WO2017209004A1 - 高屈折率重合性化合物の低粘度化剤及びそれを含む重合性組成物 - Google Patents
高屈折率重合性化合物の低粘度化剤及びそれを含む重合性組成物 Download PDFInfo
- Publication number
- WO2017209004A1 WO2017209004A1 PCT/JP2017/019752 JP2017019752W WO2017209004A1 WO 2017209004 A1 WO2017209004 A1 WO 2017209004A1 JP 2017019752 W JP2017019752 W JP 2017019752W WO 2017209004 A1 WO2017209004 A1 WO 2017209004A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- compound
- polymerizable
- formula
- refractive index
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 131
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- -1 polysiloxane Polymers 0.000 claims description 123
- 125000004432 carbon atom Chemical group C* 0.000 claims description 55
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 48
- 150000002430 hydrocarbons Chemical group 0.000 claims description 46
- 125000000217 alkyl group Chemical group 0.000 claims description 44
- 238000004519 manufacturing process Methods 0.000 claims description 30
- 239000003638 chemical reducing agent Substances 0.000 claims description 29
- 125000003118 aryl group Chemical group 0.000 claims description 28
- 125000001424 substituent group Chemical group 0.000 claims description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 22
- 229940126062 Compound A Drugs 0.000 claims description 21
- 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 claims description 21
- 239000003085 diluting agent Substances 0.000 claims description 21
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 125000005561 phenanthryl group Chemical group 0.000 claims description 13
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 12
- 125000001624 naphthyl group Chemical group 0.000 claims description 11
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000006267 biphenyl group Chemical group 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000005336 allyloxy group Chemical group 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 42
- 239000000047 product Substances 0.000 description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 21
- 230000003287 optical effect Effects 0.000 description 19
- 239000002904 solvent Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 15
- 239000003729 cation exchange resin Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000007818 Grignard reagent Substances 0.000 description 12
- 150000004795 grignard reagents Chemical class 0.000 description 12
- 238000006068 polycondensation reaction Methods 0.000 description 12
- 239000003505 polymerization initiator Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 8
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 8
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- VSYZNIXNUZCUOX-UHFFFAOYSA-N (4-ethenylphenyl)-dimethoxy-phenanthren-9-ylsilane Chemical compound CO[Si](C1=CC=C(C=C1)C=C)(C=1C2=CC=CC=C2C=2C=CC=CC=2C=1)OC VSYZNIXNUZCUOX-UHFFFAOYSA-N 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 5
- 239000002198 insoluble material Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- QTPLEVOKSWEYAC-UHFFFAOYSA-N 1,2-diphenyl-9h-fluorene Chemical compound C=1C=CC=CC=1C1=C2CC3=CC=CC=C3C2=CC=C1C1=CC=CC=C1 QTPLEVOKSWEYAC-UHFFFAOYSA-N 0.000 description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 4
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical compound C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 4
- PUFWGUZSDHANBX-UHFFFAOYSA-N 1-phenyl-9h-fluorene Chemical compound C=12CC3=CC=CC=C3C2=CC=CC=1C1=CC=CC=C1 PUFWGUZSDHANBX-UHFFFAOYSA-N 0.000 description 4
- IYDMICQAKLQHLA-UHFFFAOYSA-N 1-phenylnaphthalene Chemical compound C1=CC=CC=C1C1=CC=CC2=CC=CC=C12 IYDMICQAKLQHLA-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 4
- 229920001429 chelating resin Polymers 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 125000003010 ionic group Chemical group 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 4
- 238000012719 thermal polymerization Methods 0.000 description 4
- BHZKBFGLZZRETK-UHFFFAOYSA-N trimethoxy(phenanthren-9-yl)silane Chemical compound C1=CC=C2C([Si](OC)(OC)OC)=CC3=CC=CC=C3C2=C1 BHZKBFGLZZRETK-UHFFFAOYSA-N 0.000 description 4
- 125000005580 triphenylene group Chemical group 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 229940023913 cation exchange resins Drugs 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000004673 fluoride salts Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000005259 measurement Methods 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
- VDSONAWIXGYSJC-UHFFFAOYSA-N naphthalen-2-ylmethyl prop-2-enoate Chemical compound C1=CC=CC2=CC(COC(=O)C=C)=CC=C21 VDSONAWIXGYSJC-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MFGWMAAZYZSWMY-UHFFFAOYSA-N (2-naphthyl)methanol Chemical compound C1=CC=CC2=CC(CO)=CC=C21 MFGWMAAZYZSWMY-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- YSQZSPCQDXHJDJ-UHFFFAOYSA-N 1-(pentyldisulfanyl)pentane Chemical compound CCCCCSSCCCCC YSQZSPCQDXHJDJ-UHFFFAOYSA-N 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 description 2
- RSQXKVWKJVUZDG-UHFFFAOYSA-N 9-bromophenanthrene Chemical compound C1=CC=C2C(Br)=CC3=CC=CC=C3C2=C1 RSQXKVWKJVUZDG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 150000001502 aryl halides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 2
- ALVPFGSHPUPROW-UHFFFAOYSA-N dipropyl disulfide Chemical group CCCSSCCC ALVPFGSHPUPROW-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N phenyl mercaptan Natural products SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002195 soluble material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- FMWGRNWCOWPFFY-UHFFFAOYSA-N (3-ethenylphenanthren-9-yl)-dimethoxy-phenanthren-9-ylsilane Chemical compound CO[Si](C=1C2=CC=CC=C2C=2C=C(C=CC=2C=1)C=C)(C=1C2=CC=CC=C2C=2C=CC=CC=2C=1)OC FMWGRNWCOWPFFY-UHFFFAOYSA-N 0.000 description 1
- DKZFIPFKXAGEBP-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) benzoate Chemical compound OCC(C)(C)COC(=O)C1=CC=CC=C1 DKZFIPFKXAGEBP-UHFFFAOYSA-N 0.000 description 1
- WFSVKTVHMSQUDZ-UHFFFAOYSA-N (4-ethenylnaphthalen-1-yl)-dimethoxy-phenanthren-9-ylsilane Chemical compound CO[Si](C1=CC=C(C2=CC=CC=C12)C=C)(C=1C2=CC=CC=C2C=2C=CC=CC=2C=1)OC WFSVKTVHMSQUDZ-UHFFFAOYSA-N 0.000 description 1
- AXGCCBYOYRKUBG-UHFFFAOYSA-N (4-ethenylphenyl)-diethoxy-phenanthren-9-ylsilane Chemical compound C(C)O[Si](C1=CC=C(C=C1)C=C)(C=1C2=CC=CC=C2C=2C=CC=CC=2C=1)OCC AXGCCBYOYRKUBG-UHFFFAOYSA-N 0.000 description 1
- ONJSPIPCYCVZTK-UHFFFAOYSA-N (4-ethenylphenyl)-dimethoxy-(4-phenylphenyl)silane Chemical compound C1(=CC=C(C=C1)[Si](C1=CC=C(C=C1)C=C)(OC)OC)C1=CC=CC=C1 ONJSPIPCYCVZTK-UHFFFAOYSA-N 0.000 description 1
- ZYCRYWLQPKJDRQ-UHFFFAOYSA-N (4-ethenylphenyl)-dimethoxy-naphthalen-1-ylsilane Chemical compound CO[Si](C1=CC=C(C=C1)C=C)(C1=CC=CC2=CC=CC=C12)OC ZYCRYWLQPKJDRQ-UHFFFAOYSA-N 0.000 description 1
- IMQULICUVKWMPN-UHFFFAOYSA-N (4-ethenylphenyl)-dimethoxy-phenanthren-2-ylsilane Chemical compound CO[Si](C1=CC=C(C=C1)C=C)(C1=CC=2C=CC3=CC=CC=C3C=2C=C1)OC IMQULICUVKWMPN-UHFFFAOYSA-N 0.000 description 1
- DVNJGFKZFUKXBP-UHFFFAOYSA-N (4-ethenylphenyl)-phenanthren-9-yl-di(propan-2-yloxy)silane Chemical compound C(C)(C)O[Si](C1=CC=C(C=C1)C=C)(C=1C2=CC=CC=C2C=2C=CC=CC=2C=1)OC(C)C DVNJGFKZFUKXBP-UHFFFAOYSA-N 0.000 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- 125000004814 1,1-dimethylethylene group Chemical group [H]C([H])([H])C([*:1])(C([H])([H])[H])C([H])([H])[*:2] 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- IDJPKRIELSFBPE-UHFFFAOYSA-N 1-(decyldisulfanyl)decane Chemical compound CCCCCCCCCCSSCCCCCCCCCC IDJPKRIELSFBPE-UHFFFAOYSA-N 0.000 description 1
- GJPDBURPGLWRPW-UHFFFAOYSA-N 1-(hexyldisulfanyl)hexane Chemical compound CCCCCCSSCCCCCC GJPDBURPGLWRPW-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- TZOVOULUMXXLOJ-UHFFFAOYSA-N 1-methyl-4-[(4-methylphenyl)disulfanyl]benzene Chemical compound C1=CC(C)=CC=C1SSC1=CC=C(C)C=C1 TZOVOULUMXXLOJ-UHFFFAOYSA-N 0.000 description 1
- 125000004806 1-methylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- HKNNAYPWWDWHFR-UHFFFAOYSA-N 1-sulfanylbutan-1-ol Chemical compound CCCC(O)S HKNNAYPWWDWHFR-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 1
- MKWZLIFXFATNFR-UHFFFAOYSA-N 2,7-bis(4-ethenylphenyl)naphthalene Chemical compound C(=C)C1=CC=C(C=C1)C1=CC2=CC(=CC=C2C=C1)C1=CC=C(C=C1)C=C MKWZLIFXFATNFR-UHFFFAOYSA-N 0.000 description 1
- WKDCYKWOTYBIPG-UHFFFAOYSA-N 2-(1h-benzimidazol-2-yldisulfanyl)-1h-benzimidazole Chemical compound C1=CC=C2NC(SSC=3NC4=CC=CC=C4N=3)=NC2=C1 WKDCYKWOTYBIPG-UHFFFAOYSA-N 0.000 description 1
- XJIKEAQNTPCOLU-UHFFFAOYSA-N 2-(2,2-diethoxyethyldisulfanyl)-1,1-diethoxyethane Chemical compound CCOC(OCC)CSSCC(OCC)OCC XJIKEAQNTPCOLU-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VAZQKPWSBFZARZ-UHFFFAOYSA-N 2-(2-phenylphenoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1C1=CC=CC=C1 VAZQKPWSBFZARZ-UHFFFAOYSA-N 0.000 description 1
