JP2734101B2 - Dialkyl peroxides and their uses - Google Patents
Dialkyl peroxides and their usesInfo
- Publication number
- JP2734101B2 JP2734101B2 JP1184498A JP18449889A JP2734101B2 JP 2734101 B2 JP2734101 B2 JP 2734101B2 JP 1184498 A JP1184498 A JP 1184498A JP 18449889 A JP18449889 A JP 18449889A JP 2734101 B2 JP2734101 B2 JP 2734101B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- benzophenone
- alkyl group
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000002978 peroxides Chemical class 0.000 title claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 41
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 35
- 125000000217 alkyl group Chemical group 0.000 claims description 33
- -1 α -Cumyl group Chemical group 0.000 claims description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 description 52
- 239000003999 initiator Substances 0.000 description 27
- 238000006116 polymerization reaction Methods 0.000 description 21
- IETYNJBCXVFYIQ-UHFFFAOYSA-N [4-(2-tert-butylperoxypropan-2-yl)phenyl]-phenylmethanone Chemical compound C1=CC(C(C)(C)OOC(C)(C)C)=CC=C1C(=O)C1=CC=CC=C1 IETYNJBCXVFYIQ-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 150000008366 benzophenones Chemical class 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 238000000862 absorption spectrum Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000000016 photochemical curing Methods 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
- 239000012965 benzophenone Substances 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000003377 acid catalyst Substances 0.000 description 8
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- 238000001723 curing Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
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- 239000011347 resin Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001451 organic peroxides Chemical class 0.000 description 7
- 238000012719 thermal polymerization Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- CKFPWZPBRHQASN-UHFFFAOYSA-N phenyl-(4-propan-2-ylphenyl)methanone Chemical compound C1=CC(C(C)C)=CC=C1C(=O)C1=CC=CC=C1 CKFPWZPBRHQASN-UHFFFAOYSA-N 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
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- 238000003860 storage Methods 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 244000028419 Styrax benzoin Species 0.000 description 4
- 235000000126 Styrax benzoin Nutrition 0.000 description 4
- 235000008411 Sumatra benzointree Nutrition 0.000 description 4
- RYPMCLACFAFHHT-UHFFFAOYSA-N [4-[2-(2-methylpentan-2-ylperoxy)propan-2-yl]phenyl]-phenylmethanone Chemical compound C1=CC(C(C)(C)OOC(C)(C)CCC)=CC=C1C(=O)C1=CC=CC=C1 RYPMCLACFAFHHT-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229960002130 benzoin Drugs 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 235000019382 gum benzoic Nutrition 0.000 description 4
- 125000001867 hydroperoxy group Chemical group [*]OO[H] 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- UHQVWMLQGUZCEN-UHFFFAOYSA-N (4-bromophenyl)-[4-(2-tert-butylperoxypropan-2-yl)phenyl]methanone Chemical compound C1=CC(C(C)(C)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(Br)C=C1 UHQVWMLQGUZCEN-UHFFFAOYSA-N 0.000 description 2
- JIEVQNZSQBVZLH-UHFFFAOYSA-N (4-butoxyphenyl)-[4-(2-tert-butylperoxypropan-2-yl)phenyl]methanone Chemical compound C1=CC(OCCCC)=CC=C1C(=O)C1=CC=C(C(C)(C)OOC(C)(C)C)C=C1 JIEVQNZSQBVZLH-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- RGICCULPCWNRAB-UHFFFAOYSA-N 2-[2-(2-hexoxyethoxy)ethoxy]ethanol Chemical compound CCCCCCOCCOCCOCCO RGICCULPCWNRAB-UHFFFAOYSA-N 0.000 description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- 229920002367 Polyisobutene Polymers 0.000 description 2
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- ASDKNXKZHWMHNB-UHFFFAOYSA-N [2,6-dipropyl-4-[2-(2,4,4-trimethylpentan-2-ylperoxy)butan-2-yl]phenyl]-(2,3,4-trimethoxyphenyl)methanone Chemical compound CCCC1=CC(C(C)(CC)OOC(C)(C)CC(C)(C)C)=CC(CCC)=C1C(=O)C1=CC=C(OC)C(OC)=C1OC ASDKNXKZHWMHNB-UHFFFAOYSA-N 0.000 description 2
- COFBJNBJVDPNOX-UHFFFAOYSA-N [3-(2-tert-butylperoxypropan-2-yl)phenyl]-phenylmethanone Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 COFBJNBJVDPNOX-UHFFFAOYSA-N 0.000 description 2
- SFRLXSCEFIQIJI-UHFFFAOYSA-N [4-(2-chloropropan-2-yl)phenyl]-phenylmethanone Chemical compound C1=CC(C(C)(Cl)C)=CC=C1C(=O)C1=CC=CC=C1 SFRLXSCEFIQIJI-UHFFFAOYSA-N 0.000 description 2
- MNZMIKXZPAFZOC-UHFFFAOYSA-N [4-(2-hydroperoxypropan-2-yl)phenyl]-phenylmethanone Chemical compound C1=CC(C(C)(OO)C)=CC=C1C(=O)C1=CC=CC=C1 MNZMIKXZPAFZOC-UHFFFAOYSA-N 0.000 description 2
- PPAYGLBWYAIWPW-UHFFFAOYSA-N [4-(2-hydroxypropan-2-yl)phenyl]-phenylmethanone Chemical compound C1=CC(C(C)(O)C)=CC=C1C(=O)C1=CC=CC=C1 PPAYGLBWYAIWPW-UHFFFAOYSA-N 0.000 description 2
- ORGFWISDSOKUQK-UHFFFAOYSA-N [4-(2-tert-butylperoxypropan-2-yl)-2-methylphenyl]-phenylmethanone Chemical compound CC1=CC(C(C)(C)OOC(C)(C)C)=CC=C1C(=O)C1=CC=CC=C1 ORGFWISDSOKUQK-UHFFFAOYSA-N 0.000 description 2
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- 230000001070 adhesive effect Effects 0.000 description 2
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical class ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- SMVAGJYGTJEVDI-UHFFFAOYSA-N phenyl-[4-[2-(2,4,4-trimethylpentan-2-ylperoxy)propan-2-yl]phenyl]methanone Chemical compound C1=CC(C(C)(C)OOC(C)(C)CC(C)(C)C)=CC=C1C(=O)C1=CC=CC=C1 SMVAGJYGTJEVDI-UHFFFAOYSA-N 0.000 description 2
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- LYHBGVUSOICOJU-UHFFFAOYSA-N 4-ethenoxy-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OC=C LYHBGVUSOICOJU-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UNVOEGZIVNMUDG-UHFFFAOYSA-N [2-(2-tert-butylperoxypropan-2-yl)phenyl]-phenylmethanone Chemical compound C(C)(C)(C)OOC(C)(C)C1=C(C(=O)C2=CC=CC=C2)C=CC=C1 UNVOEGZIVNMUDG-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- YLTDNYQTDYMOBH-UHFFFAOYSA-N bis(prop-2-enyl) 2-hydroxybutanedioate Chemical compound C=CCOC(=O)C(O)CC(=O)OCC=C YLTDNYQTDYMOBH-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical group OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- LDMOUJCEIYFVQR-UHFFFAOYSA-N thioxanthen-3-one Chemical class C1=CC=C2SC3=CC(=O)C=CC3=CC2=C1 LDMOUJCEIYFVQR-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、新規なジアルキルペルオキシド、及び、そ
の用途に関する。Description: TECHNICAL FIELD The present invention relates to a novel dialkyl peroxide and its use.
（従来の技術） 光重合（光硬化）性モノマー、光重合（光硬化）性樹
脂組成物を光重合、光硬化させる重合、硬化法は、熱重
合、熱硬化法及び酸化硬化法に比べて、低温、迅速に重
合、硬化でき、生産性向上、省エネルギー、無公害など
の多くの長所があり、また、選択的硬化も可能であるた
め、印刷インキ、塗料、接着剤、樹脂凸版、プリント配
線基盤の加工、などに広く使われている。(Prior art) Photopolymerizable (photocurable) monomer, photopolymerizable (photocurable) resin composition, photopolymerization, photocuring polymerization, curing method is compared with thermal polymerization, thermosetting method and oxidation curing method. It can quickly polymerize and cure at low temperature, has many advantages such as productivity improvement, energy saving and pollution-free, and also allows selective curing, so printing ink, paint, adhesive, resin letterpress, printed wiring It is widely used for processing substrates.
光重合、光硬化方法においては、各種の開始剤が開発
されてきた。例えば、ベンゾイン、ベンゾインエーテル
類、ベンジル、アリールジアゾニウム塩、ベンゾフェノ
ン誘導体、アセトフェノン誘導体、キサンテート類、チ
オキサントン類、ハロゲン化炭化水素類などの紫外線の
作用下でラジカルを発生する光重合開始剤が知られてい
る〔ジャーナル・オブ・オイル・アンド・カラー・ケミ
スツ・アソシエーション〔J.Oil.Col.Assoc.）59巻,166
〜171頁（1976年）〕。In photopolymerization and photocuring methods, various initiators have been developed. For example, benzoin, benzoin ethers, benzyl, aryldiazonium salts, benzophenone derivatives, acetophenone derivatives, xanthates, thioxanthones, photopolymerization initiators that generate radicals under the action of ultraviolet light such as halogenated hydrocarbons are known. [Journal of Oil and Color Chemistry Association [J. Oil. Col. Assoc.] 59, 166
171 (1976)].
また、過酸化ベンゾイル、ジ−ｔ−ブチルペルオキシ
ドなどの有機過酸化物が光重合開始剤として使用できる
ことが知られている。しかし、これらの有機過酸化物
は、一般に320nm以下の光しか吸収しない〔ケミカル・
レビュー（Chem.Rev）,68巻,125〜151頁（1965年）〕。
増感剤を併用することが試みられたが、増感剤から有機
過酸化物への分子間での光エネルギーの伝達効率が低
く、有機過酸化物の光分解効率が低くなってしまい、特
に、ジアルキル型有機過酸化物であるジ−ｔ−ブチルペ
ルオキシドは、分子間では光増感分解しないと報告され
ている〔ジャーナル・オブ・ジ・アメリカン・ケミカル
・ソサイエティー（J.Am.Chem.Soc.）,87巻,3413〜3417
頁（1965年）〕。It is also known that organic peroxides such as benzoyl peroxide and di-t-butyl peroxide can be used as a photopolymerization initiator. However, these organic peroxides generally only absorb light below 320 nm [Chemical
Review (Chem. Rev), 68, 125-151 (1965)].
