WO2024070773A1 - Multifunctional vinyl compound, composition thereof, and cured product - Google Patents
Multifunctional vinyl compound, composition thereof, and cured product Download PDFInfo
- Publication number
- WO2024070773A1 WO2024070773A1 PCT/JP2023/033749 JP2023033749W WO2024070773A1 WO 2024070773 A1 WO2024070773 A1 WO 2024070773A1 JP 2023033749 W JP2023033749 W JP 2023033749W WO 2024070773 A1 WO2024070773 A1 WO 2024070773A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vinyl compound
- vinyl
- compound
- thermal conductivity
- cured product
- Prior art date
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- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 73
- -1 vinyl compound Chemical class 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims description 31
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 43
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000007870 radical polymerization initiator Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000002904 solvent Substances 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 6
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 5
- 238000007789 sealing Methods 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- 150000002440 hydroxy compounds Chemical class 0.000 description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 239000011256 inorganic filler Substances 0.000 description 11
- 229910003475 inorganic filler Inorganic materials 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 10
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 150000003934 aromatic aldehydes Chemical class 0.000 description 6
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 229940093475 2-ethoxyethanol Drugs 0.000 description 3
- 229940061334 2-phenylphenol Drugs 0.000 description 3
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 236TMPh Natural products CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical group C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
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- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 235000010292 orthophenyl phenol Nutrition 0.000 description 3
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- OGRAOKJKVGDSFR-UHFFFAOYSA-N 2,3,5-trimethylphenol Chemical compound CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-UHFFFAOYSA-N 0.000 description 2
- LVLNPXCISNPHLE-UHFFFAOYSA-N 2-[(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1O LVLNPXCISNPHLE-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
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- 229940126062 Compound A Drugs 0.000 description 2
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- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
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- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- UBXYXCRCOKCZIT-UHFFFAOYSA-N biphenyl-3-ol Chemical compound OC1=CC=CC(C=2C=CC=CC=2)=C1 UBXYXCRCOKCZIT-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- PVAONLSZTBKFKM-UHFFFAOYSA-N diphenylmethanediol Chemical compound C=1C=CC=CC=1C(O)(O)C1=CC=CC=C1 PVAONLSZTBKFKM-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000005352 hydroxybiphenyls Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical class ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008054 signal transmission Effects 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
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 238000006886 vinylation reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
Definitions
- the present invention relates to vinyl compounds, and more specifically to polyfunctional vinyl compounds with excellent solvent solubility that are useful as insulating materials for electrical and electronic components such as semiconductor encapsulation, laminates, and heat dissipation substrates, compositions thereof, and cured resins obtained by curing them that have excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric tangent, and flame retardancy.
- the thermal conductivity of the inorganic filler is overwhelmingly higher than that of the matrix resin, and even if the thermal conductivity of the matrix resin itself is increased, it does not contribute significantly to improving the thermal conductivity of the composite material, and a sufficient effect of improving thermal conductivity has not been obtained.
- Patent Document 7 proposes a tetrafunctional or higher vinyl resin with a biphenyl skeleton as a multifunctional vinyl resin that combines high thermal conductivity and low dielectric tangent, but does not describe the solvent solubility of the multifunctional vinyl resin or the polyhydric hydroxyl resin that is its raw material, nor does it mention the effect of impurities such as remaining polar groups on thermal conductivity.
- JP 2009-170493 A International Publication No. 2013/100172 Japanese Patent Application Laid-Open No. 11-147936 JP 2002-309067 A Japanese Patent Application Laid-Open No. 11-323162 Japanese Patent Application Laid-Open No. 9-118673 International Publication No. 2021-200414
- the object of the present invention is to provide a vinyl composition that is useful for sealing electric and electronic components, as a circuit board material, etc., and that gives a cured product that has excellent solvent solubility as well as excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric tangent, and flame retardancy, and to provide the cured product.
- Another object is to provide a vinyl compound that can be used in this vinyl composition.
- R1 to R4 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.
- At least one of R1 to R4 in the above multifunctional vinyl compound is a methyl group or a phenyl group.
- the present invention also relates to a multifunctional vinyl composition containing the above-mentioned multifunctional vinyl compound and a radical polymerization initiator as essential components, and a multifunctional vinyl cured product obtained by curing this multifunctional vinyl composition.
- the polyfunctional vinyl compounds of the present invention have excellent solvent solubility and are suitable for use in vinyl resin compositions and their cured products for applications such as lamination, molding, casting, and adhesion. Furthermore, these cured products also have excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric tangent, and flame retardancy, making them suitable for sealing electrical and electronic components, as circuit board materials, etc.
- Example 1 is a GPC chart of the polyfunctional vinyl compound obtained in Example 1.
- R1 to R4 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.
- an alkyl group is preferable, and from the viewpoint of heat resistance and high thermal conductivity, an aromatic group is preferable.
- an alkyl group having more than 6 carbon atoms it becomes difficult to suppress molecular motion, and there is a concern of a decrease in compatibility.
- a bulky structure with large steric hindrance increases crystallinity, which raises concerns about solvent solubility.
- a more preferable structure is a methyl group or a phenyl group.
- R1 to R4 may be a mixture of different structures.
- the substitution position of the vinyl benzyl ether is not particularly limited, but from the viewpoint of thermal conductivity and heat resistance, it is preferably in the para position relative to the methine group connecting the three aromatic rings. In particular, it is more preferable that all three vinyl benzyl ethers are in the para position.
- the number average molecular weight (Mn) of the polyfunctional vinyl compound of the present invention is preferably 2000 or less, more preferably 1500 or less.
- the compound may further contain a multi-branched structure represented by the following general formula (2), where n is the repeating number and is a number from 0 to 20.
- the average value (number average) of n is preferably in the range of 0.01 to 5.0, more preferably in the range of 0.01 to 2.0, and even more preferably in the range of 0.01 to 1.0. Therefore, the polyfunctional vinyl compound of the present invention is also called a polyfunctional vinyl resin.
- the preferred vinyl equivalent range for the polyfunctional vinyl compound of the present invention is 150 to 450 g/eq, and more preferably 200 to 300 g/eq. If it is less than this range, the reaction will occur too quickly, making it difficult to control, and if it is more than this range, there is a concern that the reactivity will decrease and it will be difficult to obtain a uniform cured product.
- the polyfunctional vinyl compound of the present invention can be obtained by reacting a trifunctional hydroxy compound with chloromethylstyrene, but if the amount of unreacted hydroxyl groups remaining is less than 5000 g/eq, the curing is insufficient, and the thermal conductivity and heat resistance are reduced.
- the hydroxyl groups are polar groups, there is a concern that the remaining hydroxyl groups may hinder the reduction of the dielectric constant and dielectric loss tangent.
- the hydroxyl group equivalent is preferably 5,000 g/eq or more, more preferably 10,000 g/eq or more.
- the chlorine component is derived from the raw material chloromethylstyrene, and if the chlorine component remains, as with the hydroxyl group, there is a concern that it will inhibit the reduction of the dielectric constant and the dielectric loss tangent, and there is a concern that the curing reaction will be inhibited by the polar group, resulting in a decrease in the thermal conductivity and heat resistance.
- the total chlorine content is preferably 2000 ppm or less, more preferably 1000 ppm or less.
- the polyfunctional vinyl compound of the present invention can be obtained by reacting a trifunctional hydroxy compound represented by formula (3) with an aromatic vinylating agent.
- R1 to R4 are the same as those of the vinyl compound of formula (1).
- the trifunctional hydroxy compound of formula (3) preferably has a hydroxyl group equivalent of 90 to 350 g/eq, more preferably 100 to 200 g/eq.
- the trifunctional hydroxy compound of formula (3) can be produced by a general method, for example, by polycondensation of a monohydric phenol compound and an aromatic aldehyde.
- monovalent phenol compounds include monoalkylphenols such as phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, p-octylphenol, p-t-butylphenol, o-cyclohexylphenol, m-cyclohexylphenol, and p-cyclohexylphenol; dialkylphenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,4-xylenol, and 2,6-xylenol; trialkylphenols such as 2,3,5-trimethylphenol and 2,3,6-trimethylphenol, and further hydroxybiphenyls such as 2-phenylphenol, 4-phenylphenol, 3-benzyl-1,1'-biphenyl-2-ol, 3-benzyl-1,1'-biphenyls
- 2,5-xylenol, 2,6-xylenol, and 2-phenylphenol are particularly preferred. These phenolic compounds can be used alone or in combination of two or more types.
- Aromatic aldehydes include, for example, hydroxybenzaldehydes such as 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, and 4-hydroxybenzaldehyde. From the standpoint of heat resistance and thermal conductivity, 4-hydroxybenzaldehyde is preferred.
- the polycondensation of the phenol compound and the aromatic aldehyde may be carried out using an acid catalyst, such as acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, manganese acetate, etc.
- an acid catalyst such as acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, manganese acetate, etc.
- These acid catalysts may be used alone or in combination of two or more. Among these acid catalysts, sulfuric acid and paratoluenesulfonic acid are preferred because of their excellent activity.
- the acid catalyst may be added before or during the reaction.
- the polycondensation of the phenol compound and the aromatic aldehyde may be carried out in the presence of a solvent, if necessary, to obtain a polycondensate.
- a solvent include monoalcohols such as methanol, ethanol, and propanol; polyols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, and glycerin; glycol ethers such as 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene
- the reaction temperature during polycondensation of the phenol compound and aromatic aldehyde is in the range of 20 to 140°C, preferably in the range of 80 to 110°C.
- the charging ratio of the phenol compound/aromatic aldehyde is in the range of 1/0.1 to 1/0.5 in molar ratio, and more preferably in the range of 1/0.3 to 1/0.5, since the phenol compound after the reaction can be easily removed by reprecipitation or the like.
- the polyfunctional vinyl compound of the present invention can be obtained by reacting a trifunctional hydroxy compound with an aromatic vinylating agent.
- the vinyl compound of the present invention represented by the above formula (1) can be obtained by reacting a trifunctional hydroxy compound represented by the above formula (3) with chloromethylstyrene.
- This reaction can be carried out in the same manner as the well-known vinylation reaction.
- the blending ratio is preferably 0.8 to 1.2 equivalents of aromatic vinylating agent (e.g., chloromethylstyrene) per 1.0 equivalent of hydroxyl group, which is the functional group of the trifunctional hydroxy compound.
- aromatic vinylating agent e.g., chloromethylstyrene
- Aromatic vinylating agents are preferably halomethylstyrenes, particularly chloromethylstyrene.
- Other examples include bromomethylstyrene and its isomers, and those with substituents.
- the substitution position of the halomethyl compound for example, in the case of halomethylstyrene, the 4-position is preferred, and it is preferable that the 4-position compound accounts for 60% or more by weight of the total.
- the reaction between a trifunctional hydroxy compound and an aromatic vinylating agent can be carried out in the absence or presence of a solvent.
- the reaction can be carried out by adding the aromatic vinylating agent to the hydroxy compound, adding a metal hydroxide, and removing the generated metal salt by a method such as filtration or washing with water.
- the solvent include, but are not limited to, methyl ethyl ketone, benzene, toluene, xylene, methyl isobutyl ketone, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, etc. From the viewpoint of reactivity, methyl ethyl ketone is preferable.
- Specific examples of the metal hydroxide include, but are not limited to, sodium hydroxide, potassium hydroxide, etc.
- the vinylization reaction is preferably carried out at a temperature of 90°C or less, more preferably 70°C or less. If the temperature is higher than this, the vinyl benzyl ether group will self-polymerize due to heat, making it difficult to control the reaction.