- QSOFJLDXOMMNNK-UHFFFAOYSA-N 2-(hydroxymethyl)-2-methylpropane-1,3-diol 3-sulfanylbutanoic acid Chemical compound CC(S)CC(O)=O.CC(S)CC(O)=O.CC(S)CC(O)=O.OCC(C)(CO)CO QSOFJLDXOMMNNK-UHFFFAOYSA-N 0.000 description 1
- HQPZDTQSGNKMOM-UHFFFAOYSA-N 2-(hydroxymethyl)-2-methylpropane-1,3-diol;3-sulfanylpropanoic acid Chemical compound OC(=O)CCS.OC(=O)CCS.OC(=O)CCS.OCC(C)(CO)CO HQPZDTQSGNKMOM-UHFFFAOYSA-N 0.000 description 1
- BKCNDTDWDGQHSD-UHFFFAOYSA-N 2-(tert-butyldisulfanyl)-2-methylpropane Chemical compound CC(C)(C)SSC(C)(C)C BKCNDTDWDGQHSD-UHFFFAOYSA-N 0.000 description 1
- RFCQDOVPMUSZMN-UHFFFAOYSA-N 2-Naphthalenethiol Chemical compound C1=CC=CC2=CC(S)=CC=C21 RFCQDOVPMUSZMN-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- CFKONAWMNQERAG-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis[2-(3-sulfanylpropanoyloxy)ethyl]-1,3,5-triazinan-1-yl]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCN1C(=O)N(CCOC(=O)CCS)C(=O)N(CCOC(=O)CCS)C1=O CFKONAWMNQERAG-UHFFFAOYSA-N 0.000 description 1
- YCPMSWJCWKUXRH-UHFFFAOYSA-N 2-[4-[9-[4-(2-prop-2-enoyloxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethyl prop-2-enoate Chemical compound C1=CC(OCCOC(=O)C=C)=CC=C1C1(C=2C=CC(OCCOC(=O)C=C)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YCPMSWJCWKUXRH-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WBEKRAXYEBAHQF-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-sulfanylbutanoic acid Chemical compound CC(S)CC(O)=O.CC(S)CC(O)=O.CC(S)CC(O)=O.CCC(CO)(CO)CO WBEKRAXYEBAHQF-UHFFFAOYSA-N 0.000 description 1
- SUODCTNNAKSRHB-UHFFFAOYSA-N 2-ethylhexyl 3-sulfanylpropanoate Chemical compound CCCCC(CC)COC(=O)CCS SUODCTNNAKSRHB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- ANCUXNXTHQXICN-UHFFFAOYSA-N 2-prop-1-en-2-ylnaphthalene Chemical compound C1=CC=CC2=CC(C(=C)C)=CC=C21 ANCUXNXTHQXICN-UHFFFAOYSA-N 0.000 description 1
- APWBGRBFKMJPLW-UHFFFAOYSA-N 3-methoxybutyl 3-sulfanylpropanoate Chemical compound COC(C)CCOC(=O)CCS APWBGRBFKMJPLW-UHFFFAOYSA-N 0.000 description 1
- MPYGLNNTOXLWOB-UHFFFAOYSA-N 3-methyl-1-(3-methylbutyldisulfanyl)butane Chemical compound CC(C)CCSSCCC(C)C MPYGLNNTOXLWOB-UHFFFAOYSA-N 0.000 description 1
- WRXOZRLZDJAYDR-UHFFFAOYSA-N 3-methylbenzenethiol Chemical compound CC1=CC=CC(S)=C1 WRXOZRLZDJAYDR-UHFFFAOYSA-N 0.000 description 1
- RQPNXPWEGVCPCX-UHFFFAOYSA-N 3-sulfanylbutanoic acid Chemical compound CC(S)CC(O)=O RQPNXPWEGVCPCX-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- LABQKWYHWCYABU-UHFFFAOYSA-N 4-(3-sulfanylbutanoyloxy)butyl 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCCCCOC(=O)CC(C)S LABQKWYHWCYABU-UHFFFAOYSA-N 0.000 description 1
- JSOVZQSFWPMPKN-UHFFFAOYSA-N 4-(3-sulfanylpropanoyloxy)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCCCOC(=O)CCS JSOVZQSFWPMPKN-UHFFFAOYSA-N 0.000 description 1
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- UVQATVZCNVYMKL-UHFFFAOYSA-N C(C(=C)C)(=O)OCC(COC(C=C)=O)O.C(C=C)(=O)O Chemical compound C(C(=C)C)(=O)OCC(COC(C=C)=O)O.C(C=C)(=O)O UVQATVZCNVYMKL-UHFFFAOYSA-N 0.000 description 1
- RVFNWEHKRMFNNK-UHFFFAOYSA-N CC(C)(C(C(C(C)C)(C)C)(C)C)SSC(C)(C(C(C(C)C)(C)C)(C)C)C Chemical compound CC(C)(C(C(C(C)C)(C)C)(C)C)SSC(C)(C(C(C(C)C)(C)C)(C)C)C RVFNWEHKRMFNNK-UHFFFAOYSA-N 0.000 description 1
- CQNIIHXRDAQULN-UHFFFAOYSA-N CO[SiH](C1=CC=C(C=C1)C=C)C=1C=CC=2C=CC3=CC=CC=C3C2C1 Chemical compound CO[SiH](C1=CC=C(C=C1)C=C)C=1C=CC=2C=CC3=CC=CC=C3C2C1 CQNIIHXRDAQULN-UHFFFAOYSA-N 0.000 description 1
- ATAGQIUEZHDXDN-UHFFFAOYSA-N CO[Si](C1=CC=2C=CC3=CC=CC=C3C=2C=C1)(OC)OC Chemical compound CO[Si](C1=CC=2C=CC3=CC=CC=C3C=2C=C1)(OC)OC ATAGQIUEZHDXDN-UHFFFAOYSA-N 0.000 description 1
- VMRZPOFAOVBZNY-UHFFFAOYSA-N CO[Si](C=1C=CC=2C=CC3=CC=CC=C3C=2C=1)(OC)OC Chemical compound CO[Si](C=1C=CC=2C=CC3=CC=CC=C3C=2C=1)(OC)OC VMRZPOFAOVBZNY-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- CUDSBWGCGSUXDB-UHFFFAOYSA-N Dibutyl disulfide Chemical compound CCCCSSCCCC CUDSBWGCGSUXDB-UHFFFAOYSA-N 0.000 description 1
- ODHAQPXNQDBHSH-UHFFFAOYSA-N Dicyclohexyl disulfide Chemical compound C1CCCCC1SSC1CCCCC1 ODHAQPXNQDBHSH-UHFFFAOYSA-N 0.000 description 1
- LZAZXBXPKRULLB-UHFFFAOYSA-N Diisopropyl disulfide Chemical compound CC(C)SSC(C)C LZAZXBXPKRULLB-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 101100389975 Mus musculus Ezhip gene Proteins 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000007875 V-40 Substances 0.000 description 1
- AVTLBBWTUPQRAY-BUHFOSPRSA-N V-59 Substances CCC(C)(C#N)\N=N\C(C)(CC)C#N AVTLBBWTUPQRAY-BUHFOSPRSA-N 0.000 description 1
- WYGWHHGCAGTUCH-ISLYRVAYSA-N V-65 Substances CC(C)CC(C)(C#N)\N=N\C(C)(C#N)CC(C)C WYGWHHGCAGTUCH-ISLYRVAYSA-N 0.000 description 1
- 239000007874 V-70 Substances 0.000 description 1
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 description 1
- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- HMSIINUKBOUHOG-UHFFFAOYSA-N [4-(4-ethenylphenyl)phenyl]-dimethoxy-phenanthren-9-ylsilane Chemical compound CO[Si](C1=CC=C(C=C1)C1=CC=C(C=C1)C=C)(C=1C2=CC=CC=C2C=2C=CC=CC=2C=1)OC HMSIINUKBOUHOG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical class C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000004190 benzothiazol-2-yl group Chemical group [H]C1=C([H])C([H])=C2N=C(*)SC2=C1[H] 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical class OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- LEDIWWJKWAMGLD-UHFFFAOYSA-N bis(2-methylundecan-2-yl) disulfide Chemical compound CCCCCCCCCC(C)(C)SSC(C)(C)CCCCCCCCC LEDIWWJKWAMGLD-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical class OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical class CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- HOXINJBQVZWYGZ-UHFFFAOYSA-N fenbutatin oxide Chemical compound C=1C=CC=CC=1C(C)(C)C[Sn](O[Sn](CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C1=CC=CC=C1 HOXINJBQVZWYGZ-UHFFFAOYSA-N 0.000 description 1
- HJUFTIJOISQSKQ-UHFFFAOYSA-N fenoxycarb Chemical compound C1=CC(OCCNC(=O)OCC)=CC=C1OC1=CC=CC=C1 HJUFTIJOISQSKQ-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- MKIJJIMOAABWGF-UHFFFAOYSA-N methyl 2-sulfanylacetate Chemical compound COC(=O)CS MKIJJIMOAABWGF-UHFFFAOYSA-N 0.000 description 1
- LDTLDBDUBGAEDT-UHFFFAOYSA-N methyl 3-sulfanylpropanoate Chemical compound COC(=O)CCS LDTLDBDUBGAEDT-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- ISVWDXGCSXKULB-UHFFFAOYSA-N naphthalen-1-yl-tri(propan-2-yloxy)silane Chemical compound C1=CC=C2C([Si](OC(C)C)(OC(C)C)OC(C)C)=CC=CC2=C1 ISVWDXGCSXKULB-UHFFFAOYSA-N 0.000 description 1
- RYTXPJWZUVQRDS-UHFFFAOYSA-N naphthalen-2-yl-tri(propan-2-yloxy)silane Chemical compound C(C)(C)O[Si](C1=CC2=CC=CC=C2C=C1)(OC(C)C)OC(C)C RYTXPJWZUVQRDS-UHFFFAOYSA-N 0.000 description 1
- UCUPUEARJPTGKU-UHFFFAOYSA-N octadecyl 3-sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCS UCUPUEARJPTGKU-UHFFFAOYSA-N 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
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- BMNCEQGZEGXDEB-UHFFFAOYSA-N phenanthren-9-yl-tri(propan-2-yloxy)silane Chemical compound C(C)(C)O[Si](C=1C2=CC=CC=C2C=2C=CC=CC=2C=1)(OC(C)C)OC(C)C BMNCEQGZEGXDEB-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- KNBRWWCHBRQLNY-UHFFFAOYSA-N piperidine-1-carbothioylsulfanyl piperidine-1-carbodithioate Chemical compound C1CCCCN1C(=S)SSC(=S)N1CCCCC1 KNBRWWCHBRQLNY-UHFFFAOYSA-N 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ZJEYUFMTCHLQQI-UHFFFAOYSA-N triethoxy(naphthalen-1-yl)silane Chemical compound C1=CC=C2C([Si](OCC)(OCC)OCC)=CC=CC2=C1 ZJEYUFMTCHLQQI-UHFFFAOYSA-N 0.000 description 1
- UYCSMKDCDZVBGS-UHFFFAOYSA-N triethoxy(naphthalen-2-yl)silane Chemical compound C1=CC=CC2=CC([Si](OCC)(OCC)OCC)=CC=C21 UYCSMKDCDZVBGS-UHFFFAOYSA-N 0.000 description 1
- WJJDBJYEDVQKGT-UHFFFAOYSA-N triethoxy(phenanthren-9-yl)silane Chemical compound C1=CC=C2C([Si](OCC)(OCC)OCC)=CC3=CC=CC=C3C2=C1 WJJDBJYEDVQKGT-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ZSOVVFMGSCDMIF-UHFFFAOYSA-N trimethoxy(naphthalen-1-yl)silane Chemical compound C1=CC=C2C([Si](OC)(OC)OC)=CC=CC2=C1 ZSOVVFMGSCDMIF-UHFFFAOYSA-N 0.000 description 1
- DIYLRQVVOHZHNA-UHFFFAOYSA-N trimethoxy(naphthalen-2-yl)silane Chemical compound C1=CC=CC2=CC([Si](OC)(OC)OC)=CC=C21 DIYLRQVVOHZHNA-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- XQEGZYAXBCFSBS-UHFFFAOYSA-N trimethoxy-(4-methylphenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=C(C)C=C1 XQEGZYAXBCFSBS-UHFFFAOYSA-N 0.000 description 1
- GDRDDMTUPOZHSD-UHFFFAOYSA-N trimethoxy-(4-phenylphenyl)silane Chemical compound C1=CC([Si](OC)(OC)OC)=CC=C1C1=CC=CC=C1 GDRDDMTUPOZHSD-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229940042596 viscoat Drugs 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
Images
Classifications
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
Definitions
- the present invention relates to a viscosity reducing agent, and more particularly to a viscosity reducing agent useful as a high refractive index diluent capable of reducing the viscosity of a polymerizable optical material having a high refractive index.