Attempts have been made to use a sensitizer in combination, but the transfer efficiency of light energy between molecules from the sensitizer to the organic peroxide is low, and the photodecomposition efficiency of the organic peroxide is low. It has been reported that di-t-butyl peroxide, a dialkyl-type organic peroxide, does not undergo photosensitization decomposition between molecules [Journal of the American Chemical Society (J. Am. Chem. Soc. .), 87 volumes, 3413-3417
Page (1965)].
この問題を解決するために、分子内に光吸収基として
ベンゾフェノン基を含有するエステル型有機過酸化物が
開発されている（米国特許第4416826号）（特開昭59−1
97401）。しかし、これらの化合物は、暗所保存安定性
が悪い、硬化した樹脂が黄変するなどの欠点があった。In order to solve this problem, an ester type organic peroxide containing a benzophenone group as a light absorbing group in the molecule has been developed (US Pat. No. 4,416,826) (Japanese Patent Application Laid-Open No. 59-1).
97401). However, these compounds have disadvantages such as poor storage stability in a dark place and yellowing of the cured resin.
（発明が解決しようとする問題点） 前記従来の光重合開始剤は、それぞれ有用であるが、
なお改良すべきいくつかの欠点を持っている。例えば、 （１）ベンゾイン、ベンゾインエーテル類は、暗所保存
安定性が悪い。(Problems to be Solved by the Invention) The conventional photopolymerization initiators are each useful,
It has some drawbacks that need to be improved. For example, (1) Benzoin and benzoin ethers have poor storage stability in dark places.
（２）ベンゾフェノン誘導体はアミン等と併用するが、
重合物、硬化物が黄変する。(2) The benzophenone derivative is used in combination with an amine or the like,
The polymer and the cured product turn yellow.
（３）チオキサントン類は、モノマー及び樹脂への溶解
度が低い。(3) Thioxanthones have low solubility in monomers and resins.
（４）光吸収基含有エステル型過酸化物は、熱安定性が
悪く、硬化した樹脂も黄変する。(4) The ester type peroxide containing a light absorbing group has poor thermal stability, and the cured resin also turns yellow.
本発明の目的は、従来の光重合開始剤の欠点を改良し
た、熱安定性が良く、重合物や硬化物の黄変が少なく、
しかも光重合、光硬化の効率のよい、工業的価値の高い
新規なペルオキシドおよびその用途を提供することにあ
る。The object of the present invention is to improve the disadvantages of the conventional photopolymerization initiator, good thermal stability, less yellowing of the polymer or cured product,
Moreover, it is an object of the present invention to provide a novel peroxide having high industrial value, which is efficient in photopolymerization and photocuring, and its use.
（発明を解決するための手段） 本発明の目的は、新規な光吸収基含有ジアルキルペル
オキシドによって達成された。Means for Solving the Invention The object of the present invention has been achieved by a novel light-absorbing group-containing dialkyl peroxide.
すなわち、本発明の第１は、一般式 （式中、R1は炭素数４〜８の三級アルキル基、またはα
−クミル基、R2,R3は炭素数１〜２のアルキル基、R4は
炭素数１〜３のアルキル基、水素原子の中から選ばれ、
R5は炭素数１〜12のアルキル基、炭素数１〜４のアルコ
キシ基、ハロゲン原子、水素原子の中から選ばれ、ｍは
１〜3,nは１〜２を表す。また、R1OOC（R2）（R3）基
は、メタ、またはパラ位である。） で示されるベンゾフェノン基含有ジアルキルペルオキシ
ドであり、本発明の第２および第３は、前記新規ジアル
キルペルオキシドを有効成分とする光分解型ラジカル発
生剤および熱分解型ラジカル発生剤である。That is, the first of the present invention is a general formula (Wherein, R 1 is a tertiary alkyl group having 4 to 8 carbon atoms, or α
-Cumyl group, R 2 , R 3 is an alkyl group having 1 to 2 carbon atoms, R 4 is an alkyl group having 1 to 3 carbon atoms, selected from hydrogen atoms,
R 5 is selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom and a hydrogen atom, m represents 1-3, and n represents 1-2. The R 1 OOC (R 2 ) (R 3 ) group is in the meta or para position. The second and third aspects of the present invention are a photodecomposition type radical generator and a thermal decomposition type radical generator containing the novel dialkyl peroxide as an active ingredient.
ここで光分解型ラジカル発生剤とは、光重合開始剤、
光硬化剤、光架橋剤等であり、熱分解型ラジカル発生剤
とは、熱によりラジカルを発生する重合開始剤、架橋
剤、硬化剤等である。Here, the photolytic radical generator is a photopolymerization initiator,
It is a photo-curing agent, a photo-crosslinking agent, etc., and the thermal decomposition type radical generator is a polymerization initiator, a cross-linking agent, a curing agent, etc. that generates a radical by heat.
本発明のベンゾフェノン基含有ジアルキルペルオキシ
ドを具体的に示すと （１）４−（１−ｔ−ブチルペルオキシ−１−メチルエ
チル）ベンゾフェノン （２）４−（１−ｔ−アミルペルオキシ−１−メチルエ
チル）ベンゾフェノン （３）４−（１−ｔ−ヘキシルペルオキシ−１−メチル
エチル）ベンゾフェノン （４）４−（１−ｔ−オクチルペルオキシ−１−メチル
エチル）ベンゾフェノン （５）４−（１−クミルペルオキシ−１−メチルエチ
ル）ベンゾフェノン （６）４−（１−ｔ−ブチルペルオキシ−１−メチルエ
チル）−２−メチルベンゾフェノン （７）４（１−ｔ−ブチルペルオキシ−１−メチルエチ
ル）−２−プロピルベンゾフェノン （８）４−（１−ｔ−ブチルペルオキシ−１−メチルエ
チル）−2,6−ジプロピルベンゾフェノン （９）４−（１−ｔ−ブチルペルオキシ−１−メチルエ
チル）−2,6−ジプロピル−４′−ｔ−ドデシルベンゾ
フェノン （10）４−（１−ｔ−ブチルペルオキシ−１−メチルエ
チル）−４′−クロルベンゾフェノン （11）４−（１−ｔ−ブチルペルオキシ−１−メチルエ
チル）−４′−ブロモベンゾフェノン （12）４−（１−ｔ−ブチルペルオキシ−１−メチルエ
チル）−４′−ブトキシベンゾフェノン （13）４−（１−ｔ−オクチルペルオキシ−１−メチル
プロピル）−2,6−ジプロピル−２′,3′,4′−トリメ
トキシベンゾフェノン （14）４−（１−ｔ−オクチルペルオキシ−１−メチル
プロピル）−２−,6−ジプロピル−３′,4′−ジエトキ
シベンゾフェノン （15）３−（１−ｔ−ブチルペルオキシ−１−メチルエ
チル）ベンゾフェノン （16）３−（１−ｔ−オクチルペルオキシ−１−メチル
プロピル）−６−プロピル−３′,4′−ジエトキシベン
ゾフェノン などがある。Specific examples of the benzophenone group-containing dialkyl peroxide of the present invention are: (1) 4- (1-t-butylperoxy-1-methylethyl) benzophenone (2) 4- (1-t-amylperoxy-1-methylethyl) ) Benzophenone (3) 4- (1-t-hexylperoxy-1-methylethyl) benzophenone (4) 4- (1-t-octylperoxy-1-methylethyl) benzophenone (5) 4- (1-cumyl) Peroxy-1-methylethyl) benzophenone (6) 4- (1-t-butylperoxy-1-methylethyl) -2-methylbenzophenone (7) 4 (1-t-butylperoxy-1-methylethyl) -2 -Propylbenzophenone (8) 4- (1-t-butylperoxy-1-methylethyl) -2,6-dipropylbenzof Non (9) 4- (1-tert-butylperoxy-1-methylethyl) -2,6-dipropyl-4'-tert-dodecylbenzophenone (10) 4- (1-tert-butylperoxy-1-methylethyl) ) -4'-Chlorobenzophenone (11) 4- (1-t-butylperoxy-1-methylethyl) -4'-bromobenzophenone (12) 4- (1-t-butylperoxy-1-methylethyl)- 4'-butoxybenzophenone (13) 4- (1-t-octylperoxy-1-methylpropyl) -2,6-dipropyl-2 ', 3', 4'-trimethoxybenzophenone (14) 4- (1- t-octylperoxy-1-methylpropyl) -2-, 6-dipropyl-3 ', 4'-diethoxybenzophenone (15) 3- (1-t-butylperoxy-1-methylethyl) benzophenone (16) 3- (1-t-octylperoxy-1-methylpropyl) -6-propyl-3 ', 4'-diethoxybenzophenone and the like.
本発明の一般式（Ｉ）で示される化合物は、次の方法
で製造することができる。第１の製造法は、以下の通り
である。即ち、 （式中、R2,R3は炭素数１〜２のアルキル基、R4は炭素
数１〜３のアルキル基、水素原子の中から選ばれ、R5は
炭素数１〜12のアルキル基、炭素数１〜４のアルコキシ
基、ハロゲン原子、水素原子の中から選ばれ、ｍは１〜
３、ｎは１〜２を表す。また、CH（R2）（R3）基は、メ
タ、またはパラ位である。） で示されるイソアルキル基置換ベンゾフェノンと、 一般式 R1OOH （II） （式中、R1は炭素数４〜８の三級アルキル基、またはα
−クルミ基を表す。） で示されるヒドロペルオキシドを、第４および第５周期
の遷移元素の中から選ばれる金属の金属塩の存在下で反
応させ、 一般式 （式中、R1,R2,R3,R4,R5は前記と同じものを示し、m,n
も前記と同じである。また、R1OOC（R2）（R3）基は、
メタ、またはパラ位である。） で示されるベンゾフェノン基含有ジアルキルペルオキシ
ドを得る。The compound represented by the general formula (I) of the present invention can be produced by the following method. The first manufacturing method is as follows. That is, (Wherein, R 2 and R 3 are an alkyl group having 1 to 2 carbon atoms, R 4 is an alkyl group having 1 to 3 carbon atoms, a hydrogen atom, and R 5 is an alkyl group having 1 to 12 carbon atoms. And m is selected from an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom.