- polymerization inhibitors such as quinones, nitro compounds, nitrophenols, nitroso and nitrone compounds, and oxygen may be used.
- the end point of the reaction can be determined by tracking the remaining amount of halomethylstyrene as an aromatic vinylating agent using various chromatograms such as GPC, and the reaction rate can be adjusted by the type and amount of metal hydroxide, the addition rate, solids concentration, etc.
- the polyfunctional vinyl compound of the present invention can be cured by itself, but it is also suitable to use it as a polyfunctional vinyl composition containing various additives.
- a radical polymerization initiator such as an azo compound or an organic peroxide may be blended to effect curing.
- the polyfunctional vinyl composition of the present invention contains a polyfunctional vinyl compound and a radical polymerization initiator as essential components, but can also contain other vinyl compounds and other thermosetting resins, such as epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polyphenylene ether resins, and benzoxazine resins.
- inorganic fillers such as glass cloth, carbon fiber, alumina, and boron nitride may be added.
- thermal conductivity is preferably 20 W/m.K or more, more preferably 30 W/m.K or more, and even more preferably 50 W/m.K or more. At least a portion of the inorganic filler, preferably 50 wt% or more, has a thermal conductivity of 20 W/m.K or more.
- the average thermal conductivity of the inorganic filler as a whole increases in the order of desirability: 20 W/m.K or more, 30 W/m.K or more, and 50 W/m.K or more.
- inorganic fillers with such thermal conductivity include inorganic powder fillers such as boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, alumina, and magnesium oxide.
- additives may be added to improve adhesive strength and ease of handling of the composition, such as silane coupling agents, defoamers, internal release agents, and flow control agents.
- the polyfunctional vinyl compound or polyfunctional vinyl composition of the present invention can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone, impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and heated and dried to obtain a prepreg, which can then be hot-press molded to obtain a cured product.
- a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone
- the resin can be applied onto a sheet-like material such as copper foil, stainless steel foil, polyimide film, or polyester film to form a laminate, and the resin sheet obtained by heating and drying can be subjected to heat press molding to obtain a cured product.
- a sheet-like material such as copper foil, stainless steel foil, polyimide film, or polyester film
- GPC Measurement A main body (HLC-8220GPC, manufactured by Tosoh Corporation) equipped with four columns (TSKgel Super Multipore HZ-N, manufactured by Tosoh Corporation) in series was used, and the column temperature was set to 40°C. Tetrahydrofuran (THF) was used as the eluent, the flow rate was set to 0.35 mL/min, and a differential refractive index detector was used as the detector. 50 ⁇ L of the measurement sample was prepared by dissolving 0.1 g of sample in 10 mL of THF and filtering through a microfilter. Data processing was performed using GPC-8020 Model II version 6.00 manufactured by Tosoh Corporation.
- THF Tetrahydrofuran
- Solvent solubility 2 g of resin and 1 g of methyl ethyl ketone were weighed and placed in a sample bottle, and after heating and dissolving, the temperature was gradually lowered in a thermostatic bath, and the temperature in the bath at which the resin precipitated was measured. The higher the precipitation temperature (°C), the poorer the solvent solubility.
- Tg Glass transition temperature
- Td5 5% weight loss temperature
- carbon residue ratio Using a thermogravimetric/differential thermal analyzer (EXSTAR TG/DTA7300 manufactured by SII NanoTechnology), the 5% weight loss temperature (Td5) was measured under conditions of a nitrogen atmosphere and a heating rate of 10°C/min. The weight loss at 700°C was also measured and calculated as the carbon residue ratio.
- Thermal Conductivity was measured by a non-steady hot wire method using a NETZSCH LFA447 type thermal conductivity meter.
- Synthesis Example 2 The same procedure as in Synthesis Example 1 was carried out except that 36.8 g (0.30 mol) of 2,5-xylenol and 28.2 g (0.30 mol) of phenol were used instead of 73.6 g of 2,5-xylenol, to obtain 60.8 g of trifunctional hydroxy compound b.
- Trifunctional hydroxy compound b was a mixture of compounds represented by formula (3) in which R1 to R4 were all hydrogen atoms or methyl groups, and had a hydroxyl group equivalent of 105 g/eg.
- Example 1 Into a 1000 ml four-neck flask, 59.0 g (0.17 mol) of the trifunctional hydroxy compound a obtained in Synthesis Example 1, 400 g of methyl ethyl ketone, and 91.6 g (0.60 mol) of chloromethylstyrene (structural formula shown below) were added. The mixture was heated to 60°C, and 33.7 g of potassium hydroxide dissolved in 101 g of methanol was added dropwise over 3 hours, followed by reaction for another 6 hours.
- Example 2 The same procedure as in Example 1 was carried out except that 52.5 g (0.17 mol) of the trifunctional hydroxy compound b obtained in Synthesis Example 2 was used instead of the trifunctional hydroxy compound a, to obtain 100.3 g of a multifunctional vinyl compound (vinyl compound B).
- the vinyl equivalent of vinyl compound B was 212 g/eg., the hydroxyl equivalent was 14,000 g/eg., and the total chlorine was 500 ppm.
- Example 3 The same procedure as in Example 1 was carried out except that 74.5 g (0.17 mol) of the trifunctional hydroxy compound c obtained in Synthesis Example 3 was used instead of the trifunctional hydroxy compound a, to obtain 121.2 g of a multifunctional vinyl compound (vinyl compound C).
- the vinyl equivalent of vinyl compound C was 260 g/eg., the hydroxyl equivalent was 11,000 g/eg., and the total chlorine was 800 ppm.
- vinyl resin F a multifunctional vinyl resin
- the vinyl equivalent of vinyl resin F was 217g/eg., the hydroxyl equivalent was 17000g/eg., and the total chlorine was 400ppm.
- Examples 4 to 6, Comparative Examples 4 to 7 As the polyfunctional vinyl compound, vinyl compounds A to F obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and vinyl resin G (OPE-2ST: manufactured by Mitsubishi Gas Chemical Company, Inc., vinyl group equivalent: 590.0 g / eq, number average molecular weight 1187) were used, and Perbutyl P (manufactured by NOF Corporation), an organic peroxide, was used as a curing accelerator (radical polymerization initiator), and Adeka STAB AO-60 (manufactured by ADEKA Corporation) was used as an antioxidant in the blending ratio shown in Table 1.
- the composition was applied to a PET film and dried at 130 ° C. for 5 minutes to obtain a resin composition.
- the composition removed from the PET film was sandwiched between mirror plates and cured under reduced pressure at 130 ° C. for 15 minutes and at 210 ° C. for 80 minutes while applying a pressure of 2 MPa.
- the properties of the obtained cured product are shown in Table 1.
- the polyfunctional vinyl compounds of the examples showed superior physical properties, including higher thermal conductivity, lower dielectric constant, and lower dielectric tangent, compared to the comparative examples.
- the polyfunctional vinyl compound of the present invention is useful as an electronic material for high-speed communication devices, as it easily dissipates heat generated from electronic components and wiring and causes little signal loss.
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Abstract
The present invention provides a vinyl compound that has excellent solvent solubility, that yields a cured product having excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric tangent, and flame retardance, and that is useful for sealing electrical and electronic components and as a circuit board material. Provided is a multifunctional vinyl compound represented by general formula (1). In formula (1), R1-R4 each independently represent a hydrogen atom or a monovalent C1-6 hydrocarbon group.
Description
本発明は、ビニル化合物に関し、詳しくは、半導体封止、積層板、放熱基板等の電気・電子部品用絶縁材料に有用な溶剤溶解性に優れた多官能ビニル化合物、その組成物、及びそれらを硬化させて得られる耐熱性、熱分解安定性、熱伝導性、低誘電率、低誘電正接、難燃性に優れる樹脂硬化物に関する。
The present invention relates to vinyl compounds, and more specifically to polyfunctional vinyl compounds with excellent solvent solubility that are useful as insulating materials for electrical and electronic components such as semiconductor encapsulation, laminates, and heat dissipation substrates, compositions thereof, and cured resins obtained by curing them that have excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric tangent, and flame retardancy.
通信機器に用いられるプリント基板、封止材、注型材などは通信速度、通信量の増大にともない信号伝送速度の向上のため高速通信技術が盛んに研究されている。このような用途における電子材料には誘電損失を低減できる材料が求められており、プリント基板用途では加えて多層化が可能な硬化性樹脂が求められている。
In order to improve signal transmission speeds in response to increases in communication speeds and data volumes, there has been active research into high-speed communication technology for printed circuit boards, sealing materials, and casting materials used in communication devices. Electronic materials for such applications require materials that can reduce dielectric loss, and for printed circuit board applications, there is also a demand for curable resins that can be multi-layered.
一方で、このような情報量の多いデータを処理する電子演算部品からの発熱は多く、熱蓄積によって電子演算部品の処理速度低下など不具合が発生する為、プリント基板ではヒートシンク等により適宜冷却する技術として銅コイン、銅インレイ等の伝熱部材を組み込む方法や（特許文献１）、配合するフィラーの形状を特殊なものにする（特許文献２）など様々な工夫が知られている。しかし、このような方法は重量の増加や機器の大型化につながり好ましくなかった。
On the other hand, electronic computing components that process such large amounts of data generate a lot of heat, and heat accumulation can cause problems such as a slowdown in the processing speed of electronic computing components, so various techniques are known for appropriately cooling printed circuit boards using heat sinks, etc., such as incorporating heat transfer components such as copper coins and copper inlays (Patent Document 1) and using special shapes for the fillers used (Patent Document 2). However, such methods are undesirable as they lead to increased weight and larger equipment.
また、封止材組成物では熱伝導率を高める方法として各種フィラーの種類と量を検討することで電子演算部品からの熱を除熱する方法がとられており、例えば、熱伝導率の大きい結晶シリカ、窒化珪素、窒化アルミニウム、球状アルミナ粉末等の無機充填材を含有させるなどの試みがなされている（特許文献３、４）。ところが、無機充填材の含有率を上げていくと成形時の粘度上昇とともに流動性が低下し、成形性が損なわれるという問題が生じる。従って、単に無機充填材の含有率を高める方法には限界があった。
Furthermore, in order to increase the thermal conductivity of sealing material compositions, methods have been adopted in which the types and amounts of various fillers are examined to remove heat from electronic computing components. For example, attempts have been made to include inorganic fillers with high thermal conductivity such as crystalline silica, silicon nitride, aluminum nitride, and spherical alumina powder (Patent Documents 3 and 4). However, as the content of inorganic fillers is increased, the viscosity during molding increases and the fluidity decreases, causing problems such as impaired moldability. Therefore, there are limitations to the method of simply increasing the content of inorganic fillers.