- Resin lenses are used in electronic devices such as mobile phones, digital cameras, and in-vehicle cameras, and are required to have excellent optical characteristics according to the purpose of the electronic device. Moreover, high durability, for example, heat resistance and weather resistance, and high productivity that can be molded with a high yield are required in accordance with the usage mode.
- a resin lens material that satisfies such requirements, for example, thermoplastic transparent resins such as polycarbonate resin, cycloolefin polymer, and methacrylic resin have been used.
- thermoplastic transparent resins such as polycarbonate resin, cycloolefin polymer, and methacrylic resin have been used.
- thermoplastic transparent resins such as polycarbonate resin, cycloolefin polymer, and methacrylic resin
- a plurality of lenses are used in the high-resolution camera module, and an optical material having high wavelength dispersion, that is, a low Abbe number is required as one of the wavelength correction lenses.
- a material characterized by a low Abbe number will require high transparency in addition to a high refractive index, but improving these optical properties will increase the viscosity of the material and significantly degrade handling. There are many. This is because, in general, components that contribute to a high refractive index have a high electron density and are therefore easily increased in viscosity, and deterioration in handling properties can be said to be an essential issue in the development of low Abbe materials.
- Patent Document 1 there is a proposal for a curable composition for a lens material that employs a liquid (meth) acrylate having a relatively high refractive index as a diluent to reduce viscosity and improve handling properties.
- Patent Document 2 there is a proposal of a curable composition that achieves a low viscosity without using a diluent by introducing an oxyalkylene group into a component that contributes to a high refractive index.
- JP 2012-255914 A Japanese Patent Laid-Open No. 2015-199952
- the curable composition (Patent Document 1) using the aforementioned diluent has an Abbe number ⁇ D of 25 or more, for example, 23 or less, although the refractive index n D at 589 nm after photocuring is around 1.61. The low Abbe number requirement is not satisfied.
- the refractive index n D after photocuring 1.60 or more is not realized, and this sufficiently satisfies the optical characteristics. It is not.
- lower Abbe and lower viscosity are in a trade-off relationship, for example, a low viscosity of 10,000 mPa ⁇ s or less is achieved, and a high refractive index of 1.60 or more in a cured product is 23 or less.
- No optical material has yet achieved excellent optical properties such as a low Abbe number.
- Conventional diluents for achieving low viscosity generally have a low refractive index.
- the present invention has been made in view of such circumstances, and has overcome the trade-off between low Abbe and low viscosity, and has low refractive index loss when blended, with high refractive index and low viscosity. It is an object of the present invention to provide an agent and a polymerizable composition containing the agent.
- a low Abbe compound that is solid at normal temperature and normal pressure and has a viscosity at 100 ° C. of 10 mPa ⁇ s or less has a high refractive index.
- the viscosity of the system is reduced to 10,000 mPa ⁇ s or less, or maintained at 10,000 mPa ⁇ s or less, and in the cured product of the system.
- excellent optical characteristics low Abbe number, high refractive index
- the present invention is a compound in which the state of a substance at 23 ° C. is solid at 1013.25 hPa and has a melting point of less than 100 ° C., and the viscosity at 100 ° C. is 10 mPa ⁇ s or less, A compound having an Abbe number of 23 or less at the D line (589.3 nm) of the cured product,
- the present invention relates to a method for use as a low-viscosity agent for a high refractive index polymerizable compound having at least one polymerizable double bond and having a refractive index at D-line (589.3 nm) of the cured product of 1.60 or more.
- the viscosity reducing agent is a phenyl group or phenylene group which may be substituted with an alkyl group having 1 to 6 carbon atoms, monovalent or divalent condensed ring carbonization having a plurality of benzene ring structures.
- a hydrogen group (which may be substituted with an alkyl group having 1 to 6 carbon atoms), and a monovalent or divalent hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded by a single bond (carbon atoms)
- a compound having at least one group having a polymerizable double bond selected from the group consisting of a vinyl group, an allyl group, a (meth) allyloxy group and a (meth) acryloyl group
- the present invention relates to the method according to the second aspect, wherein the viscosity reducing agent is a compound represented by the following formula [1].
- X represents a phenyl group having at least one substituent having a polymerizable double bond, a naphthyl group having at least one substituent having a polymerizable double bond, and a substituent having a polymerizable double bond.
- Ar 1 represents a condensed ring hydrocarbon group having a plurality of benzene ring structures (having 1 to 6 carbon atoms).
- the present invention relates to the method according to the second aspect, wherein the viscosity reducing agent is a compound represented by the following formula [2].
- Ar 2 represents a q-valent aromatic hydrocarbon residue, q represents 1 or 2
- Y represents a single bond, —O—C ( ⁇ O) — group, or —O— group
- R 2 represents a hydrogen atom or a methyl group.
- the present invention relates to the method according to the second aspect, wherein the viscosity reducing agent is a compound represented by the following formula [3-1] or [3-2].
- R 1 represents a methyl group, an ethyl group, or an isopropyl group.
- a low-viscosity agent for a high-refractive index polymerizable compound having at least one polymerizable double bond and having a refractive index of 1.60 or more at the D-line (589.3 nm) of the cured product There, A compound having a solid state at 1013.25 hPa at 23 ° C.
- the present invention relates to a polymerizable composition
- a polymerizable composition comprising 10 to 500 parts by mass of a viscosity reducing agent comprising a compound having an Abbe number of 23 or less at a line (589.3 nm).
- the high refractive index polymerizable compound (a) is a polycondensate of an alkoxysilicon compound A represented by the formula [4], and an alkoxysilicon compound A represented by the formula [4] and the formula [4]. 5]
- the polymerizable composition according to the seventh aspect which contains a reactive polysiloxane containing at least one of the polycondensates with the alkoxysilicon compound B.
- X represents a phenyl group having at least one substituent having a polymerizable double bond, a naphthyl group having at least one substituent having a polymerizable double bond, and a substituent having a polymerizable double bond.
- Ar 3 represents a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a plurality of A condensed ring hydrocarbon group having a benzene ring structure (which may be substituted with an alkyl group having 1 to 6 carbon atoms), or a hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded by a single bond ( And optionally substituted with an alkyl group having 1 to 6 carbon atoms, and R 3 represents a methyl group, an ethyl group, or an isopropyl group.)
- Ar 4 is a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, or a condensed ring hydrocarbon group having a plurality of benzene ring structures (substit
- the present invention relates to the polymerizable composition according to the seventh aspect, in which the high refractive index polymerizable compound (a) includes a fluorene compound represented by the formula [6].
- the high refractive index polymerizable compound (a) includes a fluorene compound represented by the formula [6].
- R 5 and R 6 each independently represent a hydrogen atom or a methyl group
- L 1 and L 2 each independently represent a phenylene group which may have a substituent, or a substituent.
- an optionally substituted naphthalenediyl group, L 3 and L 4 each independently represent an alkylene group having 1 to 6 carbon atoms, and m and n each independently represents 0 ⁇ m + n ⁇ 40. Represents 0 or a positive integer to satisfy.)
- the high refractive index polymerizable compound is a compound represented by the following formula [7-1], a compound having a structural unit represented by the formula [7-2], and the formula [7 -2] and the polymerizable composition according to the seventh aspect, selected from the group consisting of compounds having a structural unit represented by the formula [7-3].
- the polymerizable composition according to any one of the seventh aspect to the tenth aspect, further comprising (c) a polymerizable diluent having a liquid state at 23 ° C. under 1013.25 hPa. About.
- the present invention relates to a cured product of the polymerizable composition according to any one of the seventh aspect to the eleventh aspect.
- the present invention relates to a material for a high refractive index resin lens comprising the polymerizable composition according to any one of the seventh aspect to the eleventh aspect.
- it is related with the resin lens produced from the polymeric composition as described in any one of a 7th viewpoint thru
- the method further includes a step of taking out and releasing the obtained photopolymer from the filled space, and a step of heating the photopolymer before, during or after the release.
- the manufacturing method according to the fifteenth aspect As a seventeenth aspect, the present invention relates to the manufacturing method according to the fifteenth aspect or the sixteenth aspect, in which the molded body is a camera module lens.
- the present invention is a compound that has a solid state at 1013.25 hPa at 23 ° C. and a melting point of less than 100 ° C., and has a viscosity at 100 ° C. of 10 mPa ⁇ s or less, and the D line of the cured product
- a compound having an Abbe number of 23 or less at (589.3 nm) as a low viscosity agent for a high refractive index polymerizable compound the viscosity of the system is reduced to 10,000 mPa ⁇ s or less, or 10, 000 mPa ⁇ s or less, and excellent optical characteristics (low Abbe number, high refractive index) can be realized in the cured product.
- the polymerizable composition of the present invention achieves a low viscosity by blending the viscosity reducing agent, the handling property is improved, and the cured product is an optical device such as a lens for a high resolution camera module. Desirable optical characteristics (low Abbe number, high refractive index) can be achieved. Therefore, the high refractive index resin lens material of the present invention comprising the polymerizable composition can be suitably used as a lens for a high resolution camera module.
- the polymerizable composition of the present invention has a viscosity that can be sufficiently handled in a solvent-free form due to the blending of the viscosity reducing agent, it can be used for pressing a mold such as a mold (imprint technology). ) Can be molded, and it is excellent in releasability from the mold after molding, and a molded product can be suitably produced. Further, the production method of the present invention can efficiently produce a molded article, particularly a camera module lens, because the polymerizable composition to be used has excellent handling properties.
- FIG. 1 is a diagram showing a 1 H NMR spectrum of dimethoxy (phenanthren-9-yl) (4-vinylphenyl) silane obtained in Production Example 1.
- FIG. 2 is a diagram showing a 1 H NMR spectrum of trimethoxy (9-phenanthryl) silane obtained in Production Example 3.
- the present invention is a compound that has a solid state at 1013.25 hPa at 23 ° C. and a melting point of less than 100 ° C., and has a viscosity at 100 ° C. of 10 mPa ⁇ s or less, and the D line of the cured product Abbe number at (589.3 nm), i.e. the compound [nu D is 23 or less, a method of using a low-viscosity agent described later high refractive index polymerizable compound, and the target is also present invention the viscosity reducing agent To do. Details of the present invention will be described below.
- the viscosity reducing agent of the present invention is a solid substance at 23 ° C. under 101.25 hPa (that is, atmospheric pressure), has a melting point of less than 100 ° C., and has a viscosity at 100 ° C. of 10 mPa ⁇ s or less. And it will not specifically limit if the Abbe number in D line
- the viscosity reducing agent examples include compounds having at least one group each having an aromatic group and a polymerizable double bond.
- the term “polymerizability” refers to the property of causing a polymerization reaction when a part of a molecule undergoes a chemical reaction by an external stimulus such as heat or light and is cleaved or decomposed.
- Specific examples of the compound include a phenyl group or a phenylene group which may be substituted with an alkyl group having 1 to 6 carbon atoms, and a monovalent or divalent condensed ring hydrocarbon group having a plurality of benzene ring structures.
- the compound which has at least 1 group which has a polymerizable double bond selected from the group which consists of can be mentioned.
- the monovalent or divalent condensed ring hydrocarbon group having a plurality of benzene ring structures is derived from, for example, naphthalene, phenanthrene, anthracene, triphenylene, pyrene, chrysene, naphthacene, biphenylene, and fluorene.