3, n represents 1-2. The CH (R 2 ) (R 3 ) group is in the meta or para position. And an isoalkyl group-substituted benzophenone represented by the following formula: R 1 OOH (II) wherein R 1 is a tertiary alkyl group having 4 to 8 carbon atoms, or α
-Represents a walnut group. ) Is reacted in the presence of a metal salt of a metal selected from the fourth and fifth transition elements, (Wherein, R 1 , R 2 , R 3 , R 4 , and R 5 represent the same as described above, and m, n
Is the same as above. The R 1 OOC (R 2 ) (R 3 ) group is
Meta or para. To obtain a benzophenone group-containing dialkyl peroxide represented by the following formula:
最初の化合物（III）は、置換ベンゼンと置換ベンゾ
イルクロリドのフリーデル・クラフツ反応などにより、
容易に得られる。The first compound (III) is obtained by the Friedel-Crafts reaction between substituted benzene and substituted benzoyl chloride,
Obtained easily.
本発明の製造法の化合物（III）とヒドロペルオキシ
ド（II）との反応では、触媒として第４および第５周期
の遷移元素の中から選ばれる金属の金属塩を用いること
ができる。金属塩の金属を具体的に示すと、銅、コバル
ト、マンガン、鉄、クロム、亜鉛などであり、配位子を
具体的に示すと、ヨウ素、臭素、塩素のハロゲン、硫
酸、リン酸、硝酸、炭酸などの鉱酸、ギ酸、酢酸、ナフ
テン酸、オクテン酸、グルコン酸、などの有機酸、シア
ン、アセチルアセトナートなどである。金属塩の使用量
はヒドロペルオキシド１モルに対して0.0001〜0.1モル
である。反応条件は用いる金属塩によって異なるが、反
応温度は通常30〜100℃、反応時間は１〜50時間が好ま
しい。また、溶媒としてベンゼン、トルエンなどを用い
ることができる。In the reaction between compound (III) and hydroperoxide (II) in the production method of the present invention, a metal salt of a metal selected from the fourth and fifth transition elements can be used as a catalyst. Specific examples of the metal of the metal salt include copper, cobalt, manganese, iron, chromium, and zinc, and specific examples of the ligand include iodine, bromine, halogen of chlorine, sulfuric acid, phosphoric acid, and nitric acid. And organic acids such as mineral acids such as carbonic acid, formic acid, acetic acid, naphthenic acid, octenoic acid, and gluconic acid, and cyanide and acetylacetonate. The amount of the metal salt used is 0.0001 to 0.1 mol per 1 mol of the hydroperoxide. The reaction conditions vary depending on the metal salt used, but the reaction temperature is usually preferably 30 to 100 ° C, and the reaction time is preferably 1 to 50 hours. In addition, benzene, toluene, or the like can be used as a solvent.
第２の製造法は、α−ヒドロキシイソアルキル基置換
ベンゾフェノン誘導体（IV）を、酸触媒の存在下、ヒド
ロペルオキシド（II）と反応させることにより、一般式
（Ｉ）で示される化合物が得られる。In the second production method, a compound represented by the general formula (I) is obtained by reacting an α-hydroxyisoalkyl group-substituted benzophenone derivative (IV) with hydroperoxide (II) in the presence of an acid catalyst. .
（式中、R1,R2,R3,R4,R5,m,nおよびR1OOC（R2）（R3）
基の位置は、前記の通りである。） 最初の化合物（IV）は、化合物（III）を空気酸化し
て生成するヒドロペルオキシドを還元することにより容
易に得られる。 (Wherein R 1 , R 2 , R 3 , R 4 , R 5 , m, n and R 1 OOC (R 2 ) (R 3 )
The position of the group is as described above. The first compound (IV) can be easily obtained by reducing the hydroperoxide formed by air oxidation of compound (III).
本発明の製造法の化合物（IV）とヒドロペルオキシド
（II）との反応では、酸触媒として過塩素酸、塩酸、硫
酸、リン酸などの鉱酸を用いることができる。酸触媒の
使用量は、化合物（IV）１モルに対して0.001〜１モル
である。溶媒として酢酸などを用いることができる。ま
た、反応系中に硫酸マグネシウムなどの脱水剤を存在さ
せると、収率を向上させることができる。反応条件は、
反応温度は通常０〜70℃、反応時間は１〜10時間が好ま
しい。In the reaction between the compound (IV) and the hydroperoxide (II) in the production method of the present invention, a mineral acid such as perchloric acid, hydrochloric acid, sulfuric acid, phosphoric acid or the like can be used as an acid catalyst. The amount of the acid catalyst to be used is 0.001-1 mol per 1 mol of compound (IV). Acetic acid or the like can be used as a solvent. Further, when a dehydrating agent such as magnesium sulfate is present in the reaction system, the yield can be improved. The reaction conditions are
The reaction temperature is usually preferably from 0 to 70 ° C, and the reaction time is preferably from 1 to 10 hours.
第３の製造法は、イソアルケニル基置換ベンゾフェノ
ン誘導体（Ｖ）を、酸触媒の存在下、ヒドロペルオキシ
ド（II）と反応させることにより、一般式（Ｉ）で示さ
れる化合物が得られる。In the third production method, the compound represented by the general formula (I) is obtained by reacting the isoalkenyl group-substituted benzophenone derivative (V) with hydroperoxide (II) in the presence of an acid catalyst.
（式中、R1,R2,R3,R4,R5,R6,nおよびR1OOC（R2）（R3）
基の位置は、前記の通りである。） 最初の化合物（Ｖ）は、化合物（IV）を脱水すること
により容易に得られる。 (Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , n and R 1 OOC (R 2 ) (R 3 )
The position of the group is as described above. ) The first compound (V) can be easily obtained by dehydrating the compound (IV).
本発明の製造法の化合物（Ｖ）とヒドロペルオキシド
（II）との反応では、酸触媒として塩酸、硫酸、過塩素
酸などの鉱酸、および／または、塩化亜鉛、塩化アルミ
ニウムなどのルイス酸などが使用される。酸触媒の使用
量は、化合物（Ｖ）１モルに対して0.001〜１モルであ
る。反応条件は、反応温度は通常０〜70℃、反応時間は
１〜10時間が好ましい。また、イソプロピルアルコール
などの溶媒を用いることができる。In the reaction between the compound (V) and the hydroperoxide (II) in the production method of the present invention, a mineral acid such as hydrochloric acid, sulfuric acid, perchloric acid and / or a Lewis acid such as zinc chloride and aluminum chloride are used as an acid catalyst. Is used. The amount of the acid catalyst to be used is 0.001-1 mol per 1 mol of compound (V). Regarding the reaction conditions, the reaction temperature is preferably 0 to 70 ° C., and the reaction time is preferably 1 to 10 hours. Further, a solvent such as isopropyl alcohol can be used.
第４の製造法は、α−ハロゲン化イソアルキル基置換
ベンゾフェノン誘導体（VI）を、アルカリの存在下、ヒ
ドロペルオキシド（II）と反応させることにより、一般
式（Ｉ）で示される化合物が得られる。In the fourth production method, a compound represented by the general formula (I) is obtained by reacting an α-halogenated isoalkyl group-substituted benzophenone derivative (VI) with hydroperoxide (II) in the presence of an alkali.
（式中、R1,R2,R3,R4,R5,X,m,nおよびR1OOC（R2）
（R3）基の位置は、前記の通りである。） 最初の化合物（VI）は、化合物（III）を塩素ガス、
Ｎ−ブロモこはく酸イミドなどでハロゲン化することに
より容易に得られる。 (Wherein, R 1 , R 2 , R 3 , R 4 , R 5 , X, m, n and R 1 OOC (R 2 )
The position of the (R 3 ) group is as described above. ) The first compound (VI) is compound (III) with chlorine gas,
It can be easily obtained by halogenation with N-bromosuccinimide or the like.
本発明の製造法の化合物（VI）とヒドロペルオキシド
（II）との反応では、アルカリとして、水酸化ナトリウ
ム、水酸化カリウム、ピリジンなどを用いることができ
る。アルカリの使用量は、化合物（VI）１モルに対して
0.8〜3.0モルが好ましい。反応条件は、反応温度は通常
０〜70℃、反応時間は１〜10時間が好ましい。また、溶
媒としてヘキサン、ベンゼン、トルエン、エーテルなど
を用いることができる。In the reaction between the compound (VI) and the hydroperoxide (II) in the production method of the present invention, sodium hydroxide, potassium hydroxide, pyridine and the like can be used as the alkali. The amount of the alkali used is based on 1 mol of the compound (VI).
0.8-3.0 mol is preferred. Regarding the reaction conditions, the reaction temperature is preferably 0 to 70 ° C., and the reaction time is preferably 1 to 10 hours. Further, hexane, benzene, toluene, ether and the like can be used as the solvent.
第５の製造法は以下の通りである。即ち、 一般式 （式中、R2,R3は炭素数１〜２のアルキル基、R4は炭素
数１〜３のアルキル基、水素原子の中から選ばれ、R5は
炭素数１〜12のアルキル基、炭素数１〜４のアルコキシ
基、ハロゲン原子、水素原子の中から選ばれ、ｍは１〜
３、ｎは１〜２を表す。また、Ｃ（OOH）（R2）（R3）
基は、メタ、またはパラ位である。） で示されるα−ヒドロペルオキシイソアルキル基置換ベ
ンゾフェノンと、 一般式 R1OH （VIII） （式中、R1は炭素数４〜８の三級アルキル基、またはα
−クルミ基を表す。） で示されるアルコールを、酸触媒の存在下で反応させ、
一般式（Ｉ）で示されるベンゾフェノン基含有ジアルキ
ルペルオキシドを得る。The fifth manufacturing method is as follows. That is, the general formula (Wherein, R 2 and R 3 are an alkyl group having 1 to 2 carbon atoms, R 4 is an alkyl group having 1 to 3 carbon atoms, a hydrogen atom, and R 5 is an alkyl group having 1 to 12 carbon atoms. And m is selected from an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom.
3, n represents 1-2. In addition, C (OOH) (R 2 ) (R 3 )
The groups are in the meta or para position. Benzophenone substituted with an α-hydroperoxyisoalkyl group represented by the following formula: R 1 OH (VIII) (wherein R 1 is a tertiary alkyl group having 4 to 8 carbon atoms, or α)
-Represents a walnut group. ) Is reacted in the presence of an acid catalyst,
A benzophenone group-containing dialkyl peroxide represented by the general formula (I) is obtained.
