoxy resin was 304 g / eq. Met.
(実施例3〜6、比較例1)
実施例1で得られたフェノール樹脂(P1)ないし比較用のフェノール樹脂(P3)を、エポキシ樹脂(EP1及びEP2)、フィラー(無機充填材)、ワックス、カップリング剤、硬化促進剤を表1の割合(当量)で配合し、ミキシングロールを用いて均一に混合・混練し、硬化性樹脂組成物を得た。この硬化性樹脂組成物をミキサーにて粉砕し、更にタブレットマシーンにてタブレット化した。このタブレット化された硬化性樹脂組成物をトランスファー成型(175℃×60秒)し、更に脱型後160℃×2時間+180℃×6時間の条件で硬化し、評価用試験片を得た。この評価用試験片を用いて、耐熱性と難燃性を以下の要領で測定、評価した。試験結果を表1に示す。(Examples 3 to 6, Comparative Example 1)
The phenolic resin (P1) obtained in Example 1 or the phenolic resin (P3) for comparison was replaced with an epoxy resin (EP1 and EP2), a filler (inorganic filler), a wax, a coupling agent, and a curing accelerator. And the mixture was uniformly mixed and kneaded using a mixing roll to obtain a curable resin composition. This curable resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted curable resin composition was subjected to transfer molding (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation. Using this test piece for evaluation, heat resistance and flame retardancy were measured and evaluated in the following manner. Table 1 shows the test results.
<耐熱性試験>
動的粘弾性測定器:TA−instruments製、DMA−2980
測定温度範囲:−30℃〜280℃
温速度:2℃/分
試験片サイズ:5mm×50mmに切り出した物を使用した(厚みは約800μm)。
解析条件Tg:DMA測定に於けるTanδのピーク点(tanδMAX)をTgとした。
<難燃性試験>
・難燃性の判定:UL94に準拠して行った。ただし、サンプルサイズは幅12.5mm×長さ150mmとし、厚さは0.8mmで試験を行った。
・残炎時間:5個1組のサンプルに10回接炎したあとの残炎時間の合計。<Heat resistance test>
Dynamic viscoelasticity analyzer: manufactured by TA-instruments, DMA-2980
Measurement temperature range: -30 ° C to 280 ° C
Temperature rate: 2 ° C./min. Specimen size: Cut out to 5 mm × 50 mm (thickness was about 800 μm).
Analysis condition Tg: The peak point of Tan δ (tan δ MAX) in the DMA measurement was defined as Tg.
<Flame retardancy test>
-Determination of flame retardancy: performed in accordance with UL94. However, the test was performed with a sample size of 12.5 mm in width × 150 mm in length and a thickness of 0.8 mm.
-Afterflame time: The total afterflame time after 10 sets of flame contact with a set of five samples.
EP1:日本化薬社製 NC2000L
EP2:日本化薬社製 NC3000
P3:三井化学社製 ミレックスXLC−3L
P2:P1とP3を重量比で33:67の割合になるように混合
P4:P1とP3を重量比で5:95の割合になるように混合
P5:P1とP3を重量比で10:90の割合になるように混合
ワックス:カルナバ1号
硬化促進剤:トリフェニルフォスフィン(北興化学社製 TPP)
カップリング剤:信越化学工業社製 KBM−303
無機充填材:溶融シリカ 瀧森工業社製 MSR−2122 対樹脂83wt%
硬化促進剤使用量:
耐熱性の評価に使用する試料ではエポキシ樹脂重量に対し1%とし、難燃性の評価に使用する試料ではエポキシ樹脂重量に対し2%とした。
ワックス使用量:0.3重量% 対組成物
カップリング剤使用量:0.4重量% 対フィラー
エポキシ樹脂・硬化剤比率:1等当量EP1: NC2000L manufactured by Nippon Kayaku Co., Ltd.
EP2: NC3000 manufactured by Nippon Kayaku Co., Ltd.
P3: MIREX XLC-3L manufactured by Mitsui Chemicals, Inc.
P2: P1 and P3 are mixed at a weight ratio of 33:67. P4: P1 and P3 are mixed at a weight ratio of 5:95. P5: P1 and P3 are mixed at a weight ratio of 10:90. Wax: Carnauba No. 1 curing accelerator: triphenylphosphine (TPK, manufactured by Hokuko Chemical Co., Ltd.)
Coupling agent: KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.