- a monovalent or divalent group is mentioned.
- Examples of the monovalent or divalent hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded by a single bond include biphenyl, terphenyl, quaterphenyl, binaphthalene, phenylnaphthalene, phenylfluorene, and diphenylfluorene.
- Examples thereof include a monovalent or divalent group to be derived.
- the alkyl group having 1 to 6 carbon atoms which may be substituted are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl Groups.
- Preferred examples include a phenyl group, a naphthyl group, and a phenanthryl group.
- X represents a phenyl group having at least one group having a polymerizable double bond, a naphthyl group having at least one group having a polymerizable double bond, and a group having a polymerizable double bond.
- Ar 1 represents a condensed ring hydrocarbon group having a plurality of benzene ring structures (an alkyl having 1 to 6 carbon atoms).
- R 1 represents a methyl group, an ethyl group, or an isopropyl group.
- Examples of the phenyl group having at least one group having a polymerizable double bond represented by X include a 2-vinylphenyl group, a 3-vinylphenyl group, a 4-vinylphenyl group, a 4-vinyloxyphenyl group, 4- Examples include allylphenyl group, 4-allyloxyphenyl group, and 4-isopropenylphenyl group.
- Examples of the naphthyl group having at least one group having a polymerizable double bond represented by X include, for example, 4-vinylnaphthalen-1-yl group, 5-vinylnaphthalen-1-yl group, and 6-vinylnaphthalene-2- Yl group, 5-vinyloxynaphthalen-1-yl group, 5-allylnaphthalen-1-yl group, 4-allyloxynaphthalen-1-yl group, 5-allyloxynaphthalen-1-yl group, 8-allyloxy And naphthalen-1-yl group and 5-isopropenylnaphthalen-1-yl group.
- Examples of the biphenyl group having at least one group having a polymerizable double bond represented by X include a 4′-vinyl- [1,1′-biphenyl] -2-yl group, 4′-vinyl- [1, 1′-biphenyl] -3-yl group, 4′-vinyl- [1,1′-biphenyl] -4-yl group, 4′-vinyloxy- [1,1′-biphenyl] -4-yl group, 4 '-Allyl- [1,1'-biphenyl] -4-yl group, 4'-allyloxy- [1,1'-biphenyl] -4-yl group, 4'-isopropenyl- [1,1'-biphenyl] ] -4-yl group.
- Examples of the phenanthryl group having at least one group having a polymerizable double bond represented by X include, for example, 3-vinylphenanthren-9-yl group, 7-vinylphenanthrene-9-yl group, 10-vinylphenanthrene-9- Yl group, 7-vinylphenanthren-2-yl group, 6-vinylphenanthrene-3-yl group, 10-vinylphenanthren-3-yl group, 3-vinyloxyphenanthren-9-yl group, 3-allylphenanthrene-9 -Yl group, 3-allyloxyphenanthren-9-yl group, 3-isopropenylphenanthren-9-yl group.
- X is preferably a phenyl group having at least one group having a polymerizable double bond, and more preferably a vinylphenyl group.
- Examples of the condensed ring hydrocarbon group having a plurality of benzene ring structures represented by Ar 1 include monovalent groups derived from naphthalene, phenanthrene, anthracene, triphenylene, pyrene, chrysene, naphthacene, biphenylene, and fluorene.
- Examples of the hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded with a single bond include, for example, monovalent derivatives derived from biphenyl, terphenyl, quaterphenyl, binaphthalene, phenylnaphthalene, phenylfluorene, and diphenylfluorene. Groups.
- examples of the alkyl group having 1 to 6 carbon atoms that may be substituted include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group.
- Ar 1 is preferably a condensed ring hydrocarbon group having a plurality of benzene ring structures (which may be substituted with an alkyl group having 1 to 6 carbon atoms), and more preferably a phenanthryl group.
- the compound represented by the formula [1] include, for example, dimethoxy (9-phenanthryl) (4-vinylphenyl) silane, diethoxy (9-phenanthryl) (4-vinylphenyl) silane, diisopropoxy ( 9-phenanthryl) (4-vinylphenyl) silane, dimethoxy (9-phenanthryl) (4-vinylnaphthalen-1-yl) silane, dimethoxy (9-phenanthryl) (4′-vinyl- [1,1′-biphenyl] -4-yl) silane, dimethoxy (9-phenanthryl) (3-vinylphenanthrene-9-yl) silane, dimethoxy (1-naphthyl) (4-vinylphenyl) silane, dimethoxy (2-naphthyl) (4-vinylphenyl) ) Silane, dimethoxy (2-phenanthryl) (4-vinylphenyl) (e
- the compound represented by following formula [2] is mentioned as a specific example of the compound which has at least 1 each of the said specific aromatic group and group which has a polymerizable double bond, respectively.
- Ar 2 represents a q-valent aromatic hydrocarbon residue, q represents 1 or 2
- Y represents a single bond, —O—C ( ⁇ O) — group, or —O—.
- R 2 represents a hydrogen atom or a methyl group.
- the q-valent aromatic hydrocarbon residue in Ar 2 is benzene, a condensed ring hydrocarbon having a plurality of benzene ring structures, or a hydrocarbon ring assembly in which a plurality of aromatic rings are directly bonded by a single bond.
- Examples include a group in which q hydrogen atoms are removed, and these may be substituted with an alkyl group having 1 to 6 carbon atoms.
- a phenyl group or a phenylene group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a monovalent or divalent condensed ring hydrocarbon group having a plurality of benzene ring structures (one carbon atom) Or a monovalent or divalent hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded with a single bond (an alkyl group having 1 to 6 carbon atoms). Which may be substituted).
- Examples of the phenyl group optionally substituted by an alkyl group having 1 to 6 carbon atoms represented by Ar 2 include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, 2, 4, 6 -Trimethylphenyl group and 4-tert-butylphenyl group.
- Examples of the phenylene group which may be substituted with an alkyl group having 1 to 6 carbon atoms include phenylene group, 2,4-methylphenylene group, Examples include 2,5-methylphenylene group, 2,4,5-trimethyl-1,3-phenylene group, and 2-tert-butyl-1,4-phenylene group.
- Examples of the monovalent or divalent condensed ring hydrocarbon group having a plurality of benzene ring structures represented by Ar 2 include monovalent derivatives derived from naphthalene, phenanthrene, anthracene, triphenylene, pyrene, chrysene, naphthacene, biphenylene, and fluorene. Or a bivalent group is mentioned.
- Examples of the monovalent or divalent hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded by a single bond include biphenyl, terphenyl, quaterphenyl, binaphthalene, phenylnaphthalene, phenylfluorene, and diphenylfluorene.
- Examples thereof include a monovalent or divalent group to be derived.
- the alkyl group having 1 to 6 carbon atoms that may be substituted include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group.
- the compound represented by the formula [2] are, for example, 1-vinylnaphthalene, 2-vinylnaphthalene, 2-isopropenylnaphthalene, 2,7-bis (4-vinylphenyl) naphthalene, naphthalene-1 -Ylmethyl (meth) acrylate, naphthalen-2-ylmethyl (meth) acrylate.
- Examples of the viscosity reducing agent according to the present invention include compounds represented by the following formulas [3-1] to [3-4], among which the formulas [3-1] and [3-2]
- the compound represented by the formula [3-1] is preferable from the viewpoint of realizing the effect of reducing and maintaining the viscosity and realizing excellent optical properties (low Abbe number).
- R 1 represents a methyl group, an ethyl group, or an isopropyl group.
- a commercially available compound can be suitably used for the viscosity reducing agent according to the present invention.
- an ester compound containing a (meth) acryloyl group such as a compound represented by the formula [3-4] can be produced by a conventional method, and an alcohol and a (meth) acrylic acid halide are present in the presence of triethylamine or pyridine. It can manufacture by making it esterify under.
- the compounds represented by the above formulas [3-1] and [3-3] can be produced by conventional methods, for example, alkoxysilane compounds and Grignards.
- the conventional Grignard reaction to obtain an organoalkoxysilane compound by reacting with a reagent, or the conventional coupling reaction to obtain an organoalkoxysilane compound by reacting an alkoxyhydrosilane compound and an aryl halide using a transition metal catalyst. can be manufactured.
- a Grignard reagent having an Ar 1 group: Ar 1 —Mg—Hal is reacted with a trialkoxysilane compound having an aromatic ring group having a polymerizable double bond: X—Si (OR 1 ) 3.
- a Grignard reagent having an aromatic ring group having a polymerizable double bond: X-Mg-Hal and a trialkoxysilane compound having Ar 1 group: Ar 1 -Si (OR 1 ) 3 are reacted,
- a polymerizable silane compound represented by the formula [1] can be obtained (the above Ar 1 , X, and R 1 have the same meaning as the formula [1], and Hal represents a halogen atom).
- the Grignard reagent is obtained by reacting an aryl halide: Ar 1 -Hal or X-Hal with magnesium.
- the production of the Grignard reagent and the reaction between the Grignard reagent and the alkoxysilane compound can be carried out in an organic solvent.
- organic solvent used here include ether solvents such as diethyl ether, tetrahydrofuran and tert-butyl methyl ether; and inert organic solvents such as hydrocarbon solvents such as hexane, toluene and xylene. . You may use these organic solvents individually by 1 type or in mixture of 2 or more types.
- the above production temperature and reaction temperature are preferably in the range of 0 to 200 ° C., particularly 20 to 150 ° C.
- the Grignard reagent when oxygen is present in the Grignard reagent or in the reaction system between the Grignard reagent and the alkoxysilane compound, the Grignard reagent reacts with oxygen during the production / reaction stage, and the yield of the target polymerizable silane compound decreases. Therefore, these are preferably performed in an inert atmosphere such as nitrogen or argon.
- the above viscosity reducing agents can be used singly or in combination of two or more.
- the viscosity reducing agent according to the present invention has at least one polymerizable double bond, and has a refractive index at the D-line (589.3 nm) of the cured product, that is, a high refractive index in which n D is 1.60 or more.
- the high refractive index polymerizable compound is not particularly limited as long as it is a compound having a polymerizable group as described above and having a high refractive index of 1.60 or higher in the cured product. And reactive polysiloxanes and specific fluorene compounds.
- the reactive polysiloxane includes a polycondensate of an alkoxysilicon compound A represented by the formula [4], an alkoxysilicon compound A represented by the formula [4], and an alkoxysilicon compound B represented by the formula [5]. And at least one of polycondensates.
- X has a phenyl group having at least one substituent having a polymerizable double bond, a naphthyl group having at least one substituent having a polymerizable double bond, and a polymerizable double bond.
- Ar 3 is phenyl optionally substituted by an alkyl group having 1 to 6 carbon atoms Group, a condensed ring hydrocarbon group having a plurality of benzene ring structures (which may be substituted with an alkyl group having 1 to 6 carbon atoms), or a hydrocarbon ring in which a plurality of aromatic rings are directly bonded by a single bond It represents an assembly group (which may be substituted with an alkyl group having 1 to 6 carbon atoms), and R 3 represents a methyl group, an ethyl group, or an isopropyl group.
- X in the formula [4] include the groups exemplified as the group X in the formula [1] in the compound represented by the formula [1].
- the group mentioned as a preferable group in group X can be mentioned.
- specific examples of Ar 4 in the above formula [4] include groups exemplified as the group Ar 1 in the above formula [1], and particularly exemplified as preferred groups in the group Ar 1 in the formula [4]. The group can be mentioned.
- the compound quoted as a specific example of the compound represented by the said Formula [1] is mentioned.