第６の製造法は以下の通りである。即ち、 一般式 （式中、R2,R3は炭素数１〜２のアルキル基、R4は炭素
数１〜３のアルキル基、水素原子の中から選ばれ、R5は
炭素数１〜12のアルキル基、炭素数１〜４のアルコキシ
基、ハロゲン原子、水素原子の中から選ばれ、ｍは１〜
３、ｎは１〜２を表す。また、Ｃ（OOH）（R2）（R3）
基は、メタ、またはパラ位である。） で示されるα−ヒドロペルオキシイソアルキル基置換ベ
ンゾフェノンと、 一般式 R7R8C＝CHR9 （IX） （式中、R7は炭素数１〜５のアルキル基またはフェニル
基、R8は炭素数１〜２のアルキル基、R9は水素原子また
はメチル基を表す。） で示されるオレフィンを、酸触媒の存在下で反応させ、
一般式（Ｉ）で示されるベンゾフェノン基含有ジアルキ
ルペルオキシドを得る。The sixth manufacturing method is as follows. That is, the general formula (Wherein, R 2 and R 3 are an alkyl group having 1 to 2 carbon atoms, R 4 is an alkyl group having 1 to 3 carbon atoms, a hydrogen atom, and R 5 is an alkyl group having 1 to 12 carbon atoms. And m is selected from an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom.
3, n represents 1-2. In addition, C (OOH) (R 2 ) (R 3 )
The groups are in the meta or para position. An α-hydroperoxyisoalkyl group-substituted benzophenone represented by the following formula: R 7 R 8 C = CHR 9 (IX) (wherein, R 7 is an alkyl group having 1 to 5 carbon atoms or a phenyl group, and R 8 is An alkyl group having 1 to 2 carbon atoms, and R 9 represents a hydrogen atom or a methyl group) in the presence of an acid catalyst;
A benzophenone group-containing dialkyl peroxide represented by the general formula (I) is obtained.
第７の製造法は以下の通りである。即ち、 一般式 （式中、R2,R3は炭素数１〜２のアルキル基、R4は炭素
数１〜３のアルキル基、水素原子の中から選ばれ、R5は
炭素数１〜12のアルキル基、炭素数１〜４のアルコキシ
基、ハロゲン原子、水素原子の中から選ばれ、ｍは１〜
３、ｎは１〜２を表す。また、Ｃ（OOH）（R2）（R3）
基は、メタ、またはパラ位である。） で示されるα−ヒドロペルオキシイソアルキル基置換ベ
ンゾフェノンと、 一般式 R1X （Ｘ） （式中、R1は炭素数４〜８の三級アルキル基、またはα
−クミル基、Ｘは塩素原子または臭素原子を表す。） で示されるハロゲン化アルキルとをアルカリの存在下で
反応させ、一般式（Ｉ）で示されるベンゾフェノン基含
有ジアルキルペルオキシドを得る。The seventh manufacturing method is as follows. That is, the general formula (Wherein, R 2 and R 3 are an alkyl group having 1 to 2 carbon atoms, R 4 is an alkyl group having 1 to 3 carbon atoms, a hydrogen atom, and R 5 is an alkyl group having 1 to 12 carbon atoms. And m is selected from an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom.
3, n represents 1-2. In addition, C (OOH) (R 2 ) (R 3 )
The groups are in the meta or para position. And α- hydroperoxy isoalkyl group substituted benzophenones represented by), the general formula R 1 X (X) (wherein, R 1 is a tertiary alkyl group of 4 to 8 carbon atoms or alpha,
-A cumyl group, X represents a chlorine atom or a bromine atom. ) Is reacted in the presence of an alkali to obtain a benzophenone group-containing dialkyl peroxide represented by the general formula (I).
上記製造方法によると、ベンゾフェノン基含有ジアル
キルペルオキシドを収率よく製造することができる。According to the above-mentioned production method, a benzophenone group-containing dialkyl peroxide can be produced with high yield.
以上のようにして製造される新規なジアルキルペルオ
キシドは、常温で白色の固体または透明な粘性液体とし
て得られる。得られたそれぞれの化合物は赤外線吸収ス
ペクトル、核磁気共鳴スペクトル、紫外線吸収スペクト
ル、マススペクトルおよび元素分析により、その構造を
同定することができる。The novel dialkyl peroxide produced as described above is obtained as a white solid or a transparent viscous liquid at room temperature. The structure of each compound obtained can be identified by infrared absorption spectrum, nuclear magnetic resonance spectrum, ultraviolet absorption spectrum, mass spectrum and elemental analysis.
本発明のジアルキルペルオキシドは単独で、または他
の成分と混合し、光重合開始剤としてラジカル重合性不
飽和化合物の光重合または光硬化に使用する。この際、
１種または２種以上のラジカル重合性不飽和化合物と、
本発明の光重合開始剤との混合物中に、通常用いられて
いる顔料、フィラー、色素、熱重合禁止剤、可塑剤、溶
媒、増感剤、また、他の既知の光重合開始剤などの添加
剤を適宜配合することもでき、このような感光性組成物
が塗料、接着剤、印刷インキ、印刷凸版、プリント配線
基盤、フォトレジストなどに使用される。The dialkyl peroxide of the present invention is used alone or in combination with other components, and is used as a photopolymerization initiator for photopolymerization or photocuring of a radically polymerizable unsaturated compound. On this occasion,
One or more radically polymerizable unsaturated compounds,
In the mixture with the photopolymerization initiator of the present invention, commonly used pigments, fillers, dyes, thermal polymerization inhibitors, plasticizers, solvents, sensitizers, and other known photopolymerization initiators and the like Additives can be appropriately compounded, and such a photosensitive composition is used for a paint, an adhesive, a printing ink, a printing relief plate, a printed wiring board, a photoresist, and the like.
本発明の光重合開始剤、光硬化剤を配合して光重合、
光硬化させうるラジカル性不飽和化合物としては、重合
性単量体、重合性オリゴマー、および重合性不飽和重合
体があげられる。重合性単量体は、一つ以上の重合性二
重結合を持つ化合物であって、例えば、アクリル酸、メ
タクリル酸、マレイン酸、フマール酸、クロトン酸、イ
タコン酸などの不飽和カルボン酸、および、これらの不
飽和カルボン酸の誘導体、例えばメチル（メタ）アクリ
レート、ブチル（メタ）アクリレート、２−エチルヘキ
シル（メタ）アクリレート、フェニル（メタ）アクリレ
ート、ベンジル（メタ）アクリレート、などのモノエス
テル類、２−ヒドロキシエチル（メタ）アクリレート、
２−ヒドロキシプロピル（メタ）アクリレートなどのヒ
ドロキシエステル類、エチレングリコールジ（メタ）ア
クリレート、ポリエチレングリコールジ（メタ）アクリ
レート、ネオペンチルグリコールジ（メタ）アクリレー
ト、トリメチロールプロパントリ（メタ）アクリレー
ト、ペンタエリスリトールテトラ（メタ）アクリレート
などの多価エステル類、（メタ）アクリロニトリル、
（メタ）アクリルアミド、および、Ｎ−置換（メタ）ア
クリルアミド等、ビニルアセテート、ビニルプロピオネ
ート、ビニルアセテート、および、ビニルスクシネート
等のビニルエステル類、ビニルエーテル類、スチレン、
アルキルスチレン、ハロゲン化スチレン、ジビニルベン
ゼン、ビニルナフタレン、Ｎ−ビニルピロリドン、ジア
リルフタレート、ジアリルマレート、トリアリルイソシ
アネート、および、トリアリルホスフェートなどのビニ
ル化合物などがあげられる。The photopolymerization initiator of the present invention, photopolymerization by blending a photocuring agent,
The photocurable radically unsaturated compounds include polymerizable monomers, polymerizable oligomers, and polymerizable unsaturated polymers. The polymerizable monomer is a compound having one or more polymerizable double bonds, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, unsaturated carboxylic acids such as itaconic acid, and Derivatives of these unsaturated carboxylic acids, for example, monoesters such as methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate; -Hydroxyethyl (meth) acrylate,
Hydroxyesters such as 2-hydroxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Polyhydric esters such as tetra (meth) acrylate, (meth) acrylonitrile,
(Meth) acrylamide, N-substituted (meth) acrylamide, and the like, vinyl acetate, vinyl propionate, vinyl acetate, and vinyl esters such as vinyl succinate, vinyl ethers, styrene,
Examples thereof include vinyl compounds such as alkylstyrene, halogenated styrene, divinylbenzene, vinylnaphthalene, N-vinylpyrrolidone, diallyl phthalate, diallyl malate, triallyl isocyanate, and triallyl phosphate.
重合性オリゴマー、重合性不飽和重合体としては、例
えば、マレート基、フマレート基、アリル基、（メタ）
アクリレート基を持つ硬化性樹脂、不飽和ポリエステ
ル、不飽和アクリル樹脂、および、イソシアネート改質
アクリルオリゴマー、ポリエステルアクリルオリゴマ
ー、および、ポリエーテルアクリルオリゴマー等があげ
られる。Examples of the polymerizable oligomer and the polymerizable unsaturated polymer include a malate group, a fumarate group, an allyl group, and a (meth) group.
Curable resins having an acrylate group, unsaturated polyesters, unsaturated acrylic resins, isocyanate-modified acrylic oligomers, polyester acrylic oligomers, polyether acrylic oligomers, and the like can be given.
また、本発明の光架橋剤に使用される、架橋されるポ
リマーとしては、例えばポリエチレン、エチレンプロピ
レンコポリマー（EPM）、エチレンプロピレンジエンコ
ポリマー（EPDM）、エチレン酢酸ビニルコポリマー（EV
A）、テトラフルオロエチレンビニリデンフルオライド
ヘキサフルオロプロピレン三元コポリマー、クロルスル
ホン化ポリエチレン、塩素化ポリエチレン、ポリブテン
−１、ポリイソブテン、エチレンビニルアセテートコポ
リマー、ポリブタジエン、ポリイソプレン、ポリクロロ
プレン、ブタジエンスチレンコポリマー、天然ゴム、ポ
リアクリレートゴム、ブタジエンアクリロニトリルコポ
リマー、アクリロニトリルブタジエンスチレン三元コポ
リマー、シリコーンゴム、ポリウレタンなどが挙げられ
る。Examples of the crosslinked polymer used in the photocrosslinking agent of the present invention include polyethylene, ethylene propylene copolymer (EPM), ethylene propylene diene copolymer (EPDM), and ethylene vinyl acetate copolymer (EV
A), terpolymer of tetrafluoroethylene vinylidene fluoride hexafluoropropylene, chlorosulfonated polyethylene, chlorinated polyethylene, polybutene-1, polyisobutene, ethylene vinyl acetate copolymer, polybutadiene, polyisoprene, polychloroprene, butadiene styrene copolymer, natural rubber Polyacrylate rubber, butadiene acrylonitrile copolymer, acrylonitrile butadiene styrene terpolymer, silicone rubber, polyurethane and the like.