上記背景から、マトリックス樹脂自体の高熱伝導率化によって組成物の熱伝導率を向上する方法も検討されている。例えば、剛直なメソゲン基を有する液晶性のエポキシ樹脂およびそれを用いたエポキシ樹脂組成物が提案されている（特許文献５、６）。しかし、これらのエポキシ樹脂組成物に用いる硬化剤としては、芳香族ジアミン化合物を用いており、無機充填材の高充填率化に限界があるとともに、電気絶縁性の点でも問題があった。また、芳香族ジアミン化合物を用いた場合、硬化物の液晶性は確認できるものの、硬化物の結晶化度は低く、高熱伝導性、低熱膨張性、低吸湿性等の点で十分ではなかった。さらには液晶性発現のために、強力な磁場をかけて分子を配向させる必要があり、工業的に広く利用するためには設備的にも大きな制約があった。また、無機充填材との配合系では、マトリックス樹脂の熱伝導率に比べて無機充填材の熱伝導率が圧倒的に大きく、マトリックス樹脂自体の熱伝導率を高くしても、複合材料としての熱伝導率向上には大きく寄与しないという現実があり、十分な熱伝導率向上効果は得られていなかった。
In light of the above background, methods for improving the thermal conductivity of a composition by increasing the thermal conductivity of the matrix resin itself have also been studied. For example, liquid crystalline epoxy resins having rigid mesogen groups and epoxy resin compositions using them have been proposed (Patent Documents 5 and 6). However, aromatic diamine compounds are used as curing agents for these epoxy resin compositions, which limits the high filling rate of inorganic fillers and also poses problems in terms of electrical insulation. In addition, when aromatic diamine compounds are used, although the liquid crystallinity of the cured product can be confirmed, the crystallinity of the cured product is low, and it is not sufficient in terms of high thermal conductivity, low thermal expansion, low moisture absorption, etc. Furthermore, in order to express liquid crystallinity, it is necessary to apply a strong magnetic field to orient the molecules, and there are significant restrictions in terms of equipment for widespread industrial use. In addition, in a compounding system with an inorganic filler, the thermal conductivity of the inorganic filler is overwhelmingly higher than that of the matrix resin, and even if the thermal conductivity of the matrix resin itself is increased, it does not contribute significantly to improving the thermal conductivity of the composite material, and a sufficient effect of improving thermal conductivity has not been obtained.
特許文献７には、高熱伝導性と低誘電正接を両立する多官能ビニル樹脂として、ビフェニル骨格を有する４官能以上のビニル樹脂が提案されているが、その多官能ビニル樹脂およびその原料となる多価ヒドロキシ樹脂の溶剤溶解性について記載されておらず、残存する極性基等の不純物が熱伝導率に及ぼす影響については一切触れられていない。
Patent Document 7 proposes a tetrafunctional or higher vinyl resin with a biphenyl skeleton as a multifunctional vinyl resin that combines high thermal conductivity and low dielectric tangent, but does not describe the solvent solubility of the multifunctional vinyl resin or the polyhydric hydroxyl resin that is its raw material, nor does it mention the effect of impurities such as remaining polar groups on thermal conductivity.
本発明の目的は、溶剤溶解性に優れるとともに、耐熱性、熱分解安定性、熱伝導性、低誘電率、低誘電正接、難燃性に優れた硬化物を与える電気・電子部品類の封止、回路基板材料等に有用なビニル組成物を提供すること、及びその硬化物を提供することにある。また、他の目的はこのビニル組成物に使用されるビニル化合物を提供することにある。
The object of the present invention is to provide a vinyl composition that is useful for sealing electric and electronic components, as a circuit board material, etc., and that gives a cured product that has excellent solvent solubility as well as excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric tangent, and flame retardancy, and to provide the cured product. Another object is to provide a vinyl compound that can be used in this vinyl composition.
本発明者等は、鋭意検討し、特定の構造を有する多官能ビニル化合物が、上記の課題を解決することが期待されること、そしてその硬化物が耐熱性、熱分解安定性、熱伝導性、低誘電率、低誘電正接、難燃性に効果を発現することを見出した。
The inventors conducted extensive research and discovered that a polyfunctional vinyl compound with a specific structure is expected to solve the above problems, and that the cured product exhibits excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric tangent, and flame retardancy.
すなわち、本発明は、下記一般式（１）で表される多官能ビニル化合物である。
式（１）中、Ｒ１～Ｒ４は、それぞれ独立して、水素原子または一価の炭素数１～６の炭化水素基を示す。
That is, the present invention relates to a polyfunctional vinyl compound represented by the following general formula (1).
In formula (1), R1 to R4 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.
上記多官能ビニル化合物のＲ１～Ｒ４のうち少なくとも一つは、メチル基またはフェニル基であることが好ましい。
It is preferable that at least one of R1 to R4 in the above multifunctional vinyl compound is a methyl group or a phenyl group.
また、本発明は、上記多官能ビニル化合物とラジカル重合開始剤とを必須成分として含有する多官能ビニル組成物であり、この多官能ビニル組成物を硬化してなる多官能ビニル硬化物である。
The present invention also relates to a multifunctional vinyl composition containing the above-mentioned multifunctional vinyl compound and a radical polymerization initiator as essential components, and a multifunctional vinyl cured product obtained by curing this multifunctional vinyl composition.
本発明の多官能ビニル化合物は溶剤溶解性に優れ、積層、成形、注型、接着等の用途に使用されるビニル樹脂組成物及びその硬化物に適する。そして、この硬化物は耐熱性、熱分解安定性、熱伝導性、低誘電率、低誘電正接、難燃性にも優れたものとなるので、電気・電子部品類の封止、回路基板材料等に好適である。
The polyfunctional vinyl compounds of the present invention have excellent solvent solubility and are suitable for use in vinyl resin compositions and their cured products for applications such as lamination, molding, casting, and adhesion. Furthermore, these cured products also have excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric tangent, and flame retardancy, making them suitable for sealing electrical and electronic components, as circuit board materials, etc.
以下、本発明を詳細に説明する。
The present invention is explained in detail below.
本発明は、下記一般式（１）で表される多官能ビニル化合物である。
Ｒ１～Ｒ４は、それぞれ独立して、水素原子または一価の炭素数１～６の炭化水素基である。溶剤溶解性の観点からアルキル基が好ましく、耐熱性および高熱伝導率の観点から芳香族基が好ましい。炭素数が６より大きいアルキル基は分子運動の抑制が困難となり、相溶性の低下も懸念される。また、立体障害が大きい嵩高い構造は、結晶性が増大することにより溶剤溶解性の懸念がある。より好ましい構造としては、メチル基またはフェニル基であることがより好ましい。Ｒ１～Ｒ４は異なる構造の混合物でもよい。
The present invention relates to a polyfunctional vinyl compound represented by the following general formula (1).
R1 to R4 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. From the viewpoint of solvent solubility, an alkyl group is preferable, and from the viewpoint of heat resistance and high thermal conductivity, an aromatic group is preferable. With an alkyl group having more than 6 carbon atoms, it becomes difficult to suppress molecular motion, and there is a concern of a decrease in compatibility. Furthermore, a bulky structure with large steric hindrance increases crystallinity, which raises concerns about solvent solubility. A more preferable structure is a methyl group or a phenyl group. R1 to R4 may be a mixture of different structures.
本発明の多官能ビニル化合物において、ビニルベンジルエーテルの置換位置は、特に限定されないが、熱伝導率、耐熱性の観点から、３つの芳香環を結節するメチン基に対しパラ位であることが好ましい。特に３つのビニルベンジルエーテルが全てパラ位であることがより好ましい。
In the polyfunctional vinyl compound of the present invention, the substitution position of the vinyl benzyl ether is not particularly limited, but from the viewpoint of thermal conductivity and heat resistance, it is preferably in the para position relative to the methine group connecting the three aromatic rings. In particular, it is more preferable that all three vinyl benzyl ethers are in the para position.
本発明の多官能ビニル化合物の数平均分子量（Ｍｎ）は、２０００以下が好ましく、１５００以下がより好ましい。また、下記一般式（２）で表される多分岐体を含んでもよい。ｎは繰り返し数であり、０～２０の数を示す。好ましくは、ｎの値が異なる成分の混合物である。
熱伝導率の観点から、ｎ＝０体の含有率は５０ｗｔ％以上が好ましく、８０ｗｔ％以上がより好ましい。
式（２）において、ｎ＝０体が、式（１）で表される多官能ビニル化合物である。本発明の多官能ビニル化合物は、式（２）で表した場合、ｎの平均値（数平均）が、好ましくは０．０１～５．０の範囲、より好ましくは０．０１～２．０の範囲、さらに好ましくは０．０１～１．０の範囲である。
よって、本発明の多官能ビニル化合物は、多官能ビニル樹脂ともいう。 The number average molecular weight (Mn) of the polyfunctional vinyl compound of the present invention is preferably 2000 or less, more preferably 1500 or less. The compound may further contain a multi-branched structure represented by the following general formula (2), where n is the repeating number and is a number from 0 to 20. The compound is preferably a mixture of components having different values of n.
From the viewpoint of thermal conductivity, the content of n=0 bodies is preferably 50 wt % or more, and more preferably 80 wt % or more.
In formula (2), the compound where n=0 is a polyfunctional vinyl compound represented by formula (1). When the polyfunctional vinyl compound of the present invention is represented by formula (2), the average value (number average) of n is preferably in the range of 0.01 to 5.0, more preferably in the range of 0.01 to 2.0, and even more preferably in the range of 0.01 to 1.0.
Therefore, the polyfunctional vinyl compound of the present invention is also called a polyfunctional vinyl resin.
熱伝導率の観点から、ｎ＝０体の含有率は５０ｗｔ％以上が好ましく、８０ｗｔ％以上がより好ましい。
よって、本発明の多官能ビニル化合物は、多官能ビニル樹脂ともいう。 The number average molecular weight (Mn) of the polyfunctional vinyl compound of the present invention is preferably 2000 or less, more preferably 1500 or less. The compound may further contain a multi-branched structure represented by the following general formula (2), where n is the repeating number and is a number from 0 to 20. The compound is preferably a mixture of components having different values of n.
From the viewpoint of thermal conductivity, the content of n=0 bodies is preferably 50 wt % or more, and more preferably 80 wt % or more.
Therefore, the polyfunctional vinyl compound of the present invention is also called a polyfunctional vinyl resin.
本発明の多官能ビニル化合物は、ビニル当量の好ましい範囲が１５０～４５０ｇ／ｅｑであり、より好ましい範囲が２００～３００ｇ／ｅｑである。この範囲より小さい場合、急激に反応するために反応制御が困難となり、この範囲より大きい場合、反応性が低下し、均一な硬化物を得ることが困難となる懸念がある。
The preferred vinyl equivalent range for the polyfunctional vinyl compound of the present invention is 150 to 450 g/eq, and more preferably 200 to 300 g/eq. If it is less than this range, the reaction will occur too quickly, making it difficult to control, and if it is more than this range, there is a concern that the reactivity will decrease and it will be difficult to obtain a uniform cured product.
本発明の多官能ビニル化合物は、三官能ヒドロキシ化合物とクロロメチルスチレンと反応させることで得ることができるが、その際に未反応で残存する水酸基が５０００ｇ／ｅｑより小さい場合、硬化が不十分となり、熱伝導率および耐熱性が低下する。また、水酸基は極性基であることから、その残存は誘電率、誘電正接の低減を阻害する懸念がある。水酸基当量が、好ましくは５，０００ｇ／ｅｑ以上、より好ましくは１０，０００ｇ／ｅｑ以上である。
一方、塩素成分としては原料であるクロロメチルスチレン由来によるものであり、水酸基と同様に塩素成分が残存する場合、誘電率、誘電正接の低減を阻害する懸念があり、極性基による硬化反応の阻害が生じることで熱伝導率、耐熱性を低下する懸念がある。全塩素量が、好ましくは２０００ｐｐｍ以下、より好ましくは１０００ｐｐｍ以下である。 The polyfunctional vinyl compound of the present invention can be obtained by reacting a trifunctional hydroxy compound with chloromethylstyrene, but if the amount of unreacted hydroxyl groups remaining is less than 5000 g/eq, the curing is insufficient, and the thermal conductivity and heat resistance are reduced. In addition, since the hydroxyl groups are polar groups, there is a concern that the remaining hydroxyl groups may hinder the reduction of the dielectric constant and dielectric loss tangent. The hydroxyl group equivalent is preferably 5,000 g/eq or more, more preferably 10,000 g/eq or more.