- Ar 4 is a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a condensed ring hydrocarbon group having a plurality of benzene ring structures (an alkyl group having 1 to 6 carbon atoms) Or a hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded with a single bond (which may be substituted with an alkyl group having 1 to 6 carbon atoms), and R 4 represents a methyl group, an ethyl group, or an isopropyl group.
- Examples of the phenyl group optionally substituted by an alkyl group having 1 to 6 carbon atoms represented by Ar 4 include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, 2, 4, 6 -Trimethylphenyl group, 4-tert-butylphenyl group.
- Examples of the condensed ring hydrocarbon group having a plurality of benzene ring structures represented by Ar 4 include monovalent groups derived from naphthalene, phenanthrene, anthracene, triphenylene, pyrene, chrysene, naphthacene, biphenylene, and fluorene.
- examples of the alkyl group having 1 to 6 carbon atoms that may be substituted include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group.
- Ar 4 is preferably a condensed ring hydrocarbon group having a plurality of benzene ring structures (which may be substituted with an alkyl group having 1 to 6 carbon atoms), and more preferably a phenanthryl group.
- the compound represented by the formula [5] include, for example, trimethoxy (phenyl) silane, triethoxy (phenyl) silane, trimethoxy (p-tolyl) silane, trimethoxy (1-naphthyl) silane, triethoxy (1- Naphthyl) silane, triisopropoxy (1-naphthyl) silane, trimethoxy (2-naphthyl) silane, triethoxy (2-naphthyl) silane, triisopropoxy (2-naphthyl) silane, trimethoxy (2-phenanthryl) silane, trimethoxy ( 3-phenanthryl) silane, trimethoxy (9-phenanthryl) silane, triethoxy (9-phenanthryl) silane, triisopropoxy (9-phenanthryl) silane, [1,1′-biphenyl] -4-yltrimethoxysilane, [1
- the alkoxysilicon compound constituting the reactive polysiloxane includes the alkoxysilicon compound B represented by the formula [5] in addition to the alkoxysilicon compound A represented by the formula [4],
- the compounding molar ratio concerning a condensation reaction is not specifically limited, Usually, the range of 9 mol or less of alkoxy silicon compounds B is preferable with respect to 1 mol of alkoxy silicon compounds A from the objective of stabilizing the physical property of hardened
- the blending molar ratio of the alkoxysilicon compound B to the blending mole number of the alkoxysilicon compound A is 9 or less, a sufficient crosslinking density is obtained, the dimensional stability against heat is further improved, and a higher refractive index, A cured product having a low Abbe number can be obtained.
- the above-mentioned alkoxysilicon compound A and alkoxysilicon compound B compounds can be appropriately selected and used as necessary, and plural kinds of compounds can be used in combination. In this case, the molar ratio of the total amount of the alkoxysilicon compound A and the total molar amount of the alkoxysilicon compound B also falls within the above range.
- the polycondensation reaction of the alkoxysilicon compound A represented by the above formula [4], or the alkoxy containing the alkoxysilicon compound A represented by the above formula [4] and the alkoxysilicon compound B represented by the above formula [5] The polycondensation reaction of the silicon compound is preferably carried out in the presence of an acid or basic catalyst.
- the type of the catalyst used for the polycondensation reaction is not particularly limited as long as it is dissolved or uniformly dispersed in a solvent described later, and can be appropriately selected and used as necessary.
- catalysts examples include acidic compounds such as inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, organic acids such as acetic acid and oxalic acid; basic compounds such as alkali metal hydroxides and alkaline earth metal hydroxides. Products, ammonium hydroxide, quaternary ammonium salts, amines; examples of fluoride salts include NH 4 F and NR 4 F.
- R represents a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms.
- Examples of the acidic compound include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, and boric acid.
- Examples of the basic compound include sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, hydroxide Examples include tetrabutylammonium and triethylamine.
- fluoride salt examples include ammonium fluoride, tetramethylammonium fluoride, and tetrabutylammonium fluoride.
- one or more selected from the group consisting of hydrochloric acid, acetic acid, potassium hydroxide, calcium hydroxide, barium hydroxide and tetraethylammonium hydroxide are preferably used.
- the amount of the catalyst used is 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the total mass of the alkoxysilicon compound.
- the reaction proceeds more favorably when the amount of the catalyst used is 0.01% by mass or more. In consideration of economy, the use of 10% by mass or less is sufficient.
- the reactive polysiloxane (polycondensate) is characterized by the structure of the alkoxysilicon compound A, and the reactive group (polymerizable double bond) contained in the alkoxysilicon compound A is a radical or a cation.
- the polymer is easily polymerized, and exhibits high heat resistance after polymerization (after curing).
- the hydrolysis polycondensation reaction of the alkoxysilicon compound A or the hydrolysis polycondensation reaction of the alkoxysilicon compound A and the alkoxysilicon compound B can be carried out in the absence of a solvent.
- reaction solvent tetrahydrofuran (THF) described later.
- THF tetrahydrofuran
- a solvent inert to the alkoxysilicon compound to be used as the reaction solvent.
- the synthesis reaction of the reactive polysiloxane may be performed without a solvent as described above, but there is no problem even if a solvent is used to make the reaction more uniform.
- the solvent is not particularly limited as long as it does not react with the alkoxysilicon compound to be used and dissolves the polycondensate thereof.
- Examples of such a reaction solvent include ketones such as acetone and methyl ethyl ketone (MEK); aromatic hydrocarbons such as benzene, toluene and xylene; tetrahydrofuran (THF), 1,4-dioxane, diisopropyl ether, cyclopentylmethyl, and the like.
- Ethers such as ether (CPME); glycols such as ethylene glycol, propylene glycol, hexylene glycol; glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, diethyl carbitol; N- Examples include amides such as methyl-2-pyrrolidone (NMP) and N, N-dimethylformamide (DMF). These solvents may be used alone or in combination of two or more.
- NMP methyl-2-pyrrolidone
- DMF N-dimethylformamide
- the reactive polysiloxane used in the present invention is an alkoxysilicon compound A represented by the formula [4], or an alkoxysilicon compound A represented by the formula [4] and an alkoxysilicon compound represented by the formula [5]. It can be obtained by subjecting an alkoxysilicon compound containing B to hydrolysis polycondensation in the presence of an acid or a basic catalyst.
- the reaction temperature for the hydrolysis polycondensation is 20 to 150 ° C, more preferably 30 to 120 ° C.
- the reaction time is not particularly limited as long as it is longer than the time necessary for the molecular weight distribution of the polycondensate to increase and to stabilize the molecular weight distribution, and more specifically, several hours to several days.
- the obtained reactive polysiloxane After completion of the polycondensation reaction, it is preferable to collect the obtained reactive polysiloxane by any method such as filtration and evaporation of the solvent, and appropriately perform a purification treatment as necessary.
- an alkoxysilicon compound A represented by the formula [4] is used, or alternatively, an alkoxysilicon compound A represented by the formula [4] and the formula [5].
- Examples include a method in which an alkoxysilicon compound containing the represented alkoxysilicon compound B is polycondensed in the presence of a base and the base is removed using a cation exchange resin.
- the base and the amount used thereof may be one or more compounds selected from the group consisting of the basic compounds and fluoride salts described above, and the amount used may be employed, preferably potassium hydroxide, calcium hydroxide, hydroxide
- One or more selected from the group consisting of barium and tetraethylammonium hydroxide can be used as the base.
- the reaction conditions and the like used for the polycondensation reaction, the reaction solvent, and the like can be those described above.
- finish of reaction as a cation exchange resin used for removal of a base, the ion exchange resin which has a sulfo group as an ionic group is used preferably.
- cation exchange resin those having a base structure generally used such as styrene (styrene-divinylbenzene copolymer), acrylic and the like can be used.
- any of strong acid cation exchange resin which has a sulfo group as an ionic group, and weak acid cation exchange resin which has a carboxy group as an ionic group may be sufficient.
- a form of a cation exchange resin various things, such as granular form, fibrous form, and film form, can be used.
- these cation exchange resins commercially available ones can be suitably used.
- a strongly acidic cation exchange resin having a sulfo group as an ionic group is preferably used.
- Examples of commercially available strong acid cation exchange resins include Amberlite (registered trademark) 15, 200, 200C, 200CT, 252, 1200H, IR120B, IR120H, IR122Na, IR124, IRC50, IRC86, IRN77, IRP77, IRP-64, IRP-69, CG-50, CG-120, Amberjet (registered trademark) 1020, 1024, 1060, 1200, 1220, Amberlist (registered trademark) 15, 15 DRY, 15 JWET, 16, 16 WET, 31 WET, 35 WET, 36, Dowex (registered trademark) 50 Wx2, 50 Wx4, 50 Wx8, DR-2030, DR-G8, HCR-W2, 650C UPW, G- 6, 88, M-31, N-406, Dowex (registered trademark) Monosphere (registered trademark) 650C, 88, M-31, 99K / 320, 99K / 350, 99Ca / 320, Dowex Marathon
- Examples of commercially available weakly acidic cation exchange resins include Amberlite (registered trademark) CG-50, FPC3500, IRC50, IRC76, IRC86, IRP-64, and Dowex (registered trademark). MAC-3 [above, manufactured by Dow Chemical Co.]; Diaion (registered trademark) CWK30 / S, WK10, WK11, WK40, WK100, WT01S [above, manufactured by Mitsubishi Chemical Corporation] .
- the polycondensation compound obtained by such a reaction has a weight average molecular weight Mw measured in terms of polystyrene by GPC of 500 to 100,000, preferably 500 to 30,000. Dispersity: Mw (weight average molecular weight ) / Mn (number average molecular weight) is 1.0 to 10.
- the reactive polysiloxane is a [X (Ar 1) SiO] is a compound having at least a siloxane unit represented by, for example, [X (Ar 1) SiO] and [Ar 2 SiO 3/2] A compound having at least a siloxane unit and having a crosslinked structure.
- the fluorene compound is a compound represented by the following formula [6].
- R 5 and R 6 each independently represent a hydrogen atom or a methyl group
- L 1 and L 2 each independently represent a phenylene group optionally having a substituent, or Represents an optionally substituted naphthalenediyl group
- L 3 and L 4 each independently represent an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms.
- M and n each independently represent 0 or a positive integer satisfying 0 ⁇ m + n ⁇ 40.
- Examples of the phenylene group optionally having a substituent represented by L 1 and L 2 include an o-phenylene group, an m-phenylene group, a p-phenylene group, a 2-methylbenzene-1,4-diyl group, Examples include 2-aminobenzene-1,4-diyl group, 2,4-dibromobenzene-1,3-diyl group, and 2,6-dibromobenzene-1,4-diyl group.
- Examples of the naphthalenediyl group optionally having a substituent represented by L 1 and L 2 include 1,2-naphthalenediyl group, 1,4-naphthalenediyl group, 1,5-naphthalenediyl group, Examples include 1,8-naphthalenediyl group, 2,3-naphthalenediyl group, and 2,6-naphthalenediyl group.
- alkylene group having 1 to 6 carbon atoms represented by L 3 and L 4 examples include methylene group, ethylene group, trimethylene group, 1-methylethylene group, tetramethylene group, 1-methyltrimethylene group, 1,1 -Dimethylethylene group, pentamethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-ethyltrimethylene group, hexamethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1-ethyltetramethylene group, 1,1,2-trimethyltrimethylene group , 1,2,2-methyltrimethylene group, 1-ethyl-1-methyltrimethylene group, and a 1-ethyl-2-methylmethyl
- n and n each independently preferably satisfy 0 ⁇ m + n ⁇ 30, and more preferably satisfy 2 ⁇ m + n ⁇ 20.