本発明の光重合開始剤、光硬化剤、光架橋剤の使用量
は、基本的にはラジアル重合性不飽和化合物及び架橋さ
れるポリマーに対して0.01〜10重量％、好ましくは、0.
1〜４重量％であるが、添加剤の種類の影響を受ける。
例えば、光透過性の悪い顔料を混合する場合は、増量す
ることが必要なこともある。しかし、量が多すぎると、
重合体の中に未反応の光重合開始剤が残存し、重合物の
物性を低下するおそれがある。また、少なすぎると重合
が完結せず、未反応の不飽和化合物が残存する。The amount of the photopolymerization initiator, photocuring agent and photocrosslinking agent of the present invention is basically 0.01 to 10% by weight, preferably 0.1 to 10% by weight, based on the radially polymerizable unsaturated compound and the polymer to be crosslinked.
1 to 4% by weight, but affected by the type of additive.
For example, when a pigment having poor light transmittance is mixed, it may be necessary to increase the amount. However, if the amount is too large,
Unreacted photopolymerization initiator may remain in the polymer, and the physical properties of the polymer may be reduced. If the amount is too small, the polymerization is not completed, and unreacted unsaturated compounds remain.
本発明の光重合開始剤、光硬化剤、光架橋剤を配合し
たラジカル重合性不飽和化合物の光重合、光硬化および
光架橋は、既知の方法により250〜500nm、好ましくは、
300〜400nmの波長範囲の光の照射により行う。使用でき
る光源は、日光、水銀ランプ、水銀放電管、キセノンア
ークランプ、閃光放電管、タングステンランプ、ハロゲ
ンランプ、色素レーザー、エキシマレーザー等があげら
れる。Photopolymerization initiator of the present invention, photocuring agent, photopolymerization of a radical polymerizable unsaturated compound blended with a photocrosslinking agent, photocuring and photocrosslinking is 250 to 500 nm by a known method, preferably,
Irradiation with light in the wavelength range of 300 to 400 nm is performed. Light sources that can be used include sunlight, mercury lamps, mercury discharge tubes, xenon arc lamps, flash discharge tubes, tungsten lamps, halogen lamps, dye lasers, excimer lasers, and the like.
本発明者らは、本発明のベンゾフェノン基含有ジアル
キルペルオキシドの用途について更に追求した結果、熱
による重合および架橋においても、有効な性能を有する
ことを突き止めた。The present inventors have further pursued the use of the benzophenone group-containing dialkyl peroxide of the present invention, and as a result, have found that the dialkyl peroxide has effective performance also in thermal polymerization and crosslinking.
本発明の熱重合開始剤に使用されるビニル単量体とし
ては、例えばスチレン、α−メチルスチレン、アクリロ
ニトリル、アクリル酸エステル類、メタクリル酸エステ
ル類、マレイン酸エステル類、フマル酸エステル類、マ
レイミド類、ブタジエン、酢酸ビニル等である。Examples of the vinyl monomer used in the thermal polymerization initiator of the present invention include styrene, α-methylstyrene, acrylonitrile, acrylates, methacrylates, maleates, fumarates, and maleimides. , Butadiene, vinyl acetate and the like.
またこれらの単量体の他各種連鎖移動剤、ゴム成分あ
るいはペンタンなどの発泡剤を添加したものでもよい。Further, in addition to these monomers, various chain transfer agents, rubber components, or foaming agents such as pentane may be added.
発明に使用される熱重合開始剤は、熱分解温度の異な
るその他の開始剤と併用しても良い。The thermal polymerization initiator used in the present invention may be used in combination with other initiators having different thermal decomposition temperatures.
開始剤の添加量は重合に用いる単量体の種類あるいは
その組合せにより異なるが一般に、単量体の仕込量100
重量部に対して純品換算で0.001〜５重量部であり、好
ましくは0.01〜0.5重量部である。その量が0.001重量部
未満では重合速度が遅くなる傾向にある。また５重量部
を越えると経済的でなく、好ましくない。The amount of the initiator to be added depends on the type of the monomer used for the polymerization or the combination thereof, but generally, the amount of the monomer charged is 100%.
It is 0.001 to 5 parts by weight, preferably 0.01 to 0.5 parts by weight, in terms of a pure product based on parts by weight. If the amount is less than 0.001 part by weight, the polymerization rate tends to be slow. If it exceeds 5 parts by weight, it is not economical and is not preferable.
本発明において用いられる重合方法は、通常の塊状重
合、溶液重合あるいは懸濁重合法で重合温度は一般に80
〜150℃であり、好ましくは80〜130℃の温度範囲であ
る。重合温度は一定温度あるいは重合初期では比較的低
温で行い、重合の進行と共に段階的に昇温する方法が用
いられる。The polymerization method used in the present invention is a usual bulk polymerization, solution polymerization or suspension polymerization method, and the polymerization temperature is generally 80.
To 150 ° C, preferably in the temperature range of 80 to 130 ° C. The polymerization is carried out at a constant temperature or at a relatively low temperature at the beginning of the polymerization, and the temperature is raised stepwise as the polymerization proceeds.
本発明で得られた重合体は一般な成形材料に用いられ
るGPタイプポリスチレン、耐衝撃ポリスチレン、発泡ポ
リスチレン、ポリメタクリル酸メチル、スチレン／アク
リロニトリル共重合体、スチレン／アクリロニトリル／
フェニルマレイミド共重合体、メタクリル酸ブチル/2−
エチルヘキシルメタクリレート共重合体などの各種アク
リル酸あるいはメタクリル酸エステルの共重合体などで
ある。The polymer obtained in the present invention is used for general molding materials such as GP type polystyrene, high impact polystyrene, expanded polystyrene, polymethyl methacrylate, styrene / acrylonitrile copolymer, styrene / acrylonitrile /
Phenylmaleimide copolymer, butyl methacrylate / 2-
Various acrylic acid or methacrylic acid ester copolymers such as an ethylhexyl methacrylate copolymer and the like.
本発明の熱による架橋剤に使用される、架橋されるポ
リマーとしては、例えばポリエチレン、エチレンプロピ
レンコポリマー（EPM）、エチレンプロピレンジエンコ
ポリマー（EPDM）、エチレン酢酸ビニルコポリマー（EV
A）、テトラフルオロエチレンビニリデンフルオライド
ヘキサフルオロプロピレン三元コポリマー、クロルスル
ホン化ポリエチレン、塩素化ポリエチレン、ポリブテン
−１、ポリイソブテン、エチレンビニルアセテートコポ
リマー、ポリブタジエン、ポリイソプレン、ポリクロロ
プレン、ブタジエンスチレンコポリマー、天然ゴム、ポ
リアクリレートゴム、ブタジエンアクリロニトリルコポ
リマー、アクリロニトリルブタジエンスチレン三元コポ
リマー、シリコーンゴム、ポリウレタン、ポリスルフィ
ドが挙げられる。Examples of the polymer to be crosslinked used in the heat crosslinking agent of the present invention include polyethylene, ethylene propylene copolymer (EPM), ethylene propylene diene copolymer (EPDM), and ethylene vinyl acetate copolymer (EV).
A), terpolymer of tetrafluoroethylene vinylidene fluoride hexafluoropropylene, chlorosulfonated polyethylene, chlorinated polyethylene, polybutene-1, polyisobutene, ethylene vinyl acetate copolymer, polybutadiene, polyisoprene, polychloroprene, butadiene styrene copolymer, natural rubber Polyacrylate rubber, butadiene acrylonitrile copolymer, acrylonitrile butadiene styrene ternary copolymer, silicone rubber, polyurethane, and polysulfide.
架橋されるべきポリマーに対して本過酸化物は一般に
0.1〜10重量％、好ましくは１〜３重量％の範囲で加え
られる。The peroxide is generally used for the polymer to be crosslinked.
It is added in the range of 0.1 to 10% by weight, preferably 1 to 3% by weight.
また架橋されるべきポリマーに架橋プロセスに一般に
用いられる種々の添加剤、例えば架橋助剤、酸化防止
剤、顔料、紫外線安定剤、充填剤、可塑剤などを加える
ことができる。Various additives commonly used in the crosslinking process, such as crosslinking aids, antioxidants, pigments, UV stabilizers, fillers, plasticizers, etc., can be added to the polymer to be crosslinked.
本発明においてポリマーと有機過酸化物を混合する温
度は一般に25〜130℃が用いられる。続く架橋の温度は
一般に110〜220℃、好ましくは150〜190℃が用いられ
る。In the present invention, the temperature for mixing the polymer and the organic peroxide is generally from 25 to 130 ° C. The temperature of the subsequent crosslinking is generally from 110 to 220 ° C, preferably from 150 to 190 ° C.
（発明の効果） 本発明のベンゾフェノン基含有ジアルキルペルオキシ
ドは、従来の光重合開始剤に比べて次の特徴を持ってい
る。(Effect of the Invention) The dialkyl peroxide containing a benzophenone group of the present invention has the following characteristics as compared with the conventional photopolymerization initiator.
（１）本発明のベンゾフェノン基含有ジアルキルペルオ
キシドは、同一分子内に光吸収基とラジカル発生源を持
つため、光の照射により、効率よくラジカルを発生させ
ることができる。従って、光重合、光硬化速度が速い。(1) Since the benzophenone group-containing dialkyl peroxide of the present invention has a light absorbing group and a radical generation source in the same molecule, radicals can be efficiently generated by light irradiation. Therefore, the speed of photopolymerization and photocuring is high.
（２）本発明のベンゾフェノン基含有ジアルキルペルオ
キシドは、ジアルキル型の過酸化物であるので、熱安定
性が良く、従って、これを含む光重合組成物は、重合お
よびゲル化することなく長期間保存できる。(2) Since the benzophenone group-containing dialkyl peroxide of the present invention is a dialkyl peroxide, it has good thermal stability, and therefore, the photopolymerizable composition containing it can be stored for a long period without polymerization and gelation. it can.
（３）本発明のベンゾフェノン基含有ジアルキルペルオ
キシドを光重合開始剤、光硬化剤、光架橋剤として用い
て得られた重合体は黄変しない。(3) A polymer obtained by using the benzophenone group-containing dialkyl peroxide of the present invention as a photopolymerization initiator, a photocuring agent, or a photocrosslinking agent does not turn yellow.
（４）本発明のベンゾフェノン基含有ジアルキルペルオ
キシドは過酸化物であるため、光硬化による硬化が不十
分な場合、熱硬化によるアフターキュアが可能である。(4) Since the benzophenone group-containing dialkyl peroxide of the present invention is a peroxide, if curing by light curing is insufficient, after-curing by thermal curing is possible.