On the other hand, the chlorine component is derived from the raw material chloromethylstyrene, and if the chlorine component remains, as with the hydroxyl group, there is a concern that it will inhibit the reduction of the dielectric constant and the dielectric loss tangent, and there is a concern that the curing reaction will be inhibited by the polar group, resulting in a decrease in the thermal conductivity and heat resistance. The total chlorine content is preferably 2000 ppm or less, more preferably 1000 ppm or less.
一方、塩素成分としては原料であるクロロメチルスチレン由来によるものであり、水酸基と同様に塩素成分が残存する場合、誘電率、誘電正接の低減を阻害する懸念があり、極性基による硬化反応の阻害が生じることで熱伝導率、耐熱性を低下する懸念がある。全塩素量が、好ましくは２０００ｐｐｍ以下、より好ましくは１０００ｐｐｍ以下である。 The polyfunctional vinyl compound of the present invention can be obtained by reacting a trifunctional hydroxy compound with chloromethylstyrene, but if the amount of unreacted hydroxyl groups remaining is less than 5000 g/eq, the curing is insufficient, and the thermal conductivity and heat resistance are reduced. In addition, since the hydroxyl groups are polar groups, there is a concern that the remaining hydroxyl groups may hinder the reduction of the dielectric constant and dielectric loss tangent. The hydroxyl group equivalent is preferably 5,000 g/eq or more, more preferably 10,000 g/eq or more.
On the other hand, the chlorine component is derived from the raw material chloromethylstyrene, and if the chlorine component remains, as with the hydroxyl group, there is a concern that it will inhibit the reduction of the dielectric constant and the dielectric loss tangent, and there is a concern that the curing reaction will be inhibited by the polar group, resulting in a decrease in the thermal conductivity and heat resistance. The total chlorine content is preferably 2000 ppm or less, more preferably 1000 ppm or less.
本発明の多官能ビニル化合物は、式（３）で表される三官能ヒドロキシ化合物と芳香族ビニル化剤を反応することにより得ることができる。Ｒ１～Ｒ４は式（１）のビニル化合物と同様である。
The polyfunctional vinyl compound of the present invention can be obtained by reacting a trifunctional hydroxy compound represented by formula (3) with an aromatic vinylating agent. R1 to R4 are the same as those of the vinyl compound of formula (1).
式（３）の三官能ヒドロキシ化合物は、水酸基当量が好ましくは９０～３５０ｇ／ｅｑ、より好ましくは１００～２００ｇ／ｅｑである。
式（３）の三官能ヒドロキシ化合物は、一般的な方法で製造可能であり、例えば、一価のフェノール化合物と芳香族アルデヒドとを重縮合することにより得ることができる。 The trifunctional hydroxy compound of formula (3) preferably has a hydroxyl group equivalent of 90 to 350 g/eq, more preferably 100 to 200 g/eq.
The trifunctional hydroxy compound of formula (3) can be produced by a general method, for example, by polycondensation of a monohydric phenol compound and an aromatic aldehyde.
式（３）の三官能ヒドロキシ化合物は、一般的な方法で製造可能であり、例えば、一価のフェノール化合物と芳香族アルデヒドとを重縮合することにより得ることができる。 The trifunctional hydroxy compound of formula (3) preferably has a hydroxyl group equivalent of 90 to 350 g/eq, more preferably 100 to 200 g/eq.
The trifunctional hydroxy compound of formula (3) can be produced by a general method, for example, by polycondensation of a monohydric phenol compound and an aromatic aldehyde.
一価のフェノール化合物としては、例えば、フェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、ｏ－エチルフェノール、ｍ－エチルフェノール、ｐ－エチルフェノール、ｐ－オクチルフェノール、ｐ－ｔ－ブチルフェノール、ｏ－シクロヘキシルフェノール、ｍ－シクロヘキシルフェノール、ｐ－シクロヘキシルフェノール等のモノアルキルフェノール；２，５－キシレノール、３，５－キシレノール、３，４－キシレノール、２，４－キシレノール、２，６－キシレノールのジアルキルフェノール；２，３，５－トリメチルフェノール、２，３，６－トリメチルフェノール等のトリアルキルフェノール、さらに、２－フェニルフェノール、４－フェニルフェノール、３－ベンジル‐１，１’‐ビフェニル‐２‐オール、３－ベンジル‐１，１’‐ビフェニル‐４‐オール、３－フェニルフェノール、２，６－ジフェニルフェノール等のヒドロキシビフェニル類等が挙げられる。溶剤溶解性、反応性、供給性の面で、２，５－キシレノール、２，６－キシレノール、２－フェニルフェノールが特に好ましい。これらのフェノール化合物は、１種類のみで用いることも２種以上併用することもできる。
Examples of monovalent phenol compounds include monoalkylphenols such as phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, p-octylphenol, p-t-butylphenol, o-cyclohexylphenol, m-cyclohexylphenol, and p-cyclohexylphenol; dialkylphenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,4-xylenol, and 2,6-xylenol; trialkylphenols such as 2,3,5-trimethylphenol and 2,3,6-trimethylphenol, and further hydroxybiphenyls such as 2-phenylphenol, 4-phenylphenol, 3-benzyl-1,1'-biphenyl-2-ol, 3-benzyl-1,1'-biphenyl-4-ol, 3-phenylphenol, and 2,6-diphenylphenol. In terms of solvent solubility, reactivity, and supplyability, 2,5-xylenol, 2,6-xylenol, and 2-phenylphenol are particularly preferred. These phenolic compounds can be used alone or in combination of two or more types.
芳香族アルデヒドとしては、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等のヒドロキシベンズアルデヒドが挙げられる。耐熱性、熱伝導率の観点から４－ヒドロキシベンズアルデヒドが好ましい。
Aromatic aldehydes include, for example, hydroxybenzaldehydes such as 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, and 4-hydroxybenzaldehyde. From the standpoint of heat resistance and thermal conductivity, 4-hydroxybenzaldehyde is preferred.
フェノール化合物と芳香族アルデヒドの重縮合は酸触媒を用いてもよく、例えば例えば、酢酸、シュウ酸、硫酸、塩酸、フェノールスルホン酸、パラトルエンスルホン酸、酢酸亜鉛、酢酸マンガン等が挙げられる。これらの酸触媒は、１種類のみで用いることも２種以上併用することもできる。また、これらの酸触媒の中でも、活性に優れる点から、硫酸、パラトルエンスルホン酸が好ましい。なお、酸触媒は、反応前に加えても、反応途中で加えても構わない。
The polycondensation of the phenol compound and the aromatic aldehyde may be carried out using an acid catalyst, such as acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, manganese acetate, etc. These acid catalysts may be used alone or in combination of two or more. Among these acid catalysts, sulfuric acid and paratoluenesulfonic acid are preferred because of their excellent activity. The acid catalyst may be added before or during the reaction.
フェノール化合物と芳香族アルデヒドの重縮合は、必要に応じて溶媒の存在下で重縮合物を得ても良い。溶媒としては、例えば、メタノール、エタノール、プロパノール等のモノアルコール；エチレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，７－ヘプタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、トリメチレングリコール、ジエチレングリコール、ポリエチレングリコール、グリセリン等のポリオール；２－エトキシエタノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノペンチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールエチルメチルエーテル、エチレングリコールモノフェニルエーテル等のグリコールエーテル；１，３－ジオキサン、１，４－ジオキサン、テトラヒドロフラン等の環状エーテル；エチレングリコールアセテート等のグリコールエステル；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトンなどが挙げられる。これらの溶媒は、１種類のみで用いることも２種以上併用することもできる。また、これらの溶媒の中でも、得られる化合物の溶解性に優れる点から、２－エトキシエタノールが好ましい。
The polycondensation of the phenol compound and the aromatic aldehyde may be carried out in the presence of a solvent, if necessary, to obtain a polycondensate. Examples of the solvent include monoalcohols such as methanol, ethanol, and propanol; polyols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, and glycerin; glycol ethers such as 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, and ethylene glycol monophenyl ether; cyclic ethers such as 1,3-dioxane, 1,4-dioxane, and tetrahydrofuran; glycol esters such as ethylene glycol acetate; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. These solvents can be used alone or in combination of two or more. Among these solvents, 2-ethoxyethanol is preferred because it has excellent solubility for the resulting compound.
フェノール化合物と芳香族アルデヒドの重縮合する際の反応温度は、２０～１４０℃の範囲であり、好ましくは８０～１１０℃の範囲である。
The reaction temperature during polycondensation of the phenol compound and aromatic aldehyde is in the range of 20 to 140°C, preferably in the range of 80 to 110°C.
フェノール化合物／芳香族アルデヒドの仕込み比率は、反応後のフェノール化合物を再沈殿等により容易に除去可能であることから、モル比で１／０．１～１／０．５の範囲であり、より好ましくは、１／０．３～１／０．５の範囲である。
The charging ratio of the phenol compound/aromatic aldehyde is in the range of 1/0.1 to 1/0.5 in molar ratio, and more preferably in the range of 1/0.3 to 1/0.5, since the phenol compound after the reaction can be easily removed by reprecipitation or the like.
本発明の多官能ビニル化合物は、三官能ヒドロキシ化合物を芳香族ビニル化剤と反応させることにより、好適に得ることができる。例えば、上記式（３）で表される三官能ヒドロキシ化合物とクロロメチルスチレンとの反応により、上記式（１）で表される本発明のビニル化合物を得ることができる。この反応は周知のビニル化反応と同様に行うことができる。
配合割合は、三官能ヒドロキシ化合物の官能基である水酸基１．０当量に対して、好ましくは芳香族ビニル化剤（例えばクロロメチルスチレン）を０．８～１．２当量である。ただし、三官能ヒドロキシ化合物の反応性が低い場合、芳香族ビニル化剤を過剰量仕込み、反応後に除去するとよい。 The polyfunctional vinyl compound of the present invention can be obtained by reacting a trifunctional hydroxy compound with an aromatic vinylating agent.For example, the vinyl compound of the present invention represented by the above formula (1) can be obtained by reacting a trifunctional hydroxy compound represented by the above formula (3) with chloromethylstyrene.This reaction can be carried out in the same manner as the well-known vinylation reaction.
The blending ratio is preferably 0.8 to 1.2 equivalents of aromatic vinylating agent (e.g., chloromethylstyrene) per 1.0 equivalent of hydroxyl group, which is the functional group of the trifunctional hydroxy compound. However, when the reactivity of the trifunctional hydroxy compound is low, it is advisable to charge an excess amount of aromatic vinylating agent and remove it after the reaction.
配合割合は、三官能ヒドロキシ化合物の官能基である水酸基１．０当量に対して、好ましくは芳香族ビニル化剤（例えばクロロメチルスチレン）を０．８～１．２当量である。ただし、三官能ヒドロキシ化合物の反応性が低い場合、芳香族ビニル化剤を過剰量仕込み、反応後に除去するとよい。 The polyfunctional vinyl compound of the present invention can be obtained by reacting a trifunctional hydroxy compound with an aromatic vinylating agent.For example, the vinyl compound of the present invention represented by the above formula (1) can be obtained by reacting a trifunctional hydroxy compound represented by the above formula (3) with chloromethylstyrene.This reaction can be carried out in the same manner as the well-known vinylation reaction.