- the compound represented by the formula [6] include 9,9-bis (4- (2- (meth) acryloyloxyethoxy) phenyl) -9H-fluorene, Ogsol (registered trademark) EA- 0200, EA-0300, EA-F5003, EA-F5503, EA-F5510, EA-F5710, GA-5000 [above, manufactured by Osaka Gas Chemical Co., Ltd.], NK Ester A-BPEF [New Nakamura Chemical Co., Ltd.], but is not limited thereto (in the present invention, (meth) acryloyl group means both acryloyl group and methacryloyl group).
- compounds suitable as the high refractive index polymerizable compound include compounds represented by the following formula [7-1], compounds having a structural unit represented by the formula [7-2], and formula [7-2] And a structural unit represented by the formula [7-3].
- two Q's are the same group and each represents a group selected from the group consisting of a vinyloxy group, an allyloxy group and a (meth) acryloyloxy group, and two p's are the same An integer of 0 to 3 is shown.
- Ar 5 and Ar 6 each independently represent a phenyl group, a naphthyl group, or a phenanthryl group.
- Particularly suitable compounds as the high refractive index polymerizable compound include compounds represented by the following formula [7-1-1], compounds having a structural unit represented by the formula [7-2-1], and formula [7 -2-1] and a compound having a structural unit represented by the formula [7-3-1].
- the above high refractive index polymerizable compounds can be used singly or in combination of two or more.
- the present invention is also directed to a polymerizable composition
- a polymerizable composition comprising (a) 100 parts by mass of the high refractive index polymerizable compound and (b) 10 to 500 parts by mass of the viscosity reducing agent.
- any one of (a) a high refractive index polymerizable compound and (b) a viscosity reducing agent can be used alone or in combination of two or more.
- the polymerizable composition may further contain (c) a polymerizable diluent whose substance at 23 ° C. is liquid under 1013.25 hPa, and (d) a polymerization initiator.
- the polymerizable diluent that can be used in the polymerizable composition of the present invention is a compound in which the state of a substance at 23 ° C. is 1013.25 hPa and is also called a liquid diluent.
- the polymerizable diluent can be used for the purpose of 1) adjusting the viscosity of the polymerizable composition and 2) adjusting the cross-linking density when the polymerizable composition is cured.
- Use of the polymerizable diluent can further enhance the effect of reducing and maintaining the viscosity of the above-described viscosity reducing agent.
- polymerizable diluent examples include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, tricyclo [5.2.
- the polymerizable diluent is available as a commercial product. Specific examples thereof include NK ester 701A, A-DCP, A-DON-N, A-HD-N, A-NOD- N, DCP, DOD-N, HD-N, NOD-N, NPG, A-TMM-3, A-TMM-3L, A-TMM-3LMN, A-TMPT, TMPT, A-TMMT, AD-TMP, A-DPH, A-9550, A-9530, ADP-51EH, ATM-31EH, UA-7100, A-LEN-10 Nakamura Chemical Co., Ltd.], KAYARAD (registered trademark) T-1420, D-330, D-320, D-310, DPCA-20, DPCA-30, DPCA-60, DPCA -120, the same TMPTA, the same ET-30, the DPHA, the DPHA-2C [manufactured by Nippon Kayaku Co., Ltd.], and.
- the polymerizable diluent may be used alone or in combination of two or more.
- the addition amount is 10 to 500 parts by mass with respect to 100 parts by mass of component (a), and 0.1 to 40 parts by mass when the entire polymerizable composition is 100 parts by mass. It is preferably 5 to 30 parts by mass. If the amount exceeds 30 parts by mass, the refractive index may drop, and the high refractive index that is the main purpose of the present invention may not be maintained.
- the polymerizable composition of the present invention may further contain a polymerization initiator.
- a polymerization initiator any of a photopolymerization initiator and a thermal polymerization initiator can be used.
- photopolymerization initiator examples include alkylphenones, benzophenones, Michler's ketones, acylphosphine oxides, benzoylbenzoates, oxime esters, tetramethylthiuram monosulfides, and thioxanthones.
- photocleavable photoradical polymerization initiators are preferred.
- commercially available radical photopolymerization initiators include IRGACURE (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, and CGI 1850.
- thermal polymerization initiator examples include azos and organic peroxides.
- thermal polymerization initiator examples include azos and organic peroxides.
- examples of commercially available azo-based thermal polymerization initiators include V-30, V-40, V-59, V-60, V-65, and V-70 [above, manufactured by Wako Pure Chemical Industries, Ltd.] Can be mentioned.
- examples of commercially available organic peroxide thermal polymerization initiators include, for example, Parkadox (registered trademark) CH, BC-FF, 14, 16 and Trigonox (registered trademark) 22, 23, 121.
- the polymerization initiators may be used alone or in combination of two or more. Further, the addition amount thereof is preferably 0.1 to 20 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the polymerizable component, that is, the components (a) and (b) (and optionally (c) component if desired). Is 0.3 to 10 parts by mass.
- the polymerizable composition of the present invention is, for example, a chain transfer agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a leveling agent, and a rheology modifier as long as the effects of the present invention are not impaired. Further, it can contain an adhesion aid such as a silane coupling agent, a pigment, a dye, and an antifoaming agent.
- chain transfer agent examples include, as thiol compounds, methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, 3-methoxybutyl 3-mercaptopropionate, n-mercaptopropionate n- Octyl, stearyl 3-mercaptopropionate, 1,4-bis (3-mercaptopropionyloxy) butane, 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolethane tris (3-mercaptopropionate) , Trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mer) Ptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipenta
- the chain transfer agent When a chain transfer agent is added, the chain transfer agent may be used alone or in combination of two or more.
- the addition amount thereof is preferably 0.01 to 20 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the polymerizable component, that is, the above component (a) and component (b) (and optionally (c) component). Is 0.1 to 10 parts by mass.
- antioxidants examples include phenol-based antioxidants, phosphoric acid-based antioxidants, sulfide-based antioxidants, etc. Among them, phenol-based antioxidants are preferable.
- phenolic antioxidant examples include IRGANOX (registered trademark) 245, 1010, 1035, 1076, 1135 [above, manufactured by BASF Japan Ltd.], Sumilizer (registered trademark) GA-80, GP MDP-S, BBM-S, WX-R [above, manufactured by Sumitomo Chemical Co., Ltd.], ADK STAB (registered trademark) AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 [above, manufactured by ADEKA Corporation].
- the antioxidants When adding an antioxidant, the antioxidants may be used alone or in combination of two or more.
- the addition amount thereof is preferably 0.01 to 20 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the polymerizable component, that is, the above component (a) and component (b) (and optionally (c) component). Is 0.1 to 10 parts by mass.
- the method for preparing the polymerizable composition of the present embodiment is not particularly limited.
- a preparation method for example, the components (a) and (b) and, if necessary, the components (c) and (d) are mixed at a predetermined ratio, and other additives are further added as necessary.
- a method of making a uniform solution, among these components for example, after mixing a part of component (a) and component (b) to make a uniform solution, add the remaining components, and add others as desired Examples thereof include a method in which an agent is further added and mixed to form a uniform solution, or a method in which a conventional solvent is used in addition to these components.
- the ratio of the solid content in the present polymerizable composition is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1 to 50% by mass, or 1 to 30 % By mass or 1 to 25% by mass.
- the solid content is obtained by removing the solvent component from all components of the polymerizable composition.
- the solution of the polymerizable composition is preferably used after being filtered using a filter having a pore size of 0.1 to 5 ⁇ m.
- the polymerizable composition can be exposed (photocured) or heated (thermally cured) to obtain a cured product, and the present invention is also directed to a cured product of the polymerizable compound.
- light rays to be exposed include ultraviolet rays, electron beams, and X-rays.
- the light source used for ultraviolet irradiation for example, sunlight, chemical lamp, low-pressure mercury lamp, high-pressure mercury lamp, metal halide lamp, xenon lamp, or UV-LED can be used.
- the post-baking method is not particularly limited, but is usually performed in a range of 50 to 260 ° C.
- thermosetting The heating conditions in the thermosetting are not particularly limited, but are usually appropriately selected from the range of 50 to 300 ° C. and 1 to 120 minutes. Moreover, it does not specifically limit as a heating means, For example, a hotplate and oven are mentioned.
- a cured product obtained by curing the polymerizable composition of the present invention has a refractive index as high as 1.620 or more at a wavelength of 589.3 nm (D-line), and further has a Abbe number of 23 or less. It is also possible to produce a product, and since it can be expected to have dimensional stability by suppressing generation of cracks and peeling from the support by heating, it is suitable as a material for high refractive index resin lenses. Can be used for
- the polymerizable composition of the present invention can be formed into various molded products in parallel with the formation of a cured product by using a conventional molding method such as compression molding (imprinting, etc.), casting, injection molding, blow molding and the like. Can be easily manufactured.
- the molded body thus obtained is also an object of the present invention.
- a step of filling the polymerizable composition of the present invention into a space between a supporting substrate and a mold that are in contact with each other or a space inside a mold that can be divided, the filled composition A step of exposing and photopolymerizing the obtained photopolymerized product from the space filled with the mold, and a step of heating the photopolymerized product before, during or after the mold release.
- the method of including is mentioned.
- the exposure and photopolymerization step can be carried out by applying the conditions shown in the above ⁇ cured product >>.
- the conditions for the heating step are not particularly limited, but are usually appropriately selected from the range of 50 to 260 ° C. and 1 to 120 minutes. Moreover, it does not specifically limit as a heating means, For example, a hotplate, oven, etc. are mentioned.
- the molded body produced by such a method can be suitably used as a camera module lens.
- Microscope stage automatic temperature control system ThermoPlate (registered trademark) Temperature rising rate: 0.5 ° C./second Measuring method: The temperature at which a part of the sample started to melt visually was taken as the melting point.
- Viscosity Device EMS-1000 manufactured by Kyoto Electronics Industry Co., Ltd.
- Transmittance UV-Vis near-infrared spectrophotometer V-670 manufactured by JASCO Corporation Reference: Air
- NMA Naphthalen-2-ylmethyl acrylate
- VN 2-vinylnaphthalene [manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.]
- SPeDMS dimethoxy (phenanthren-9-yl) (4-vinylphenyl) silane
- BPOEA 2-([1,1′-biphenyl] -2-yloxy) ethyl acrylate
- BnA benzyl acrylate [Osaka Organic Chemical Co., Ltd.
- I184 1-hydroxycyclohexyl phenyl ketone [IRGACURE (registered trademark) 184, manufactured by BASF Japan Ltd.]
- TPO Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide [IRGACURE (registered trademark) TPO manufactured by BASF Japan Ltd.]
- PGMEA Propylene glycol monomethyl ether acetate
- THF Tetrahydrofuran
- a Grignard reagent was prepared.
- 131.9 g (0.58 mol) of STMS and 259 g of THF were charged, and the air in the flask was replaced with nitrogen using a nitrogen balloon.
- the above Grignard reagent was added dropwise over 30 minutes under reflux (approximately 66 ° C.), and the mixture was further refluxed for 24 hours.
- THF was distilled off under reduced pressure using an evaporator. After adding 1,000 g of hexane to the obtained residue and refluxing for 1 hour to dissolve the soluble matter, the insoluble matter was filtered off.
- a cation exchange resin [Amberlyst (registered trademark) 15JWET] manufactured by Dow Chemical Co., Ltd.] preliminarily washed with THF and a filter aid [KC Flock W-100GK manufactured by Nippon Paper Industries Co., Ltd.] were added to this reaction mixture.
- a filter aid [KC Flock W-100GK manufactured by Nippon Paper Industries Co., Ltd.] were added to this reaction mixture.