（５）本発明のベンゾフェノン基含有ジアルキルペルオ
キシドは、熱による重合開始剤、架橋剤としても有効で
ある。(5) The benzophenone group-containing dialkyl peroxide of the present invention is also effective as a thermal polymerization initiator and a crosslinking agent.
以上のように、本発明のベンゾフェノン基含有ジアル
キルペルオキシドは光重合、硬化、架橋剤、および、熱
重合、架橋剤として優れた特徴を持つ新規な化合物であ
り、工業的価値は極めて高い。As described above, the benzophenone group-containing dialkyl peroxide of the present invention is a novel compound having excellent characteristics as a photopolymerization, curing, crosslinking agent, thermal polymerization, and crosslinking agent, and has extremely high industrial value.
（実施例） 次に、実施例により、本発明を具体的に説明するが、
本発明はこれにより限定されるものではない。(Examples) Next, the present invention will be described specifically with reference to Examples.
The present invention is not limited by this.
実施例１ 攪拌装置及び温度計を備えた200mlの四つ口フラスコ
に４−イソプロピルベンゾフェノン〔これは、クメンと
ベンゾイルクロリドから得られる〕11.2g（0.05モ
ル）、ｔ−ブチルヒドロペルオキシド13.5g（0.15モ
ル）、塩化第一銅0.05gおよびベンゼン50mlの懸濁液
を、窒素雰囲気下、70℃で25時間攪拌を続け、次いで10
％塩酸、10％水酸化ナトリウム水溶液、水で順次洗浄
し、硫酸マグネシウムで乾燥、溶媒留去後、メタノール
中結晶化、またはカラムクロマトグラフィーにより白色
固体7.8gを得た。この化合物について、赤外線吸収スペ
クトル、核磁気共鳴スペクトル、紫外線吸収スペクト
ル、マススペクトル、元素分析、および、融点の測定を
行った結果、下記のとおりであり、この化合物が４−
（１−ｔ−ブチルペルオキシ−１−メチルエチル）ベン
ゾフェノンであることを確認した。Example 1 In a 200 ml four-necked flask equipped with a stirrer and a thermometer, 11.2 g (0.05 mol) of 4-isopropylbenzophenone [obtained from cumene and benzoyl chloride], 13.5 g of t-butyl hydroperoxide (0.15 g) Mol), 0.05 g of cuprous chloride and 50 ml of benzene were stirred at 70 ° C. for 25 hours under a nitrogen atmosphere, and then stirred for 10 hours.
The mixture was washed successively with a 10% aqueous solution of hydrochloric acid, a 10% aqueous solution of sodium hydroxide and water, dried over magnesium sulfate, evaporated, and then crystallized in methanol or column chromatography to obtain 7.8 g of a white solid. This compound was subjected to an infrared absorption spectrum, a nuclear magnetic resonance spectrum, an ultraviolet absorption spectrum, a mass spectrum, an elemental analysis, and a measurement of a melting point, and as a result, the following results were obtained.
It was confirmed to be (1-t-butylperoxy-1-methylethyl) benzophenone.
赤外線吸収スペクトル 870cm-1（Ｏ−Ｏ結合） 1660cm-1（Ｃ−Ｏ結合） 核磁気共鳴スペクトル（δ） 1.27ppm（9H） 1.62ppm（6H） 7.4〜8.2ppm（9H） 紫外線吸収スペクトル（ジオキサン中） 342nm（ε 160） 256nm（ε 18800） マススペクトル 312m/e（分子イオンピーク） 元素分析 C;76.83％（計算値76.89％） H; 7.7％ （計算値 7.74％） 融点 48〜49℃ 実施例２〜５ ｔ−ブチルヒドロペルオキシドの代わりに、それぞれ
ｔ−アミルヒドロペルオキシド、ｔ−ヘキシルヒドロペ
ルオキシド、ｔ−オクチルヒドロペルオキシド、クメン
ヒドロペルオキシドを用いて実施例１に述べた製造方法
に準じた方法で操作して、粘性の液体を得た。これらの
化合物についてそれぞれ実施例１と同様に各分析を行っ
た結果、これらの化合物が目的のペルオキシドであるこ
とを確認した。得られた化合物および各分析の結果を第
１表にまとめて示す。 Infrared absorption spectrum 870 cm -1 (O-O bond) 1660 cm -1 (C-O bond) Nuclear magnetic resonance spectrum (δ) 1.27ppm (9H) 1.62ppm (6H) 7.4~8.2ppm (9H) ultraviolet absorption spectrum (in dioxane Medium) 342 nm (ε 160) 256 nm (ε 18800) Mass spectrum 312 m / e (molecular ion peak) Elemental analysis C; 76.83% (calculated value 76.89%) H; 7.7% (calculated value 7.74%) Melting point 48-49 ° C Examples 2 to 5 The method according to the production method described in Example 1 using t-amyl hydroperoxide, t-hexyl hydroperoxide, t-octyl hydroperoxide and cumene hydroperoxide instead of t-butyl hydroperoxide, respectively. To obtain a viscous liquid. Each of these compounds was analyzed in the same manner as in Example 1, and as a result, it was confirmed that these compounds were the target peroxides. Table 1 summarizes the obtained compounds and the results of each analysis.
実施例６〜９ ４−イソプロピルベンゾフェノンの代わりに、種々の
置換基の付いた４−イソプロピルベンゾフェノンを用い
る以外は、実施例１に述べた製造方法に準じた方法で操
作して、得られた化合物についてそれぞれ実施例１と同
様に各分析を行った結果、これらの化合物が目的のペル
オキシドであることを確認した。得られた化合物および
各分析の結果を第２表にまとめて示す。 Examples 6 to 9 Compounds obtained by operating according to the production method described in Example 1 except that 4-isopropylbenzophenone having various substituents is used instead of 4-isopropylbenzophenone. Was analyzed in the same manner as in Example 1, and as a result, it was confirmed that these compounds were the target peroxides. Table 2 summarizes the obtained compounds and the results of each analysis.
実施例10〜14 ４−イソプロピルベンゾフェノンの代わりに種々の置
換基を持つ３−イソプロピルベンゾフェノンを用いる以
外は、実施例１に述べた製造方法に準じた方法で操作し
て、得られた化合物についてそれぞれ実施例１と同様に
各分析を行った結果、これらの化合物が目的のペルオキ
シドであることを確認した。得られた化合物および各分
析の結果を第３表にまとめて示す。Examples 10 to 14 Except that 4-isopropylbenzophenone having various substituents was used in place of 4-isopropylbenzophenone, the same procedure as in Example 1 was repeated to obtain a compound. As a result of performing each analysis in the same manner as in Example 1, it was confirmed that these compounds were the target peroxides. Table 3 summarizes the obtained compounds and the results of each analysis.
実施例15 攪拌装置及び温度計を備えた100mlの四つ口フラスコ
に４−（α−ヒドロキシイソプロピル）ベンゾフェノン
12.0g（0.05モル）、ｔ−ブチルヒドロペルオキシド5.0
g（0.055モル）、硫酸マグネシウム2.0gの懸濁液中に１
％過塩素酸の酢酸溶液5.0g（0.0005モル）を、25℃以下
に保ちながら滴下し、40℃に昇温後２時間攪拌を続け
た。冷却後、５％水酸化ナトリウム水溶液、次いで水で
洗浄し、無水硫酸マグネシウムで乾燥、溶媒留去後、メ
タノール中結晶化、またはカラムクロマトグラフィーに
より白色固体11.8gを得た。この化合物について、赤外
線吸収スペクトル、核磁気共鳴スペクトル、紫外線吸収
スペクトル、マススペクトル、元素分析、および、融点
の測定を行った結果、この化合物が４−（１−ｔ−ブチ
ルペルオキシ−１−メチルエチル）ベンゾフェノンであ
ることを確認した。 Example 15 4- (α-hydroxyisopropyl) benzophenone was placed in a 100 ml four-necked flask equipped with a stirrer and a thermometer.
12.0 g (0.05 mol), t-butyl hydroperoxide 5.0
g (0.055 mol) in a suspension of 2.0 g of magnesium sulfate.
5.0 g (0.0005 mol) of a acetic acid solution of 25% perchloric acid was added dropwise while maintaining the temperature at 25 ° C. or lower, and after the temperature was raised to 40 ° C., stirring was continued for 2 hours. After cooling, the mixture was washed with a 5% aqueous sodium hydroxide solution and then with water, dried over anhydrous magnesium sulfate, and after distilling off the solvent, 11.8 g of a white solid was obtained by crystallization in methanol or column chromatography. This compound was subjected to an infrared absorption spectrum, a nuclear magnetic resonance spectrum, an ultraviolet absorption spectrum, a mass spectrum, an elemental analysis, and a measurement of a melting point. As a result, the compound was found to be 4- (1-t-butylperoxy-1-methylethyl). ) It was confirmed to be benzophenone.
実施例16 攪拌装置及び温度計を備えた100mlの四つ口フラスコ
に４−イソプロペニルベンゾフェノン11.1g（0.05モ
ル）のイソプロピルアルコール溶液中に、濃塩酸1.0g
（0.01モル）、次いでｔ−ブチルヒドロペルオキシド5.
0g（0.055モル）を、25℃以下に保ちながら滴下し、40
℃に昇温後２時間攪拌を続けた。冷却後、５％水酸化ナ
トリウム水溶液、次いで水で洗浄し、硫酸マグネシウム
で乾燥、溶媒留去後、メタノール中結晶化、またはカラ
ムクロマトグラフィーにより白色固体10.7gを得た。こ
の化合物について、赤外線吸収スペクトル、核磁気共鳴
スペクトル、紫外線吸収スペクトル、マススペクトル、
元素分析、および、融点の測定を行った結果、この化合
物が４−（１−ｔ−ブチルペルオキシ１−メチルエチ
ル）ベンゾフェノンであることを確認した。Example 16 In a 100 ml four-necked flask equipped with a stirrer and a thermometer, a solution of 11.1 g (0.05 mol) of 4-isopropenylbenzophenone in isopropyl alcohol was mixed with 1.0 g of concentrated hydrochloric acid.
(0.01 mol), followed by t-butyl hydroperoxide 5.
0 g (0.055 mol) was added dropwise while maintaining the temperature below 25 ° C.