The blending ratio is preferably 0.8 to 1.2 equivalents of aromatic vinylating agent (e.g., chloromethylstyrene) per 1.0 equivalent of hydroxyl group, which is the functional group of the trifunctional hydroxy compound. However, when the reactivity of the trifunctional hydroxy compound is low, it is advisable to charge an excess amount of aromatic vinylating agent and remove it after the reaction.
芳香族ビニル化剤としては、ハロメチルスチレン、特にクロロメチルスチレンが好ましい。その他、ブロモメチルスチレン及びその異性体、置換基を持ったものなどが挙げられる。ハロメチル体の置換位置について、例えば、ハロメチルスチレンの場合、４－位が好ましく、４－位体が全体の６０重量％以上であることが好ましい。
Aromatic vinylating agents are preferably halomethylstyrenes, particularly chloromethylstyrene. Other examples include bromomethylstyrene and its isomers, and those with substituents. Regarding the substitution position of the halomethyl compound, for example, in the case of halomethylstyrene, the 4-position is preferred, and it is preferable that the 4-position compound accounts for 60% or more by weight of the total.
三官能ヒドロキシ化合物と芳香族ビニル化剤との反応は、無溶剤下または溶媒の存在下行うことができる。ヒドロキシ化合物に芳香族ビニル化剤を加え、水酸化金属を加えて反応を行い、生成した金属塩をろ過や水洗などの方法により除去して反応が可能である。
溶媒はメチルエチルケトン、ベンゼン、トルエン、キシレン、メチルイソブチルケトン、ジエチレングリコールジメチルエーテル、シクロペンタノン、シクロヘキサノンなどが挙げられるがこれらに限定されるものではない。反応性の観点で、メチルエチルケトンが好ましい。水酸化金属の具体例としては水酸化ナトリウム、水酸化カリウムなどが挙げられるがこれらに限定されるものではない。 The reaction between a trifunctional hydroxy compound and an aromatic vinylating agent can be carried out in the absence or presence of a solvent. The reaction can be carried out by adding the aromatic vinylating agent to the hydroxy compound, adding a metal hydroxide, and removing the generated metal salt by a method such as filtration or washing with water.
Examples of the solvent include, but are not limited to, methyl ethyl ketone, benzene, toluene, xylene, methyl isobutyl ketone, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, etc. From the viewpoint of reactivity, methyl ethyl ketone is preferable. Specific examples of the metal hydroxide include, but are not limited to, sodium hydroxide, potassium hydroxide, etc.
溶媒はメチルエチルケトン、ベンゼン、トルエン、キシレン、メチルイソブチルケトン、ジエチレングリコールジメチルエーテル、シクロペンタノン、シクロヘキサノンなどが挙げられるがこれらに限定されるものではない。反応性の観点で、メチルエチルケトンが好ましい。水酸化金属の具体例としては水酸化ナトリウム、水酸化カリウムなどが挙げられるがこれらに限定されるものではない。 The reaction between a trifunctional hydroxy compound and an aromatic vinylating agent can be carried out in the absence or presence of a solvent. The reaction can be carried out by adding the aromatic vinylating agent to the hydroxy compound, adding a metal hydroxide, and removing the generated metal salt by a method such as filtration or washing with water.
Examples of the solvent include, but are not limited to, methyl ethyl ketone, benzene, toluene, xylene, methyl isobutyl ketone, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, etc. From the viewpoint of reactivity, methyl ethyl ketone is preferable. Specific examples of the metal hydroxide include, but are not limited to, sodium hydroxide, potassium hydroxide, etc.
ビニル化の反応は、好ましくは９０℃以下、より好ましくは７０℃以下の温度である。この温度より高い場合、ビニルベンジルエーテル基の熱による自己重合が進行して反応制御が困難となる。自己重合を抑えるためにキノン類、ニトロ化合物、ニトロフェノール類、ニトロソ，ニトロン化合物、酸素などの重合禁止剤を使用してもよい。
The vinylization reaction is preferably carried out at a temperature of 90°C or less, more preferably 70°C or less. If the temperature is higher than this, the vinyl benzyl ether group will self-polymerize due to heat, making it difficult to control the reaction. To suppress self-polymerization, polymerization inhibitors such as quinones, nitro compounds, nitrophenols, nitroso and nitrone compounds, and oxygen may be used.
反応終点は、芳香族ビニル化剤としてのハロメチルスチレンの残存量をＧＰＣ等の各種クロマトグラムにて追跡を行うことで決定でき、反応速度は、水酸化金属の種類や量、添加速度、固形分濃度等で調整可能である。
The end point of the reaction can be determined by tracking the remaining amount of halomethylstyrene as an aromatic vinylating agent using various chromatograms such as GPC, and the reaction rate can be adjusted by the type and amount of metal hydroxide, the addition rate, solids concentration, etc.
本発明の多官能ビニル化合物は、単独でも硬化させることができるが、各種添加剤を配合した多官能ビニル組成物として使用することも好適である。
特に、硬化促進のためにアゾ化合物、有機過酸化物などのラジカル重合開始剤を配合して硬化させることができる。 The polyfunctional vinyl compound of the present invention can be cured by itself, but it is also suitable to use it as a polyfunctional vinyl composition containing various additives.
In particular, in order to accelerate curing, a radical polymerization initiator such as an azo compound or an organic peroxide may be blended to effect curing.
特に、硬化促進のためにアゾ化合物、有機過酸化物などのラジカル重合開始剤を配合して硬化させることができる。 The polyfunctional vinyl compound of the present invention can be cured by itself, but it is also suitable to use it as a polyfunctional vinyl composition containing various additives.
In particular, in order to accelerate curing, a radical polymerization initiator such as an azo compound or an organic peroxide may be blended to effect curing.
本発明の多官能ビニル組成物は、多官能ビニル化合物およびラジカル重合開始剤を必須成分とするが、それ以外のビニル化合物や他の熱硬化性樹脂を配合でき、例えばエポキシ樹脂、オキセタン樹脂、マレイミド樹脂、アクリレート樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリフェニレンエーテル樹脂、ベンゾオキサジン樹脂などが挙げられる。
The polyfunctional vinyl composition of the present invention contains a polyfunctional vinyl compound and a radical polymerization initiator as essential components, but can also contain other vinyl compounds and other thermosetting resins, such as epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polyphenylene ether resins, and benzoxazine resins.
熱伝導率を高める為、例えば、ガラスクロス、カーボンファイバー、アルミナ、窒化ホウ素などの無機充填材を配合してもよい。
In order to increase thermal conductivity, inorganic fillers such as glass cloth, carbon fiber, alumina, and boron nitride may be added.
無機充填材は、より高い熱伝導率を付与する目的で、熱伝導率が高いものほど好ましい。好ましくは２０Ｗ／ｍ・Ｋ以上、より好ましくは３０Ｗ／ｍ・Ｋ以上、さらに好ましくは５０Ｗ／ｍ・Ｋ以上である。そして、無機充填材の少なくとも一部、好ましくは５０ｗｔ％以上が２０Ｗ／ｍ・Ｋ以上の熱伝導率を有する。そして、無機充填材全体としての平均の熱伝導率が、２０Ｗ／ｍ・Ｋ以上、３０Ｗ／ｍ・Ｋ以上、及び５０Ｗ／ｍ・Ｋ以上の順に好ましさが向上する。
In order to provide a higher thermal conductivity, inorganic fillers with higher thermal conductivity are preferred. Thermal conductivity is preferably 20 W/m.K or more, more preferably 30 W/m.K or more, and even more preferably 50 W/m.K or more. At least a portion of the inorganic filler, preferably 50 wt% or more, has a thermal conductivity of 20 W/m.K or more. The average thermal conductivity of the inorganic filler as a whole increases in the order of desirability: 20 W/m.K or more, 30 W/m.K or more, and 50 W/m.K or more.
このような熱伝導率を有する無機充填材の例としては、窒化ホウ素、窒化アルミニウム、窒化ケイ素、炭化ケイ素、窒化チタン、酸化亜鉛、炭化タングステン、アルミナ、酸化マグネシウム等の無機粉末充填材等が挙げられる。
Examples of inorganic fillers with such thermal conductivity include inorganic powder fillers such as boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, alumina, and magnesium oxide.
接着力の向上や組成物の取り扱い作業の向上の為、各種添加剤を添加してもよく、例えばシランカップリング剤や消泡剤、内部離型剤や流れ調整剤などが挙げられる。
Various additives may be added to improve adhesive strength and ease of handling of the composition, such as silane coupling agents, defoamers, internal release agents, and flow control agents.
本発明の多官能ビニル化合物または多官能ビニル組成物は、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等の溶剤に溶解させ、ガラス繊維，カ－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，紙などの基材に含浸させ加熱乾燥して得たプリプレグを熱プレス成形して硬化物を得ることなどもできる。
The polyfunctional vinyl compound or polyfunctional vinyl composition of the present invention can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone, impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and heated and dried to obtain a prepreg, which can then be hot-press molded to obtain a cured product.
また、場合により銅箔、ステンレス箔、ポリイミドフィルム、ポリエステルフィルム等のシート状物上に塗布することにより積層物とすることができ、加熱乾燥して得た樹脂シートを熱プレス成形して硬化物を得ることもできる。
In some cases, the resin can be applied onto a sheet-like material such as copper foil, stainless steel foil, polyimide film, or polyester film to form a laminate, and the resin sheet obtained by heating and drying can be subjected to heat press molding to obtain a cured product.
以下、実施例及び比較例を挙げて本発明を具体的に説明する。ただし、本発明はこれらに限定されるものではない。特に断りがない限り、「部」は重量部を表し、「％」は重量％を表す。また、測定方法はそれぞれ以下の方法により測定した。
The present invention will be specifically explained below with reference to examples and comparative examples. However, the present invention is not limited to these. Unless otherwise specified, "parts" refers to parts by weight, and "%" refers to % by weight. In addition, the following methods were used for the measurement.
１）ＯＨ当量（水酸基当量）
電位差滴定装置を用い、１，４－ジオキサンを溶媒に用い、１．５ｍｏｌ／Ｌ塩化アセチルでアセチル化を行い、過剰の塩化アセチルを水で分解して０．５ｍｏｌ／Ｌ－水酸化カリウムを使用して滴定した。 1) OH equivalent (hydroxyl group equivalent)
Using a potentiometric titrator, acetylation was carried out with 1.5 mol/L acetyl chloride using 1,4-dioxane as a solvent, and excess acetyl chloride was decomposed with water, followed by titration with 0.5 mol/L potassium hydroxide.
電位差滴定装置を用い、１，４－ジオキサンを溶媒に用い、１．５ｍｏｌ／Ｌ塩化アセチルでアセチル化を行い、過剰の塩化アセチルを水で分解して０．５ｍｏｌ／Ｌ－水酸化カリウムを使用して滴定した。 1) OH equivalent (hydroxyl group equivalent)
Using a potentiometric titrator, acetylation was carried out with 1.5 mol/L acetyl chloride using 1,4-dioxane as a solvent, and excess acetyl chloride was decomposed with water, followed by titration with 0.5 mol/L potassium hydroxide.
２）ビニル当量
試料にウィイス液（一塩化ヨウ素溶液）を反応させ、暗所に放置し、その後、過剰の塩化ヨウ素をヨウ素に還元し、ヨウ素分をチオ硫酸ナトリウムで滴定してヨウ素価を算出した。ヨウ素価をビニル当量に換算した。 2) Vinyl equivalent The sample was reacted with Wies's solution (iodine monochloride solution) and left in the dark, after which the excess iodine chloride was reduced to iodine, and the iodine content was titrated with sodium thiosulfate to calculate the iodine value. The iodine value was converted to vinyl equivalent.