- 1.2 g was added and the reaction was stopped by stirring for 1 hour.
- the cation exchange resin and the filter aid were filtered through a membrane filter having a pore size of 0.5 ⁇ m, and further washed with 30 g of ethyl acetate.
- the filtrate and washing solution were combined and added to 897 g of methanol to precipitate the polymer.
- the precipitate was filtered and dried to obtain 18.9 g of the target high refractive index polymerizable compound 1 (hereinafter sometimes abbreviated as PSPeDMS).
- the weight average molecular weight Mw of the obtained compound measured in terms of polystyrene by GPC was 610, and the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) was 1.2.
- the cation exchange resin and the filter aid were filtered through a membrane filter having a pore size of 0.5 ⁇ m, and further washed with 18 g of ethyl acetate.
- the filtrate and the washing solution were combined and added to 538 g of methanol to precipitate the polymer.
- the precipitate was filtered and dried to obtain 14.8 g of a target high refractive index polymerizable compound 2 (hereinafter sometimes abbreviated as XPe55).
- the weight average molecular weight Mw of the obtained compound measured in terms of polystyrene by GPC was 1,000, and the degree of dispersion: Mw / Mn was 1.0.
- the SPeDMS, NMA, VN, or BPOEA 100 parts by mass, I184 1 part by mass, and PGMEA 233 parts by mass were mixed.
- This solution was filtered with a PTFE syringe filter having a pore size of 0.2 ⁇ m to obtain a varnish with a solid content concentration of 30% by mass.
- Each varnish was spin-coated (1,500 rpm ⁇ 30 seconds) on a silicon wafer and dried by heating on a hot plate at 80 ° C. for 1 minute.
- This coating film was exposed to UV at 20 mW / cm 2 for 250 seconds under a nitrogen atmosphere, and further heated on a hot plate at 150 ° C. for 20 minutes to produce a cured film having a thickness of 1.0 ⁇ m.
- the Abbe number ⁇ D at a wavelength of 589 nm (D line) of the obtained cured film was measured. The results are also shown in Table 1.
- Example 1 Preparation of polymerizable composition 1 2 parts by mass of VN as a viscosity reducing agent for component (b), 6 parts by mass of FDA as a high refractive index polymerizable compound for component (a), and polymerizability for component (c)
- a diluent 2 parts by mass of BnA was blended and stirred at 40 ° C. for 2 hours.
- 0.1 part by mass of I184 and 0.07 part by mass of TPO were added as a polymerization initiator for the component (d), and the mixture was stirred at 40 ° C. for 1 hour.
- 0.3 mass part of DDT was added here as a chain transfer agent (reaction accelerator), and the polymerizable composition 1 was obtained as a uniform transparent varnish by stirring at room temperature (approximately 23 ° C.) for 2 hours.
- Table 3 shows the viscosity of each polymerizable composition at 25 ° C.
- Example 2 by blending the low-viscosity agent of the present invention, a lower viscosity and a lower Abbe number ⁇ D are realized, and the refractive index n D and transmission are compared with the case of not blending the low-viscosity agent. The results were also obtained that the rate could be improved to the same or higher value (see Examples 1 and 3 and Comparative Example 1, Example 4 and Comparative Example 2, Example 5 and Comparative Example 3).
- Example 2 low viscosity and high refractive index and high transmittance were realized by blending the low viscosity agent, but the ratio of the high refractive index polymerizable compound in the polymerizable composition was reduced. As a result, the Abbe number increased.
- BPOEA which is a conventional liquid diluent, was able to maintain a reduced viscosity or a viscosity of 10,000 mPa ⁇ s or less as in the case of the present invention, but the Abbe number increased (Examples). 5 and Comparative Example 5, Example 7 and Comparative Example 6, Example 9 and Comparative Example 7). In addition, compared with the example without a viscosity reducing agent, BPOEA resulted in an increase in Abbe number on the contrary (see Comparative Examples 3 and 5 and Comparative Examples 4 and 7).
- This coating film was exposed to UV at 20 mW / cm 2 for 250 seconds under a nitrogen atmosphere, and further heated on a hot plate at 150 ° C. for 20 minutes to produce a cured film having a thickness of 1.0 ⁇ m.
- the refractive index and Abbe number ⁇ D at a wavelength of 589 nm (D line) of the obtained cured film were measured. The results are shown in Table 4.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
そして近年、樹脂レンズの製造にあたり、歩留まりや生産効率向上、さらにはレンズ積層時の光軸ずれの抑制のために、熱可塑性樹脂の射出成型から、室温で液状の硬化性樹脂を使った押し付け成形によるウェハレベル成形への移行が盛んに検討されている。
低アッベ数を特徴とした材料においては、高い屈折率に加え高い透明性も求められることとなるが、これらの光学特性の向上を図ると材料の粘度が増加し、ハンドリング性が著しく悪化することが多い。これは一般に、高屈折率に寄与する成分は電子密度が高く、そのため高粘度化し易いことに起因するものであり、ハンドリング性の悪化は低アッベ材料の開発において本質的な課題といえる。
前述したように、低アッベ化と低粘度化はトレードオフの関係にあり、例えば10,000mPa・s以下の低い粘度を実現するとともに、硬化物において1.60以上の高い屈折率、23以下の低アッベ数といった優れた光学特性を実現した光学材料は未だ無い。
また、従来の低粘度化を達成するための希釈剤は一般に低屈折率であり、一方、近年の高解像度カメラモジュール用レンズ向けなどの光学材料に求められる光学特性(高屈折率・低アッベ数・高透明性)はより一層高まっていることから、従来の希釈剤(低粘度化剤)の配合によって却って光学材料の高アッベ化を招き得るものとなっている。
本発明は、このような事情に鑑みてなされたものであり、低アッベ化と低粘度化とのトレードオフを打破し、配合した際に屈折率の損失が少ない、高屈折率な低粘度化剤とそれを含む重合性組成物を提供することを課題とするものである。
重合性二重結合を少なくとも1つ有し、その硬化物のD線(589.3nm)における屈折率が1.60以上である高屈折率重合性化合物の低粘度化剤として使用する方法に関する。
第2観点として、前記低粘度化剤が、炭素原子数1乃至6のアルキル基で置換されていてもよいフェニル基又はフェニレン基、複数のベンゼン環構造を有する1価又は2価の縮合環炭化水素基(炭素原子数1乃至6のアルキル基で置換されていてもよい)、及び、複数の芳香環が単結合で直接結合している1価又は2価の炭化水素環集合基(炭素原子数1乃至6のアルキル基で置換されていてもよい)からなる群から選択される芳香族基を少なくとも1つ有し、且つ、
ビニル基、アリル基、(メタ)アリルオキシ基及び(メタ)アクリロイル基からなる群から選択される重合性二重結合を有する基を少なくとも1つ有する化合物である、
第1観点に記載の方法に関する。
第3観点として、前記低粘度化剤が、下記式[1]で表される化合物である、第2観点に記載の方法に関する。
(式中、Xは重合性二重結合を有する置換基を少なくとも1つ有するフェニル基、重合性二重結合を有する置換基を少なくとも1つ有するナフチル基、重合性二重結合を有する置換基を少なくとも1つ有するビフェニル基、又は重合性二重結合を有する置換基を少なくとも1つ有するフェナントリル基を表し、Ar1は複数のベンゼン環構造を有する縮合環炭化水素基(炭素原子数1乃至6のアルキル基で置換されていてもよい)、又は複数の芳香環が単結合で直接結合している炭化水素環集合基(炭素原子数1乃至6のアルキル基で置換されていてもよい)を表し、R1はメチル基、エチル基、又はイソプロピル基を表す。)
第4観点として、前記低粘度化剤が、下記式[2]で表される化合物である、第2観点に記載の方法に関する。
(式中、Ar2はq価の芳香族炭化水素残基を表し、qは1又は2を表し、
Yは単結合、-O-C(=O)-基、又は-O-基を表し、R2は水素原子又はメチル基を表す。)
第5観点として、前記低粘度化剤が、下記式[3-1]又は式[3-2]で表される化合物である、第2観点に記載の方法に関する。
(式中、R1はメチル基、エチル基、又はイソプロピル基を表す。)
第6観点として、重合性二重結合を少なくとも1つ有し、その硬化物のD線(589.3nm)における屈折率が1.60以上である高屈折率重合性化合物の低粘度化剤であって、
1013.25hPa下、23℃における物質の状態が固体であり、100℃未満の融点を有する化合物であって、100℃における粘度が10mPa・s以下であり、その硬化物のD線(589.3nm)におけるアッベ数が23以下である化合物からなる、低粘度化剤に関する。