After the temperature was raised to 0 ° C, stirring was continued for 2 hours. After cooling, the mixture was washed with a 5% aqueous sodium hydroxide solution and then with water, dried over magnesium sulfate, and after evaporating the solvent, crystallization in methanol or column chromatography to give 10.7 g of a white solid. For this compound, infrared absorption spectrum, nuclear magnetic resonance spectrum, ultraviolet absorption spectrum, mass spectrum,
Elemental analysis and measurement of the melting point confirmed that this compound was 4- (1-t-butylperoxy 1-methylethyl) benzophenone.
実施例17 攪拌装置及び温度計を備えた200mlの四つ口フラスコ
に40％水酸化ナトリウム水溶液12.5g（0.125モル）とベ
ンゼン25g、ジオキサン75gをいれて攪拌し、氷冷して３
〜６℃に保ちながら、ｔ−ブチルヒドロペルオキシド1
1.3g（0.125モル）および４−（α−クロロイソプロピ
ル）ベンゾフェノン25.9g（0.10モル）を加えた。その
後５℃で４〜５時間反応を継続した。この反応混合物か
ら有機層を取り出し、10％水酸化ナトリウムで２回、次
いで飽和食塩水で２から３回洗浄した後、無水硫酸マグ
ネシウムで乾燥、溶媒留去後、メタノール中結晶化、ま
たはカラムクロマトグラフィーにより白色固体22.1gを
得た。この化合物について、赤外線吸収スペクトル、核
磁気共鳴スペクトル、紫外線吸収スペクトル、マススペ
クトル、元素分析、および、融点の測定を行った結果、
この化合物が４−（１−ｔ−ブチルペルオキシ−１−メ
チルエチル）ベンゾフェノンであることを確認した。Example 17 12.5 g (0.125 mol) of a 40% aqueous sodium hydroxide solution, 25 g of benzene and 75 g of dioxane were placed in a 200 ml four-necked flask equipped with a stirrer and a thermometer, and the mixture was stirred.
While maintaining the temperature at -6 ° C, t-butyl hydroperoxide 1
1.3 g (0.125 mol) and 25.9 g (0.10 mol) of 4- (α-chloroisopropyl) benzophenone were added. Thereafter, the reaction was continued at 5 ° C for 4 to 5 hours. The organic layer was taken out of the reaction mixture, washed twice with 10% sodium hydroxide, then twice or three times with a saturated saline solution, dried over anhydrous magnesium sulfate, distilled off the solvent, and then crystallized in methanol or subjected to column chromatography. Chromatography gave 22.1 g of a white solid. For this compound, the results of infrared absorption spectrum, nuclear magnetic resonance spectrum, ultraviolet absorption spectrum, mass spectrum, elemental analysis, and measurement of melting point,
This compound was confirmed to be 4- (1-t-butylperoxy-1-methylethyl) benzophenone.
実施例18 ４−（α−ヒドロキシイソプロピル）ベンゾフェノン
およびｔ−ブチルヒドロペルオキシドの代わりに、ｔ−
ブチルアルコールおよび４−（α−ヒドロペルオキシイ
ソプロピル）ベンゾフェノンを用いる以外は、実施例15
に述べた製造方法に準じた方法で操作して、得られた化
合物についてそれぞれ実施例15と同様に各分析を行った
結果、これらの化合物が４−（１−ｔ−ブチルペルオキ
シド−１−メチルエチル）ベンゾフェノンであることを
確認した。Example 18 Instead of 4- (α-hydroxyisopropyl) benzophenone and t-butyl hydroperoxide, t-
Example 15 except that butyl alcohol and 4- (α-hydroperoxyisopropyl) benzophenone were used.
Each compound was analyzed in the same manner as in Example 15 by operating according to the production method described in Example 1. As a result, these compounds were found to be 4- (1-t-butyl peroxide-1-methyl). (Ethyl) benzophenone.
実施例19 ４−イソプロペニルベンゾフェノンおよびｔ−ブチル
ヒドロペルオキシドの代わりに、２−メチル−１−ペン
テンおよび４−（α−ヒドロペルオキシイソプロピル）
ベンゾフェノンを用いる以外は、実施例16に述べた製造
方法に準じた方法で操作して、得られた化合物について
それぞれ実施例16と同様に各分析を行った結果、これら
の化合物が４−（１−ｔ−ヘキシルペルオキシ−１−メ
チルエチル）ベンゾフェノンであることを確認した。Example 19 Instead of 4-isopropenylbenzophenone and t-butyl hydroperoxide, 2-methyl-1-pentene and 4- (α-hydroperoxyisopropyl)
Except for using benzophenone, the same procedure as in Example 16 was performed for each of the obtained compounds by operating according to the production method described in Example 16, and as a result, these compounds were found to be 4- (1 -T-hexylperoxy-1-methylethyl) benzophenone.
実施例20 ４−（α−クロロイソプロピル）ベンゾフェノンおよ
びｔ−ブチルヒドロペルオキシドの代わりに、塩化ｔ−
ブチルおよび４−（α−ヒドロペルオキシイソプロピ
ル）ベンゾフェノンを用いる以外は、実施例17に述べた
製造方法に準じた方法で操作して、得られた化合物につ
いてそれぞれ実施例17と同様に各分析を行った結果、こ
れらの化合物が４−（１−ｔ−ヘキシルペルオキシ−１
−メチルエチル）ベンゾフェノンであることを確認し
た。Example 20 Instead of 4- (α-chloroisopropyl) benzophenone and t-butyl hydroperoxide, t-chloride
Except for using butyl and 4- (α-hydroperoxyisopropyl) benzophenone, the same procedure as in Example 17 was carried out for each of the obtained compounds by operating according to the production method described in Example 17. As a result, these compounds were converted to 4- (1-t-hexylperoxy-1).
-Methylethyl) benzophenone.
実施例21〜25 石英製光重合管に、重合禁止剤を含まないメタクリル
酸メチルに本発明の光重合開始剤をそれぞれ0.01mol/
添加し、凍結融解法で窒素置換した後、20℃の恒温槽で
メリーゴーランド型光照射装置（大科工業社製、商品名
MGR−Ｐ型）を用い、400W高圧水銀灯（UTV36Aフィルタ
ー使用）で365nmの紫外線を8cmの距離から30分照射した
後、メタノール沈降法による重量法で重合転化率および
重合速度（Rp）を測定した。得られた結果を第４表に示
す。Examples 21 to 25 Photopolymerization tube made of quartz, the photopolymerization initiator of the present invention in methyl methacrylate containing no polymerization inhibitor 0.01 mol / each
After adding and purging with nitrogen by freeze-thaw method, a merry-go-round type light irradiator (trade name, manufactured by Daika Kogyo Co., Ltd.)
(MGR-P type), using a 400 W high-pressure mercury lamp (using a UTV36A filter), irradiating ultraviolet rays of 365 nm from a distance of 8 cm for 30 minutes, and then measuring the polymerization conversion rate and polymerization rate (Rp) by a gravimetric method by a methanol precipitation method. . Table 4 shows the obtained results.
比較例１ 本発明の光重合開始剤に変え、第４表に示される従来
の光重合開始剤を用いた以外は、実施例21に準じてメタ
クリル酸メチルを重合し、重合転化率、および重合速度
を測定した。その結果を第４表に示す。Comparative Example 1 Methyl methacrylate was polymerized in the same manner as in Example 21 except that the conventional photopolymerization initiator shown in Table 4 was used instead of the photopolymerization initiator of the present invention. The speed was measured. Table 4 shows the results.
第４表の結果は、本発明の化合物が有効な光重合性能
を持っていることを示している。 The results in Table 4 show that the compounds of the present invention have effective photopolymerization performance.
実施例26 メタクリル酸メチルに本発明の４−（１−ｔ−ブチル
ペルオキシ−１−メチルエチル）ベンゾフェノンを0.01
mol/添加し、実施例21と同じ装置を使い、同じ操作
で、光照射時間を変えて重合させ、重合転化率を測定し
た。得られた照射時間と重合転化率の関係を第１図に示
す。Example 26 0.01% of 4- (1-tert-butylperoxy-1-methylethyl) benzophenone of the present invention was added to methyl methacrylate.
mol / addition, and polymerization was carried out using the same apparatus as in Example 21 with the same operation while changing the light irradiation time, and the polymerization conversion was measured. FIG. 1 shows the relationship between the obtained irradiation time and the polymerization conversion.
比較例２ 本発明の光重合開始剤に変え、第４表に示された従来
の光重合開始剤を用いた以外は、実施例26に準じてメタ
クリル酸メチルを重合し、得られた照射時間と重合転化
率との関係を第１図に示す。Comparative Example 2 The irradiation time was obtained by polymerizing methyl methacrylate according to Example 26, except that the conventional photopolymerization initiator shown in Table 4 was used instead of the photopolymerization initiator of the present invention. FIG. 1 shows the relationship between the polymerization rate and the polymerization conversion.
第１図から、本発明の光重合開始剤を用いると、重合
活性が大きいことがわかる。FIG. 1 shows that the use of the photopolymerization initiator of the present invention has a large polymerization activity.
実施例27 ガラスプレート上に、本発明の４−（１−ｔ−ブチル
ペルオキシ−１−メチルエチル）ベンゾフェノンを２重
量部添加したエステルアクリレート樹脂〔組成は「アロ
ニックスＭ−8060」（東亜合成社製品名）／「アロニッ
クスＭ−5700」（東亜合成社製品名＝4/6〕を、100μｍ
の膜厚に塗布し、コンベア式紫外線硬化装置（集光型）
を用いて樹脂を硬化させた。この樹脂の、目視での黄変
はなかった。Example 27 An ester acrylate resin obtained by adding 2 parts by weight of 4- (1-t-butylperoxy-1-methylethyl) benzophenone of the present invention on a glass plate [composition is "Aronix M-8060" (product of Toa Gosei Co., Ltd.) Name) / “Aronix M-5700” (Toa Gosei Co., Ltd. product name = 4/6)
Conveyor type UV curing device (light collecting type)
Was used to cure the resin. There was no visual yellowing of this resin.
比較例３ ４−（１−ｔ−ブチルペルオキシ−１−メチルエチ
ル）ベンゾフェノンの代わりに、1,2−ジフェニル−2,2
−ジメトキシエタン−１−オンを用いる以外は実施例27
に準じてエステルアクリレート樹脂で硬化させた。この
樹脂は、黄変していた。Comparative Example 3 Instead of 4- (1-t-butylperoxy-1-methylethyl) benzophenone, 1,2-diphenyl-2,2
Example 27 except for using -dimethoxyethane-1-one
Cured with an ester acrylate resin according to The resin had turned yellow.