試料にウィイス液（一塩化ヨウ素溶液）を反応させ、暗所に放置し、その後、過剰の塩化ヨウ素をヨウ素に還元し、ヨウ素分をチオ硫酸ナトリウムで滴定してヨウ素価を算出した。ヨウ素価をビニル当量に換算した。 2) Vinyl equivalent The sample was reacted with Wies's solution (iodine monochloride solution) and left in the dark, after which the excess iodine chloride was reduced to iodine, and the iodine content was titrated with sodium thiosulfate to calculate the iodine value. The iodine value was converted to vinyl equivalent.
３）全塩素
試料１．０ｇをブチルカルビトール２５ｍｌに溶解後、１Ｎ－ＫＯＨプロピレングリコール溶液２５ｍｌを加え１０分間加熱還流した後、室温まで冷却し、さらに８０％アセトン水１００ｍｌを加え、０．００２Ｎ－ＡｇＮＯ3水溶液で電位差滴定を行うことにより測定した。 3) Total chlorine: 1.0 g of a sample was dissolved in 25 ml of butyl carbitol, 25 ml of 1N KOH propylene glycol solution was added, and the mixture was heated under reflux for 10 minutes. The mixture was then cooled to room temperature, and 100 ml of 80% acetone water was added. The total chlorine was measured by potentiometric titration with a 0.002N AgNO3 aqueous solution.
試料１．０ｇをブチルカルビトール２５ｍｌに溶解後、１Ｎ－ＫＯＨプロピレングリコール溶液２５ｍｌを加え１０分間加熱還流した後、室温まで冷却し、さらに８０％アセトン水１００ｍｌを加え、０．００２Ｎ－ＡｇＮＯ3水溶液で電位差滴定を行うことにより測定した。 3) Total chlorine: 1.0 g of a sample was dissolved in 25 ml of butyl carbitol, 25 ml of 1N KOH propylene glycol solution was added, and the mixture was heated under reflux for 10 minutes. The mixture was then cooled to room temperature, and 100 ml of 80% acetone water was added. The total chlorine was measured by potentiometric titration with a 0.002N AgNO3 aqueous solution.
４）ＧＰＣ測定
本体（東ソー株式会社製、ＨＬＣ－８２２０ＧＰＣ）にカラム（東ソー株式会社製、ＴＳＫｇｅｌＳｕｐｅｒＭｕｌｔｉｐｏｒｅＨＺ―Ｎ４本）を直列に備えたものを使用し、カラム温度は４０℃にした。また、溶離液にはテトラヒドロフラン（ＴＨＦ）を使用し、０．３５ｍＬ／分の流速とし、検出器は示差屈折率検出器を使用した。測定試料はサンプル０．１ｇを１０ｍＬのＴＨＦに溶解し、マイクロフィルターで濾過したものを５０μＬ使用した。データ処理は、東ソー株式会社製ＧＰＣ－８０２０モデルＩＩバージョン６．００を使用した。 4) GPC Measurement A main body (HLC-8220GPC, manufactured by Tosoh Corporation) equipped with four columns (TSKgel Super Multipore HZ-N, manufactured by Tosoh Corporation) in series was used, and the column temperature was set to 40°C. Tetrahydrofuran (THF) was used as the eluent, the flow rate was set to 0.35 mL/min, and a differential refractive index detector was used as the detector. 50 μL of the measurement sample was prepared by dissolving 0.1 g of sample in 10 mL of THF and filtering through a microfilter. Data processing was performed using GPC-8020 Model II version 6.00 manufactured by Tosoh Corporation.
本体（東ソー株式会社製、ＨＬＣ－８２２０ＧＰＣ）にカラム（東ソー株式会社製、ＴＳＫｇｅｌＳｕｐｅｒＭｕｌｔｉｐｏｒｅＨＺ―Ｎ４本）を直列に備えたものを使用し、カラム温度は４０℃にした。また、溶離液にはテトラヒドロフラン（ＴＨＦ）を使用し、０．３５ｍＬ／分の流速とし、検出器は示差屈折率検出器を使用した。測定試料はサンプル０．１ｇを１０ｍＬのＴＨＦに溶解し、マイクロフィルターで濾過したものを５０μＬ使用した。データ処理は、東ソー株式会社製ＧＰＣ－８０２０モデルＩＩバージョン６．００を使用した。 4) GPC Measurement A main body (HLC-8220GPC, manufactured by Tosoh Corporation) equipped with four columns (TSKgel Super Multipore HZ-N, manufactured by Tosoh Corporation) in series was used, and the column temperature was set to 40°C. Tetrahydrofuran (THF) was used as the eluent, the flow rate was set to 0.35 mL/min, and a differential refractive index detector was used as the detector. 50 μL of the measurement sample was prepared by dissolving 0.1 g of sample in 10 mL of THF and filtering through a microfilter. Data processing was performed using GPC-8020 Model II version 6.00 manufactured by Tosoh Corporation.
５）溶剤溶解性（析出温度）
サンプル瓶に樹脂２ｇ、メチルエチルケトン１ｇを秤量し、加熱溶解させた後、恒温槽内にて徐々に温度を低下させ、樹脂が析出した槽内の温度を測定した。析出温度（℃）が高いほど、溶剤溶解性が劣る。 5) Solvent solubility (precipitation temperature)
2 g of resin and 1 g of methyl ethyl ketone were weighed and placed in a sample bottle, and after heating and dissolving, the temperature was gradually lowered in a thermostatic bath, and the temperature in the bath at which the resin precipitated was measured. The higher the precipitation temperature (°C), the poorer the solvent solubility.
サンプル瓶に樹脂２ｇ、メチルエチルケトン１ｇを秤量し、加熱溶解させた後、恒温槽内にて徐々に温度を低下させ、樹脂が析出した槽内の温度を測定した。析出温度（℃）が高いほど、溶剤溶解性が劣る。 5) Solvent solubility (precipitation temperature)
2 g of resin and 1 g of methyl ethyl ketone were weighed and placed in a sample bottle, and after heating and dissolving, the temperature was gradually lowered in a thermostatic bath, and the temperature in the bath at which the resin precipitated was measured. The higher the precipitation temperature (°C), the poorer the solvent solubility.
６）ガラス転移点（Ｔｇ）
熱機械測定装置（エスアイアイ・ナノテクノロジー株式会社製 ＥＸＳＴＡＲ ＴＭＡ／７１００）により、昇温速度１０℃／分の条件でＴｇを求めた。 6) Glass transition temperature (Tg)
The Tg was determined using a thermomechanical measurement device (EXSTAR TMA/7100 manufactured by SII NanoTechnology Inc.) at a temperature rise rate of 10° C./min.
熱機械測定装置（エスアイアイ・ナノテクノロジー株式会社製 ＥＸＳＴＡＲ ＴＭＡ／７１００）により、昇温速度１０℃／分の条件でＴｇを求めた。 6) Glass transition temperature (Tg)
The Tg was determined using a thermomechanical measurement device (EXSTAR TMA/7100 manufactured by SII NanoTechnology Inc.) at a temperature rise rate of 10° C./min.
７）５％重量減少温度（Ｔｄ５）、残炭率
熱重量／示差熱分析装置（エスアイアイ・ナノテクノロジー製 ＥＸＳＴＡＲ ＴＧ／ＤＴＡ７３００）を用いて、窒素雰囲気下、昇温速度１０℃／分の条件において、５％重量減少温度（Ｔｄ５）を測定した。また、７００℃における重量減少を測定し、残炭率として算出した。 7) 5% weight loss temperature (Td5), carbon residue ratio Using a thermogravimetric/differential thermal analyzer (EXSTAR TG/DTA7300 manufactured by SII NanoTechnology), the 5% weight loss temperature (Td5) was measured under conditions of a nitrogen atmosphere and a heating rate of 10°C/min. The weight loss at 700°C was also measured and calculated as the carbon residue ratio.
熱重量／示差熱分析装置（エスアイアイ・ナノテクノロジー製 ＥＸＳＴＡＲ ＴＧ／ＤＴＡ７３００）を用いて、窒素雰囲気下、昇温速度１０℃／分の条件において、５％重量減少温度（Ｔｄ５）を測定した。また、７００℃における重量減少を測定し、残炭率として算出した。 7) 5% weight loss temperature (Td5), carbon residue ratio Using a thermogravimetric/differential thermal analyzer (EXSTAR TG/DTA7300 manufactured by SII NanoTechnology), the 5% weight loss temperature (Td5) was measured under conditions of a nitrogen atmosphere and a heating rate of 10°C/min. The weight loss at 700°C was also measured and calculated as the carbon residue ratio.
８）熱伝導率
熱伝導率は、ＮＥＴＺＳＣＨ製ＬＦＡ４４７型熱伝導率計を用いて非定常熱線法により測定した。 8) Thermal Conductivity The thermal conductivity was measured by a non-steady hot wire method using a NETZSCH LFA447 type thermal conductivity meter.
熱伝導率は、ＮＥＴＺＳＣＨ製ＬＦＡ４４７型熱伝導率計を用いて非定常熱線法により測定した。 8) Thermal Conductivity The thermal conductivity was measured by a non-steady hot wire method using a NETZSCH LFA447 type thermal conductivity meter.
９）誘電率及び誘電正接
ＪＩＳ Ｃ ２１３８規格に従って測定した。測定周波数は１ＧＨｚの値で示した。 9) Dielectric constant and dielectric loss tangent Measured in accordance with JIS C 2138. The measurement frequency was 1 GHz.
ＪＩＳ Ｃ ２１３８規格に従って測定した。測定周波数は１ＧＨｚの値で示した。 9) Dielectric constant and dielectric loss tangent Measured in accordance with JIS C 2138. The measurement frequency was 1 GHz.
（合成例１）
１０００ｍＬの４口フラスコに、２，５－キシレノール（下記構造式）７３．６ｇ（０．６０モル）、
ｐ－ヒドロキシベンズアルデヒド（下記構造式）２４．４ｇ（０．２０モル）
を仕込み、２－エトキシエタノール２００．０ｇに溶解させた。氷浴中で冷却しながら硫酸２０．０ｇを加えた後、１００℃で３時間加熱、攪拌し反応させた。反応後、得られた溶液を水で再沈殿操作を行い、水洗、ろ過、真空乾燥を行うことによって、三官能ヒドロキシ化合物ａを６５．０ｇ得た。三官能ヒドロキシ化合物ａは、式（３）においてＲ１～Ｒ４がいずれもメチル基であり、水酸基当量は１１８ｇ／ｅｇ．であった。
(Synthesis Example 1)
Into a 1000 mL four-neck flask, 73.6 g (0.60 mol) of 2,5-xylenol (structural formula below),
p-Hydroxybenzaldehyde (structural formula below) 24.4 g (0.20 mol)
and dissolved in 200.0 g of 2-ethoxyethanol. While cooling in an ice bath, 20.0 g of sulfuric acid was added, and then the mixture was heated at 100°C for 3 hours with stirring to cause a reaction. After the reaction, the resulting solution was reprecipitated with water, washed with water, filtered, and dried in vacuum to obtain 65.0 g of trifunctional hydroxy compound a. In trifunctional hydroxy compound a, R1 to R4 in formula (3) are all methyl groups, and the hydroxyl group equivalent was 118 g/eg.