Inorganic filler: fused silica MSR-2122 manufactured by Takimori Kogyo Co., Ltd. 83 wt% of resin
Curing accelerator usage:
The sample used for evaluation of heat resistance was 1% based on the weight of the epoxy resin, and the sample used for evaluation of flame retardancy was 2% based on the weight of the epoxy resin.
Wax usage: 0.3% by weight: Composition coupling agent usage: 0.4% by weight: Filler epoxy resin / hardener ratio: 1 equivalent
上記表から明らかなように、本発明のフェノール樹脂は、比較例のフェノール樹脂と比較して、耐熱性、難燃性共に優れるという結果が示された。 As is clear from the above table, the results showed that the phenolic resin of the present invention was superior in both heat resistance and flame retardancy as compared with the phenolic resin of the comparative example.
本発明を特定の態様を参照して詳細に説明したが、本発明の精神と範囲を離れることなく様々な変更および修正が可能であることは、当業者にとって明らかである。
なお、本出願は、2013年10月9日付で出願された日本国特許出願(特願2013−211750)に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。Although the present invention has been described in detail with reference to particular embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on Oct. 9, 2013 (Japanese Patent Application No. 2013-212750), which is incorporated by reference in its entirety. Also, all references cited herein are incorporated in their entirety.
本発明のフェノール樹脂は、エポキシ樹脂組成物に用いることができ、該エポキシ樹脂組成物の硬化物は優れた耐熱性、難燃性を示すことから、半導体封止材料、プリプレグを始めとする各種複合材料、接着剤、塗料等に使用する場合に有用である。
The phenolic resin of the present invention can be used for an epoxy resin composition, and a cured product of the epoxy resin composition exhibits excellent heat resistance and flame retardancy. It is useful when used for composite materials, adhesives, paints and the like.
Claims (7)
(式(4)中、R1はそれぞれ独立に、水素原子、炭素数1〜10の置換若しくは無置換のアルキル基、炭素数6〜10の置換若しくは無置換のアリール基、水酸基、ニトロ基又は炭素数1〜10の置換若しくは無置換のアルコキシ基のいずれかを表し、R2はそれぞれ独立に水素原子、炭素数1〜10の置換若しくは無置換のアルキル基、炭素数6〜10の置換若しくは無置換のアリール基、水酸基、ニトロ基、ホルミル基、アリル基又は炭素数1〜10の置換若しくは無置換のアルコキシ基のいずれかを表し、kはR2の数を表し、0〜4の整数であり、mはR1の数を表し、0〜4の整数であり、Zは水素原子又は下記式(5)の構造を表し、複数存在するZのうち少なくとも一つは下記式(5)の構造を表す。)
(式(5)中、R3はそれぞれ独立に水素原子、アルキル基又は芳香族基を表す。) It is represented by the following formula (4) and has a hydroxyl equivalent of 220 to 750 g / eq. Der Ru phenolic resin.
(In the formula (4), R 1 is each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group or R 2 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 6 to 10 carbon atoms, Represents an unsubstituted aryl group, hydroxyl group, nitro group, formyl group, allyl group or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, k represents the number of R 2 , and an integer of 0 to 4 And m represents the number of R 1 , an integer of 0 to 4, Z represents a hydrogen atom or a structure represented by the following formula (5), and at least one of a plurality of Zs is represented by the following formula (5) Represents the structure of
(In the formula (5), R 3 independently represents a hydrogen atom, an alkyl group, or an aromatic group.)
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2014
- 2014-10-08 JP JP2015541604A patent/JP6671958B2/en not_active Expired - Fee Related
- 2014-10-08 KR KR1020167002775A patent/KR20160068728A/en not_active Application Discontinuation
- 2014-10-08 WO PCT/JP2014/076877 patent/WO2015053298A1/en active Application Filing
- 2014-10-08 CN CN201480055628.XA patent/CN105612190B/en not_active Expired - Fee Related
- 2014-10-09 TW TW103135174A patent/TW201527345A/en unknown
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Publication number | Publication date |
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CN105612190A (en) | 2016-05-25 |
WO2015053298A1 (en) | 2015-04-16 |
JPWO2015053298A1 (en) | 2017-03-09 |
KR20160068728A (en) | 2016-06-15 |
CN105612190B (en) | 2017-11-10 |
TW201527345A (en) | 2015-07-16 |
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