実施例28〜32 ガラスびん中に、本発明の光重合開始剤をそれぞれ２
重量部添加したエステルアクリレート樹脂〔組成は、実
施例27で用いた樹脂と同じ〕を入れ、インキュベーター
内、60℃で暗所保存安定性を調べた。結果は、目視でゲ
ル化の生じた日数で表した。得られた暗所保存安定性を
第５表に示す。Examples 28 to 32 In a glass bottle, 2 parts of the photopolymerization initiator of the present invention was added.
Ester acrylate resin (the composition is the same as that used in Example 27) added by weight was added, and the storage stability in a dark place at 60 ° C. in an incubator was examined. The results were visually expressed as the number of days when gelation occurred. Table 5 shows the obtained storage stability in a dark place.
比較例４〜６ 本発明の光重合開始剤に変えて、第５表に示される従
来の光重合開始剤を用いる以外は、実施例28に準じて暗
所保存安定性を測定した。得られた結果を第５表に示
す。Comparative Examples 4 to 6 The storage stability in a dark place was measured according to Example 28 except that the conventional photopolymerization initiator shown in Table 5 was used instead of the photopolymerization initiator of the present invention. Table 5 shows the obtained results.
実施例33 容量20mlのガラス製アンプル管に本発明の４−（ｔ−
ブチルペルオキシ−１−メチルエチル）ベンゾフェノン
0.005mol/を添加したスチレン10gを入れ、真空脱気
後、封管した。このアンプル管を120℃の恒温油浴槽中
で所定時間重合させた。重合物をそれぞれメタノールに
投入し、再沈澱を行い、得られた白色粉体の重量より重
合転化率を計算した。また、ゲルパーミエーションクロ
マトグラフィー（GPC）により、重合平均分子量（Mw）
を測定した。結果を第６表に示す。 Example 33 A 20-ml glass ampule tube of the present invention was prepared using 4- (t-
Butyl peroxy-1-methylethyl) benzophenone
10 g of styrene to which 0.005 mol / was added was added, and after degassing under vacuum, the tube was sealed. The ampoule was polymerized in a constant temperature oil bath at 120 ° C. for a predetermined time. Each polymer was put into methanol and reprecipitated, and the polymerization conversion was calculated from the weight of the obtained white powder. The average molecular weight (Mw) was determined by gel permeation chromatography (GPC).
Was measured. The results are shown in Table 6.
比較例７ ４−（ｔ−ブチルペルオキシ−１−メチルエチル）ベ
ンゾフェノンの代わりにｔ−ブチルクミルペルオキシド
0.005mol/を添加したスチレン10gを用いる以外は実施
例33に記載した方法に準じて重合を行い、結果を第６表
に示す。Comparative Example 7 t-butylcumyl peroxide in place of 4- (t-butylperoxy-1-methylethyl) benzophenone
Polymerization was carried out according to the method described in Example 33 except that 10 g of styrene added with 0.005 mol / was used. The results are shown in Table 6.
第６表より本発明の化合物が熱による重合開始剤とし
て有効な性能を有することがわかる。 Table 6 shows that the compound of the present invention has an effective performance as a polymerization initiator by heat.
実施例34 容量75のヘンシエルミキサー（攪拌翼：標準型）に
見かけ比重0.45、粒径ASTM30メッシュ99.5％パス、MI3
0.5、密度0.956の粉末状ポリエチレン20kgと４−（ｔ−
ブチルペルオキシ−１−メチルエチル）ベンゾフェノン
0.2kgを同時に投入し、約750rpmで２分、1500rpmで８分
間混合した。Example 34 Appearance specific gravity 0.45, particle size ASTM30 mesh 99.5% pass, MI3 with a Hensiel mixer (stirring blade: standard type) having a capacity of 75
0.5 kg of powdered polyethylene having a density of 0.956 and 20 kg of 4- (t-
Butyl peroxy-1-methylethyl) benzophenone
0.2 kg was simultaneously charged and mixed at about 750 rpm for 2 minutes and at 1500 rpm for 8 minutes.
得られた混合物を用いて鋳造金型を用い、２軸回転成
形法により製品を得た。得られた製品の外観および機械
物性は第７表のとおりであった。A product was obtained by a biaxial rotation molding method using a casting mold using the obtained mixture. The appearance and mechanical properties of the obtained product were as shown in Table 7.
比較例８ ４−（ｔ−ブチルペルオキシ−１−メチルエチル）ベ
ンゾフェノンの代わりにジクミルペルオキシドを用いる
以外は実施例34に記載した方法に準じて操作し、結果を
第７表に示す。Comparative Example 8 The procedure of Example 34 was repeated, except that dicumyl peroxide was used instead of 4- (t-butylperoxy-1-methylethyl) benzophenone. The results are shown in Table 7.
第１図は、本発明における実施例26および比較例２にお
ける光重合開始剤の照射時間と重合転化率との関係を示
す線図である。FIG. 1 is a graph showing the relationship between the irradiation time of a photopolymerization initiator and the polymerization conversion rate in Example 26 and Comparative Example 2 in the present invention.
Claims (3)
−クミル基、R2,R3は炭素数１〜２のアルキル基、R4は
炭素数１〜３のアルキル基、水素原子の中から選ばれ、
R5は炭素数１〜12のアルキル基、炭素数１〜４のアルコ
キシ基、ハロゲン原子、水素原子の中から選ばれ、ｍは
１〜３、ｎは１〜２を表す。また、R1OOC（R2）（R3）
基は、メタ、またはパラ位である。） で示されるベンゾフェノン基含有ジアルキルペルオキシ
ド。(1) General formula (Wherein, R 1 is a tertiary alkyl group having 4 to 8 carbon atoms, or α
-Cumyl group, R 2 , R 3 is an alkyl group having 1 to 2 carbon atoms, R 4 is an alkyl group having 1 to 3 carbon atoms, selected from hydrogen atoms,
R 5 is selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom and a hydrogen atom, m represents 1 to 3, and n represents 1 to 2. Also, R 1 OOC (R 2 ) (R 3 )
The groups are in the meta or para position. A benzophenone group-containing dialkyl peroxide represented by the formula:
−クミル基、R2,R3は炭素数１〜２のアルキル基、R4は
炭素数１〜３のアルキル基、水素原子の中から選ばれ、
R5は炭素数１〜12のアルキル基、炭素数１〜４のアルコ
キシ基、ハロゲン原子、水素原子の中から選ばれ、ｍは
１〜３、ｎは１〜２を表す。また、R1OOC（R2）（R3）
基は、メタ、またはパラ位である。） で示されるベンゾフェノン基含有ジアルキルペルオキシ
ドを有効成分とする光分解型ラジカル発生剤。2. The general formula (Wherein, R 1 is a tertiary alkyl group having 4 to 8 carbon atoms, or α
-Cumyl group, R 2 , R 3 is an alkyl group having 1 to 2 carbon atoms, R 4 is an alkyl group having 1 to 3 carbon atoms, selected from hydrogen atoms,
R 5 is selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom and a hydrogen atom, m represents 1 to 3, and n represents 1 to 2. Also, R 1 OOC (R 2 ) (R 3 )
The groups are in the meta or para position. A photolytic radical generator comprising a benzophenone group-containing dialkyl peroxide represented by the formula (1) as an active ingredient.
−クミル基、R2,R3は炭素数１〜２のアルキル基、R4は
炭素数１〜３のアルキル基、水素原子の中から選ばれ、
R5は炭素数１〜12のアルキル基、炭素数１〜４のアルコ
キシ基、ハロゲン原子、水素原子の中から選ばれ、ｍは
１〜３、ｎは１〜２を表す。また、R1OOC（R2）（R3）
基は、メタ、またはパラ位である。） で示されるベンゾフェノン基含有ジアルキルペルオキシ
ドを有効成分とする光分解型ラジカル発生剤。3. The general formula (Wherein, R 1 is a tertiary alkyl group having 4 to 8 carbon atoms, or α
-Cumyl group, R 2 , R 3 is an alkyl group having 1 to 2 carbon atoms, R 4 is an alkyl group having 1 to 3 carbon atoms, selected from hydrogen atoms,
R 5 is selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom and a hydrogen atom, m represents 1 to 3, and n represents 1 to 2. Also, R 1 OOC (R 2 ) (R 3 )
The groups are in the meta or para position. A photolytic radical generator comprising a benzophenone group-containing dialkyl peroxide represented by the formula (1) as an active ingredient.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1184498A JP2734101B2 (en) | 1989-07-19 | 1989-07-19 | Dialkyl peroxides and their uses |
| US07/550,901 US5091586A (en) | 1989-07-19 | 1990-07-11 | Novel dialkyl peroxides, production method and use thereof |
| EP90307737A EP0409520B1 (en) | 1989-07-19 | 1990-07-16 | Novel dialkyl peroxides, production method and use thereof |
| DE69012472T DE69012472T2 (en) | 1989-07-19 | 1990-07-16 | Dialkyl peroxides, process for their preparation and their use. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1184498A JP2734101B2 (en) | 1989-07-19 | 1989-07-19 | Dialkyl peroxides and their uses |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0352856A JPH0352856A (en) | 1991-03-07 |
| JP2734101B2 true JP2734101B2 (en) | 1998-03-30 |
Family
ID=16154241
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1184498A Expired - Fee Related JP2734101B2 (en) | 1989-07-19 | 1989-07-19 | Dialkyl peroxides and their uses |
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| Country | Link |
|---|---|
| JP (1) | JP2734101B2 (en) |
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| US8581094B2 (en) | 2006-09-20 | 2013-11-12 | Dow Global Technologies, Llc | Electronic device module comprising polyolefin copolymer |
| US20080115825A1 (en) | 2006-09-20 | 2008-05-22 | Patel Rajen M | Electronic Device Module Comprising an Ethylene Multi-Block Copolymer |
| WO2020067118A1 (en) * | 2018-09-26 | 2020-04-02 | 日油株式会社 | Dialkyl peroxide including thioxanthone skeleton and polymerizable composition containing said compound |
| JP7354891B2 (en) * | 2020-03-19 | 2023-10-03 | 日油株式会社 | light curing ink |
| JP7694115B2 (en) * | 2021-03-31 | 2025-06-18 | 日油株式会社 | Thermally conductive composition and thermally conductive sheet |
| CN118215691A (en) * | 2022-03-28 | 2024-06-18 | 日油株式会社 | Polymerization initiator, polymerizable composition and cured product, and hydroperoxide having thioxanthone skeleton |
-
1989
- 1989-07-19 JP JP1184498A patent/JP2734101B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0352856A (en) | 1991-03-07 |
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