１０００ｍＬの４口フラスコに、２，５－キシレノール（下記構造式）７３．６ｇ（０．６０モル）、
Into a 1000 mL four-neck flask, 73.6 g (0.60 mol) of 2,5-xylenol (structural formula below),
（合成例２）
２，５－キシレノール７３．６ｇの代わりに２，５－キシレノール３６．８ｇ（０．３０モル）、フェノール２８．２ｇ（０．３０モル）を用いた以外は合成例１と同様の操作を行い、三官能ヒドロキシ化合物ｂを６０．８ｇ得た。三官能ヒドロキシ化合物ｂは、式（３）においてＲ１～Ｒ４がいずれも水素原子またはメチル基である化合物の混合物であり、水酸基当量は１０５ｇ／ｅｇ．であった。 (Synthesis Example 2)
The same procedure as in Synthesis Example 1 was carried out except that 36.8 g (0.30 mol) of 2,5-xylenol and 28.2 g (0.30 mol) of phenol were used instead of 73.6 g of 2,5-xylenol, to obtain 60.8 g of trifunctional hydroxy compound b. Trifunctional hydroxy compound b was a mixture of compounds represented by formula (3) in which R1 to R4 were all hydrogen atoms or methyl groups, and had a hydroxyl group equivalent of 105 g/eg.
２，５－キシレノール７３．６ｇの代わりに２，５－キシレノール３６．８ｇ（０．３０モル）、フェノール２８．２ｇ（０．３０モル）を用いた以外は合成例１と同様の操作を行い、三官能ヒドロキシ化合物ｂを６０．８ｇ得た。三官能ヒドロキシ化合物ｂは、式（３）においてＲ１～Ｒ４がいずれも水素原子またはメチル基である化合物の混合物であり、水酸基当量は１０５ｇ／ｅｇ．であった。 (Synthesis Example 2)
The same procedure as in Synthesis Example 1 was carried out except that 36.8 g (0.30 mol) of 2,5-xylenol and 28.2 g (0.30 mol) of phenol were used instead of 73.6 g of 2,5-xylenol, to obtain 60.8 g of trifunctional hydroxy compound b. Trifunctional hydroxy compound b was a mixture of compounds represented by formula (3) in which R1 to R4 were all hydrogen atoms or methyl groups, and had a hydroxyl group equivalent of 105 g/eg.
（合成例３）
２，５－キシレノール７３．６ｇの代わりに２－フェニルフェノール（下記構造式）１０２．０ｇ（０．６０モル）
を用いた以外は合成例１と同様の操作を行い、三官能ヒドロキシ化合物ｃを８１．０ｇ得た。三官能ヒドロキシ化合物ｃは、式（３）においてＲ１～Ｒ４がいずれもフェニル基であり、水酸基当量は１４９ｇ／ｅｇ．であった。
(Synthesis Example 3)
102.0 g (0.60 mol) of 2-phenylphenol (structural formula below) instead of 73.6 g of 2,5-xylenol
The same procedure as in Synthesis Example 1 was carried out except that the above was used, to obtain 81.0 g of trifunctional hydroxy compound c. In trifunctional hydroxy compound c, R1 to R4 in formula (3) were all phenyl groups, and the hydroxyl group equivalent was 149 g/eg.
２，５－キシレノール７３．６ｇの代わりに２－フェニルフェノール（下記構造式）１０２．０ｇ（０．６０モル）
102.0 g (0.60 mol) of 2-phenylphenol (structural formula below) instead of 73.6 g of 2,5-xylenol
（実施例１）
１０００ｍｌの４口フラスコに合成例１で得られた三官能ヒドロキシ化合物ａを５９．０ｇ（０．１７モル）、メチルエチルケトン４００ｇ、クロロメチルスチレン（下記構造式）９１．６ｇ（０．６０モル）
を加え、６０℃に昇温し、メタノール１０１ｇに溶解した水酸化カリウム３３．７ｇを３時間かけて滴下し、さらに６時間反応した。反応終了後、濾過し、溶剤を留去し、メタノールにて再沈殿し、大量の水で水洗し、減圧乾燥により多官能ビニル化合物１０２．４ｇを得た（ビニル化合物Ａ）。ビニル化合物Ａのビニル当量は２２５ｇ／ｅｇ．、水酸基当量は１２０００ｇ／ｅｇ．、全塩素は６００ｐｐｍであった。
Example 1
Into a 1000 ml four-neck flask, 59.0 g (0.17 mol) of the trifunctional hydroxy compound a obtained in Synthesis Example 1, 400 g of methyl ethyl ketone, and 91.6 g (0.60 mol) of chloromethylstyrene (structural formula shown below) were added.
The mixture was heated to 60°C, and 33.7 g of potassium hydroxide dissolved in 101 g of methanol was added dropwise over 3 hours, followed by reaction for another 6 hours. After the reaction was completed, the mixture was filtered, the solvent was removed by distillation, and the mixture was reprecipitated in methanol, washed with a large amount of water, and dried under reduced pressure to obtain 102.4 g of a multifunctional vinyl compound (vinyl compound A). The vinyl equivalent of vinyl compound A was 225 g/eg., the hydroxyl equivalent was 12,000 g/eg., and the total chlorine was 600 ppm.
１０００ｍｌの４口フラスコに合成例１で得られた三官能ヒドロキシ化合物ａを５９．０ｇ（０．１７モル）、メチルエチルケトン４００ｇ、クロロメチルスチレン（下記構造式）９１．６ｇ（０．６０モル）
Into a 1000 ml four-neck flask, 59.0 g (0.17 mol) of the trifunctional hydroxy compound a obtained in Synthesis Example 1, 400 g of methyl ethyl ketone, and 91.6 g (0.60 mol) of chloromethylstyrene (structural formula shown below) were added.
（実施例２）
三官能ヒドロキシ化合物ａの代わりに合成例２で得られた三官能ヒドロキシ化合物ｂを５２．５ｇ（０．１７モル）用いた以外は実施例１と同様の操作を行い、多官能ビニル化合物１００．３ｇを得た（ビニル化合物Ｂ）。ビニル化合物Ｂのビニル当量は２１２ｇ／ｅｇ．、水酸基当量は１４０００ｇ／ｅｇ．、全塩素は５００ｐｐｍであった。 Example 2
The same procedure as in Example 1 was carried out except that 52.5 g (0.17 mol) of the trifunctional hydroxy compound b obtained in Synthesis Example 2 was used instead of the trifunctional hydroxy compound a, to obtain 100.3 g of a multifunctional vinyl compound (vinyl compound B). The vinyl equivalent of vinyl compound B was 212 g/eg., the hydroxyl equivalent was 14,000 g/eg., and the total chlorine was 500 ppm.
三官能ヒドロキシ化合物ａの代わりに合成例２で得られた三官能ヒドロキシ化合物ｂを５２．５ｇ（０．１７モル）用いた以外は実施例１と同様の操作を行い、多官能ビニル化合物１００．３ｇを得た（ビニル化合物Ｂ）。ビニル化合物Ｂのビニル当量は２１２ｇ／ｅｇ．、水酸基当量は１４０００ｇ／ｅｇ．、全塩素は５００ｐｐｍであった。 Example 2
The same procedure as in Example 1 was carried out except that 52.5 g (0.17 mol) of the trifunctional hydroxy compound b obtained in Synthesis Example 2 was used instead of the trifunctional hydroxy compound a, to obtain 100.3 g of a multifunctional vinyl compound (vinyl compound B). The vinyl equivalent of vinyl compound B was 212 g/eg., the hydroxyl equivalent was 14,000 g/eg., and the total chlorine was 500 ppm.
（実施例３）
三官能ヒドロキシ化合物ａの代わりに合成例３で得られた三官能ヒドロキシ化合物ｃを７４．５ｇ（０．１７モル）用いた以外は実施例１と同様の操作を行い、多官能ビニル化合物１２１．２ｇを得た（ビニル化合物Ｃ）。ビニル化合物Ｃのビニル当量は２６０ｇ／ｅｇ．、水酸基当量は１１０００ｇ／ｅｇ．、全塩素は８００ｐｐｍであった。 Example 3
The same procedure as in Example 1 was carried out except that 74.5 g (0.17 mol) of the trifunctional hydroxy compound c obtained in Synthesis Example 3 was used instead of the trifunctional hydroxy compound a, to obtain 121.2 g of a multifunctional vinyl compound (vinyl compound C). The vinyl equivalent of vinyl compound C was 260 g/eg., the hydroxyl equivalent was 11,000 g/eg., and the total chlorine was 800 ppm.
三官能ヒドロキシ化合物ａの代わりに合成例３で得られた三官能ヒドロキシ化合物ｃを７４．５ｇ（０．１７モル）用いた以外は実施例１と同様の操作を行い、多官能ビニル化合物１２１．２ｇを得た（ビニル化合物Ｃ）。ビニル化合物Ｃのビニル当量は２６０ｇ／ｅｇ．、水酸基当量は１１０００ｇ／ｅｇ．、全塩素は８００ｐｐｍであった。 Example 3
The same procedure as in Example 1 was carried out except that 74.5 g (0.17 mol) of the trifunctional hydroxy compound c obtained in Synthesis Example 3 was used instead of the trifunctional hydroxy compound a, to obtain 121.2 g of a multifunctional vinyl compound (vinyl compound C). The vinyl equivalent of vinyl compound C was 260 g/eg., the hydroxyl equivalent was 11,000 g/eg., and the total chlorine was 800 ppm.
（比較例１）
三官能ヒドロキシ化合物ａの代わりに１，１，１－トリス（ｐ－ヒドロキシフェニル）エタン（下記構造式）５１．０ｇ
用いた以外は実施例１と同様の操作を行い、多官能ビニル化合物９３．３ｇを得た（ビニル化合物Ｄ）。ビニル化合物Ｄのビニル当量は２１４ｇ／ｅｇ．、水酸基当量は７０００ｇ／ｅｇ．、全塩素は１５００ｐｐｍであった。
(Comparative Example 1)
Instead of the trifunctional hydroxy compound a, 51.0 g of 1,1,1-tris(p-hydroxyphenyl)ethane (structural formula below)
The same procedure as in Example 1 was carried out except that 93.3 g of a polyfunctional vinyl compound was obtained (vinyl compound D). The vinyl equivalent of vinyl compound D was 214 g/eg., the hydroxyl equivalent was 7000 g/eg., and the total chlorine was 1500 ppm.
三官能ヒドロキシ化合物ａの代わりに１，１，１－トリス（ｐ－ヒドロキシフェニル）エタン（下記構造式）５１．０ｇ
Instead of the trifunctional hydroxy compound a, 51.0 g of 1,1,1-tris(p-hydroxyphenyl)ethane (structural formula below)
（比較例２）
１０００ｍｌの４口フラスコに、４，４’－ビス（クロロメチル）ビフェニル（下記構造式）４０．８ｇ、
４，４’－ビフェノール（下記構造式）７５．５ｇ、
ジエチレングリコールジメチルエーテル１２０ｇを仕込み、窒素気流下、攪拌しながら１６０℃まで昇温して１０時間反応させた。続いて、７０℃にし、ジエチレングリコールジメチルエーテルを２８０ｇ、クロロメチルスチレンを１２９．５ｇ加え、４８％水酸化カリウム１００．０ｇを滴下しながら反応を行い、ガスクロマトグラフィーにて残存クロロメチルスチレンが無いことを確認し溶剤を減圧回収した。得られた樹脂をトルエンに溶解し中和、水洗を行い、多官能ビニル樹脂ｇを得た（ビニル樹脂Ｅ）。得られたビニル樹脂Ｅのビニル当量は２５６ｇ／ｅｑ．、水酸基当量は１５００ｇ／ｅｑ．、全塩素は１２７０ｐｐｍであった。
(Comparative Example 2)
Into a 1000 ml four-neck flask, 40.8 g of 4,4'-bis(chloromethyl)biphenyl (structural formula below),
4,4'-biphenol (structural formula below) 75.5 g,
120g of diethylene glycol dimethyl ether was charged, and the mixture was heated to 160°C under nitrogen flow while stirring, and reacted for 10 hours. Then, the temperature was raised to 70°C, 280g of diethylene glycol dimethyl ether and 129.5g of chloromethylstyrene were added, and the reaction was carried out while dropping 100.0g of 48% potassium hydroxide. It was confirmed by gas chromatography that there was no remaining chloromethylstyrene, and the solvent was recovered under reduced pressure. The obtained resin was dissolved in toluene, neutralized, and washed with water to obtain a multifunctional vinyl resin g (vinyl resin E). The vinyl equivalent of the obtained vinyl resin E was 256g/eq., the hydroxyl equivalent was 1500g/eq., and the total chlorine was 1270ppm.
１０００ｍｌの４口フラスコに、４，４’－ビス（クロロメチル）ビフェニル（下記構造式）４０．８ｇ、
Into a 1000 ml four-neck flask, 40.8 g of 4,4'-bis(chloromethyl)biphenyl (structural formula below),
（比較例３）
１０００ｍｌの４口フラスコに、ジヒドロキシジフェニルメタン（４，４’－ジヒドロキシジフェニルメタン（下記構造式）：３６．２％、２，４’－ジヒドロキシジフェニルメタン：４６．６％、２，２’―ジヒドロキシジフェニルメタン：１７．２％からなる異性体混合物）５０．０ｇ、
メチルエチルケトン４００ｇ、クロロメチルスチレン８０．１ｇを加え、６０℃に昇温し、メタノール８８ｇに溶解した水酸化カリウム２９．５ｇを３時間かけて滴下し、さらに６時間反応した。反応終了後、濾過し、溶剤を留去し、メタノールにて再沈殿し、大量の水で水洗し、減圧乾燥により多官能ビニル樹脂９５．４ｇを得た（ビニル樹脂Ｆ）。ビニル樹脂Ｆのビニル当量は２１７ｇ／ｅｇ．、水酸基当量は１７０００ｇ／ｅｇ．、全塩素は４００ｐｐｍであった。
(Comparative Example 3)
Into a 1000 ml four-neck flask, 50.0 g of dihydroxydiphenylmethane (an isomer mixture consisting of 36.2% 4,4'-dihydroxydiphenylmethane (structural formula below), 46.6% 2,4'-dihydroxydiphenylmethane, and 17.2% 2,2'-dihydroxydiphenylmethane) was added.
400g of methyl ethyl ketone and 80.1g of chloromethylstyrene were added, and the temperature was raised to 60°C. 29.5g of potassium hydroxide dissolved in 88g of methanol was added dropwise over 3 hours, and the reaction was continued for another 6 hours. After the reaction was completed, the mixture was filtered, the solvent was removed by distillation, and the mixture was reprecipitated with methanol, washed with a large amount of water, and dried under reduced pressure to obtain 95.4g of a multifunctional vinyl resin (vinyl resin F). The vinyl equivalent of vinyl resin F was 217g/eg., the hydroxyl equivalent was 17000g/eg., and the total chlorine was 400ppm.
１０００ｍｌの４口フラスコに、ジヒドロキシジフェニルメタン（４，４’－ジヒドロキシジフェニルメタン（下記構造式）：３６．２％、２，４’－ジヒドロキシジフェニルメタン：４６．６％、２，２’―ジヒドロキシジフェニルメタン：１７．２％からなる異性体混合物）５０．０ｇ、
Into a 1000 ml four-neck flask, 50.0 g of dihydroxydiphenylmethane (an isomer mixture consisting of 36.2% 4,4'-dihydroxydiphenylmethane (structural formula below), 46.6% 2,4'-dihydroxydiphenylmethane, and 17.2% 2,2'-dihydroxydiphenylmethane) was added.
実施例４～６、比較例４～７
多官能ビニル化合物として、実施例１～３、比較例１～３で得たビニル化合物Ａ～Ｆ及びビニル樹脂Ｇ（ＯＰＥ－２ＳＴ：三菱ガス化学株式会社製、ビニル基当量：５９０．０ｇ／ｅｑ、数平均分子量１１８７）を使用し、硬化促進剤（ラジカル重合開始剤）として有機過酸化物であるパーブチルＰ（日油株式会社製）、酸化防止剤としてアデカスタブＡＯ－６０（株式会社ＡＤＥＫＡ製）を表１に示す配合割合で混合し、溶剤に溶解して均一な組成物とした。本組成物をＰＥＴフィルムに塗布し、１３０℃で５分乾燥を行い、樹脂組成物を得た。ＰＥＴフィルムから取り出した組成物を鏡面板に挟み、減圧下１３０℃で１５分及び２１０℃で８０分２ＭＰａの圧力をかけながら硬化した。得られた硬化物の特性を表１に示す。 Examples 4 to 6, Comparative Examples 4 to 7
As the polyfunctional vinyl compound, vinyl compounds A to F obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and vinyl resin G (OPE-2ST: manufactured by Mitsubishi Gas Chemical Company, Inc., vinyl group equivalent: 590.0 g / eq, number average molecular weight 1187) were used, and Perbutyl P (manufactured by NOF Corporation), an organic peroxide, was used as a curing accelerator (radical polymerization initiator), and Adeka STAB AO-60 (manufactured by ADEKA Corporation) was used as an antioxidant in the blending ratio shown in Table 1. The composition was applied to a PET film and dried at 130 ° C. for 5 minutes to obtain a resin composition. The composition removed from the PET film was sandwiched between mirror plates and cured under reduced pressure at 130 ° C. for 15 minutes and at 210 ° C. for 80 minutes while applying a pressure of 2 MPa. The properties of the obtained cured product are shown in Table 1.
多官能ビニル化合物として、実施例１～３、比較例１～３で得たビニル化合物Ａ～Ｆ及びビニル樹脂Ｇ（ＯＰＥ－２ＳＴ：三菱ガス化学株式会社製、ビニル基当量：５９０．０ｇ／ｅｑ、数平均分子量１１８７）を使用し、硬化促進剤（ラジカル重合開始剤）として有機過酸化物であるパーブチルＰ（日油株式会社製）、酸化防止剤としてアデカスタブＡＯ－６０（株式会社ＡＤＥＫＡ製）を表１に示す配合割合で混合し、溶剤に溶解して均一な組成物とした。本組成物をＰＥＴフィルムに塗布し、１３０℃で５分乾燥を行い、樹脂組成物を得た。ＰＥＴフィルムから取り出した組成物を鏡面板に挟み、減圧下１３０℃で１５分及び２１０℃で８０分２ＭＰａの圧力をかけながら硬化した。得られた硬化物の特性を表１に示す。 Examples 4 to 6, Comparative Examples 4 to 7
As the polyfunctional vinyl compound, vinyl compounds A to F obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and vinyl resin G (OPE-2ST: manufactured by Mitsubishi Gas Chemical Company, Inc., vinyl group equivalent: 590.0 g / eq, number average molecular weight 1187) were used, and Perbutyl P (manufactured by NOF Corporation), an organic peroxide, was used as a curing accelerator (radical polymerization initiator), and Adeka STAB AO-60 (manufactured by ADEKA Corporation) was used as an antioxidant in the blending ratio shown in Table 1. The composition was applied to a PET film and dried at 130 ° C. for 5 minutes to obtain a resin composition. The composition removed from the PET film was sandwiched between mirror plates and cured under reduced pressure at 130 ° C. for 15 minutes and at 210 ° C. for 80 minutes while applying a pressure of 2 MPa. The properties of the obtained cured product are shown in Table 1.
実施例の多官能ビニル化合物は、比較例に比べて、熱伝導率が高く、尚且つ低誘電率、低誘電正接という優れた物性を示した。
The polyfunctional vinyl compounds of the examples showed superior physical properties, including higher thermal conductivity, lower dielectric constant, and lower dielectric tangent, compared to the comparative examples.
本発明の多官能ビニル化合物は、高速通信機器の電子材料として電子部品や配線からの発熱を逃がしやすく信号損失か少ない材料として有用である。
The polyfunctional vinyl compound of the present invention is useful as an electronic material for high-speed communication devices, as it easily dissipates heat generated from electronic components and wiring and causes little signal loss.
The polyfunctional vinyl compound of the present invention is useful as an electronic material for high-speed communication devices, as it easily dissipates heat generated from electronic components and wiring and causes little signal loss.
Claims (4)
- 下記一般式（１）で表される多官能ビニル化合物。
- Ｒ１～Ｒ４のうち少なくとも一つが、メチル基またはフェニル基である請求項１に記載の多官能ビニル化合物。 The polyfunctional vinyl compound according to claim 1, in which at least one of R1 to R4 is a methyl group or a phenyl group.
- 請求項１または２に記載の多官能ビニル化合物とラジカル重合開始剤とを必須成分として含有する多官能ビニル組成物。 A polyfunctional vinyl composition comprising the polyfunctional vinyl compound according to claim 1 or 2 and a radical polymerization initiator as essential components.
- 請求項３に記載の多官能ビニル組成物を硬化してなる多官能ビニル硬化物。
A multifunctional vinyl cured product obtained by curing the multifunctional vinyl composition according to claim 3.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1171332A (en) * | 1997-06-17 | 1999-03-16 | Sumitomo Chem Co Ltd | Triphenylmethane derivative and its use |
| JP2014062243A (en) * | 2012-08-30 | 2014-04-10 | Nippon Steel & Sumikin Chemical Co Ltd | Aromatic vinyl benzyl ether compound, and curable composition containing the same |
| WO2020059625A1 (en) * | 2018-09-18 | 2020-03-26 | Dic株式会社 | Phenol compound, active ester resin, production method for active ester resin, thermosetting resin composition, and cured product of thermosetting resin composition |
| JP2023068626A (en) * | 2021-11-02 | 2023-05-17 | 信越化学工業株式会社 | Molecular resist composition and patterning process |
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2023
- 2023-09-15 WO PCT/JP2023/033749 patent/WO2024070773A1/en unknown
- 2023-09-23 TW TW112136489A patent/TW202413454A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1171332A (en) * | 1997-06-17 | 1999-03-16 | Sumitomo Chem Co Ltd | Triphenylmethane derivative and its use |
| JP2014062243A (en) * | 2012-08-30 | 2014-04-10 | Nippon Steel & Sumikin Chemical Co Ltd | Aromatic vinyl benzyl ether compound, and curable composition containing the same |
| WO2020059625A1 (en) * | 2018-09-18 | 2020-03-26 | Dic株式会社 | Phenol compound, active ester resin, production method for active ester resin, thermosetting resin composition, and cured product of thermosetting resin composition |
| JP2023068626A (en) * | 2021-11-02 | 2023-05-17 | 信越化学工業株式会社 | Molecular resist composition and patterning process |
Non-Patent Citations (1)
| Title |
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| ITSUNO, SHINICHI ET AL.: "Design and synthesis of chiral hyperbranched polymers containing cinchona squaramide moieties and their catalytic activity in the asymmetric Michael addition reaction", JOURNAL OF CATALYSIS., vol. 377, 2019, pages 543 - 549, XP085834023, Retrieved from the Internet <URL:https://doi.org/10.1016/j.jcat.2019.07.060> DOI: 10.1016/j.jcat.2019.07.060 * |
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