第7観点として、(a)重合性二重結合を少なくとも1つ有し、その硬化物のD線(589.3nm)における屈折率が1.60以上である高屈折率重合性化合物 100質量部、及び
(b)1013.25hPa下、23℃における物質の状態が固体であり、100℃未満の融点を有する化合物であって、100℃における粘度が10mPa・s以下であり、その硬化物のD線(589.3nm)におけるアッベ数が23以下である化合物からなる、低粘度化剤 10~500質量部
を含む、重合性組成物に関する。
第8観点として、前記(a)高屈折率重合性化合物が、式[4]で表されるアルコキシケイ素化合物Aの重縮合物、及び式[4]で表されるアルコキシケイ素化合物Aと式[5]で表されるアルコキシケイ素化合物Bとの重縮合物の少なくとも一方を含む、反応性ポリシロキサンを含む、第7観点に記載の重合性組成物に関する。
(式中、Xは重合性二重結合を有する置換基を少なくとも1つ有するフェニル基、重合性二重結合を有する置換基を少なくとも1つ有するナフチル基、重合性二重結合を有する置換基を少なくとも1つ有するビフェニル基、又は重合性二重結合を有する置換基を少なくとも1つ有するフェナントリル基を表し、Ar3は炭素原子数1乃至6のアルキル基で置換されていてもよいフェニル基、複数のベンゼン環構造を有する縮合環炭化水素基(炭素原子数1乃至6のアルキル基で置換されていてもよい)、又は複数の芳香環が単結合で直接結合している炭化水素環集合基(炭素原子数1乃至6のアルキル基で置換されていてもよい)を表し、R3はメチル基、エチル基、又はイソプロピル基を表す。)
(式中、Ar4は炭素原子数1乃至6のアルキル基で置換されていてもよいフェニル基、複数のベンゼン環構造を有する縮合環炭化水素基(炭素原子数1乃至6のアルキル基で置換されていてもよい)、又は複数の芳香環が単結合で直接結合している炭化水素環集合基(炭素原子数1乃至6のアルキル基で置換されていてもよい)を表し、R4はメチル基、エチル基、又はイソプロピル基を表す。)、
第9観点として、前記(a)高屈折率重合性化合物が、式[6]で表されるフルオレン化合物を含む、第7観点に記載の重合性組成物に関する。
(式中、R5及びR6はそれぞれ独立して、水素原子又はメチル基を表し、L1及びL2はそれぞれ独立して、置換基を有していてもよいフェニレン基、又は置換基を有していてもよいナフタレンジイル基を表し、L3及びL4はそれぞれ独立して、炭素原子数1乃至6のアルキレン基を表し、m及びnはそれぞれ独立して、0≦m+n≦40を満たす0又は正の整数を表す。)
第10観点として、前記(a)高屈折率重合性化合物が、下記式[7-1]で表される化合物、式[7-2]で表される構造単位を有する化合物、並びに式[7-2]で表される構造単位及び式[7-3]で表される構造単位を有する化合物からなる群から選択される、第7観点に記載の重合性組成物に関する。
(式中、2つのQはそれぞれ同一の基であって、ビニルオキシ基、アリルオキシ基及び(メタ)アクリロイルオキシ基からなる群から選択される基を表し、2つのpはそれぞれ同一に0乃至3の整数を示す。)
(式中、Ar5及びAr6は、それぞれ独立して、フェニル基、ナフチル基、又はフェナントリル基を表す。)
第11観点として、(c)1013.25hPa下、23℃における物質の状態が液体である重合性希釈剤をさらに含む、第7観点乃至第10観点のうち何れか一に記載の重合性組成物に関する。
第12観点として、第7観点乃至第11観点の何れか一に記載の重合性組成物の硬化物に関する。
第13観点として、第7観点乃至第11観点の何れか一に記載の重合性組成物からなる高屈折率樹脂レンズ用材料に関する。
第14観点として、第7観点乃至第11観点の何れか一に記載の重合性組成物から作製された、樹脂レンズに関する。
第15観点として、第7観点乃至第11観点の何れか一に記載の重合性組成物を、接し合う支持体と鋳型との間の空間、又は分割可能な鋳型の内部の空間に充填する工程、及び当該充填された組成物を露光して光重合する工程、を含む成形体の製造方法に関する。
第16観点として、さらに、得られた光重合物を充填された前記空間から取り出して離型する工程、並びに、該光重合物を該離型の前、中途又は後において加熱する工程、を含む第15観点に記載の製造方法に関する。
第17観点として、前記成形体がカメラモジュール用レンズである、第15観点又は第16観点に記載の製造方法に関する。
したがって、上記重合性組成物からなる本発明の高屈折率樹脂レンズ用材料は、高解像カメラモジュール用のレンズとして好適に使用することができる。
さらに本発明の製造方法は、使用する上記重合性組成物がハンドリング性に優れたものとなっていることから、成形体、特にカメラモジュール用レンズを効率的に製造することができる。
以下、本発明の詳細を説明する。
本発明の低粘度化剤は、上記の通り、1013.25hPa(すなわち大気圧)下、23℃において固体の物質であり且つ100℃未満の融点を有し、100℃における粘度が10mPa・s以下であり、そしてその硬化物のD線(589.3nm)におけるアッベ数が23以下の化合物であれば特に限定されない。
上記化合物としては、具体的には、炭素原子数1乃至6のアルキル基で置換されていてもよいフェニル基又はフェニレン基、複数のベンゼン環構造を有する1価又は2価の縮合環炭化水素基(炭素原子数1乃至6のアルキル基で置換されていてもよい)、及び、複数の芳香環が単結合で直接結合している1価又は2価の炭化水素環集合基(炭素原子数1乃至6のアルキル基で置換されていてもよい)からなる群から選択される芳香族基を少なくとも1つ有し、且つ、ビニル基、アリル基、(メタ)アリルオキシ基及び(メタ)アクリロイル基からなる群から選択される重合性二重結合を有する基を少なくとも1つ有する化合物を挙げることができる。
また複数の芳香環が単結合で直接結合している1価又は2価の炭化水素環集合基としては、例えば、ビフェニル、テルフェニル、クアテルフェニル、ビナフタレン、フェニルナフタレン、フェニルフルオレン、ジフェニルフルオレンから誘導される1価又は2価の基が挙げられる。
なお、上記フェニル基又はフェニレン基、1価又は2価の縮合環炭化水素基及び1価又は2価の炭化水素環集合基において、置換基として有し得る炭素原子数1乃至6のアルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、シクロペンチル基、n-ヘキシル基、シクロヘキシル基が挙げられる。
これら芳香族基の中でも、溶解性や、粘度低下や低粘度化の維持における効果、また配合物において優れた光学特性(高透明性、高屈折率、低アッベ数)を実現し得る観点から、フェニル基、ナフチル基、フェナントリル基を好ましい基として挙げることができる。
上記式[1]中、Xは重合性二重結合を有する基を少なくとも1つ有するフェニル基、重合性二重結合を有する基を少なくとも1つ有するナフチル基、重合性二重結合を有する基を少なくとも1つ有するビフェニル基、又は重合性二重結合を有する基を少なくとも1つ有するフェナントリル基を表し、Ar1は複数のベンゼン環構造を有する縮合環炭化水素基(炭素原子数1乃至6のアルキル基で置換されていてもよい)、又は複数の芳香環が単結合で直接結合している炭化水素環集合基(炭素原子数1乃至6のアルキル基で置換されていてもよい)を表し、R1はメチル基、エチル基、又はイソプロピル基を表す。
また複数の芳香環が単結合で直接結合している炭化水素環集合基としては、例えば、ビフェニル、テルフェニル、クアテルフェニル、ビナフタレン、フェニルナフタレン、フェニルフルオレン、ジフェニルフルオレンから誘導される1価の基が挙げられる。
なお上記縮合環炭化水素基及び炭化水素環集合基において、置換基として有し得る炭素原子数1乃至6のアルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、シクロペンチル基、n-ヘキシル基、シクロヘキシル基が挙げられる。
上記式[2]中、Ar2はq価の芳香族炭化水素残基を表し、qは1又は2を表し、Yは単結合、-O-C(=O)-基、又は-O-基を表し、R2は水素原子又はメチル基を表す。
具体的には、炭素原子数1乃至6のアルキル基で置換されていてもよいフェニル基又はフェニレン基、複数のベンゼン環構造を有する1価又は2価の縮合環炭化水素基(炭素原子数1乃至6のアルキル基で置換されていてもよい)、又は複数の芳香環が単結合で直接結合している1価又は2価の炭化水素環集合基(炭素原子数1乃至6のアルキル基で置換されていてもよい)が挙げられる。
Ar2が表す複数のベンゼン環構造を有する1価又は2価の縮合環炭化水素基としては、例えば、ナフタレン、フェナントレン、アントラセン、トリフェニレン、ピレン、クリセン、ナフタセン、ビフェニレン、フルオレンから誘導される1価又は2価の基が挙げられる。
また複数の芳香環が単結合で直接結合している1価又は2価の炭化水素環集合基としては、例えば、ビフェニル、テルフェニル、クアテルフェニル、ビナフタレン、フェニルナフタレン、フェニルフルオレン、ジフェニルフルオレンから誘導される1価又は2価の基が挙げられる。
なお上記縮合環炭化水素基及び炭化水素環集合基において、置換基として有し得る炭素原子数1乃至6のアルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、シクロペンチル基、n-ヘキシル基、シクロヘキシル基が挙げられる。
上記式中、R1はメチル基、エチル基、又はイソプロピル基を表す。
また例えば、式[3-4]で表される化合物などの(メタ)アクリロイル基を含有するエステル化合物は慣用の方法にて製造し得、アルコール及び(メタ)アクリル酸ハロゲン化物をトリエチルアミン又はピリジン存在下でエステル化反応させることにより製造可能である。
詳細には、Ar1基を有するグリニャール試薬:Ar1-Mg-Halと、重合性二重結合を有する芳香環基を有するトリアルコキシシラン化合物:X-Si(OR1)3とを反応させて、又は、重合性二重結合を有する芳香環基を有するグリニャール試薬:X-Mg-Halと、Ar1基を有するトリアルコキシシラン化合物:Ar1-Si(OR1)3とを反応させて、式[1]で表される重合性シラン化合物を得ることができる(上記Ar1、X、R1は前記式[1]と同じ意味を表し、Halはハロゲン原子を表す)。
前記グリニャール試薬は、ハロゲン化アリール:Ar1-Hal又はX-Halと、マグネシウムとの反応により、得られる。
上記の製造温度並びに反応温度は、0~200℃、特に20~150℃の範囲が好ましい。
また、グリニャール試薬の製造時や、グリニャール試薬とアルコキシシラン化合物との反応系に酸素が存在すると、製造・反応段階でグリニャール試薬が酸素と反応し、目的物である重合性シラン化合物の収率低下の原因となるので、これらは窒素、アルゴン等の不活性雰囲気下で行うことがよい。
本発明に係る低粘度化剤は、重合性二重結合を少なくとも1つ有し、その硬化物のD線(589.3nm)における屈折率、すなわちnDが1.60以上である高屈折率重合性化合物に対して用いられる。
上記高屈折率重合性化合物としては、上述の通り重合可能な基を有し、そしてその硬化物において1.60以上の高い屈折率を有する化合物であれば特に限定されないが、例えば以下に示す特定の反応性ポリシロキサンや、特定のフルオレン化合物を挙げることができる。
上記反応性ポリシロキサンは、式[4]で表されるアルコキシケイ素化合物Aの重縮合物、及び式[4]で表されるアルコキシケイ素化合物Aと式[5]で表されるアルコキシケイ素化合物Bとの重縮合物の少なくとも一方を含む。
上記式[4]中、Xは重合性二重結合を有する置換基を少なくとも1つ有するフェニル基、重合性二重結合を有する置換基を少なくとも1つ有するナフチル基、重合性二重結合を有する置換基を少なくとも1つ有するビフェニル基、又は重合性二重結合を有する置換基を少なくとも1つ有するフェナントリル基を表し、Ar3は炭素原子数1乃至6のアルキル基で置換されていてもよいフェニル基、複数のベンゼン環構造を有する縮合環炭化水素基(炭素原子数1乃至6のアルキル基で置換されていてもよい)、又は複数の芳香環が単結合で直接結合している炭化水素環集合基(炭素原子数1乃至6のアルキル基で置換されていてもよい)を表し、R3はメチル基、エチル基、又はイソプロピル基を表す。
また上記式[4]中のAr4の具体例としては、前記式[1]中の基Ar1として挙げた基が挙げられ、特に式[4]中の基Ar1において好ましい基として挙げた基を挙げることができる。
そして上記式[4]で表される化合物の具体例としては、前記式[1]で表される化合物の具体例として挙げた化合物が挙げられる。
式[5]中、Ar4は炭素原子数1乃至6のアルキル基で置換されていてもよいフェニル基、複数のベンゼン環構造を有する縮合環炭化水素基(炭素原子数1乃至6のアルキル基で置換されていてもよい)、又は複数の芳香環が単結合で直接結合している炭化水素環集合基(炭素原子数1乃至6のアルキル基で置換されていてもよい)を表し、R4はメチル基、エチル基、又はイソプロピル基を表す。)
Ar4が表す複数のベンゼン環構造を有する縮合環炭化水素基としては、例えば、ナフタレン、フェナントレン、アントラセン、トリフェニレン、ピレン、クリセン、ナフタセン、ビフェニレン、フルオレンから誘導される1価の基が挙げられる。
また複数の芳香環が単結合で直接結合している炭化水素環集合基としては、例えば、ビフェニル、テルフェニル、クアテルフェニル、ビナフタレン、フェニルナフタレン、フェニルフルオレン、ジフェニルフルオレンから誘導される1価の基が挙げられる。
なお上記縮合環炭化水素基及び炭化水素環集合基において、置換基として有し得る炭素原子数1乃至6のアルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、シクロペンチル基、n-ヘキシル基、シクロヘキシル基が挙げられる。
上述のアルコキシケイ素化合物A及びアルコキシケイ素化合物Bは、必要に応じて適宜化合物を選択して用いることができ、またそれぞれ複数種の化合物を併用することもできる。この場合の配合モル比も、アルコキシケイ素化合物Aのモル量の総計と、アルコキシケイ素化合物Bのモル量の総計の比が、上記の範囲となる。
上記式[4]で表されるアルコキシケイ素化合物Aの重縮合反応、あるいはまた上記式[4]で表されるアルコキシケイ素化合物Aと上記式[5]で表されるアルコキシケイ素化合物Bを含むアルコキシケイ素化合物の重縮合反応は、酸又は塩基性触媒の存在下で好適に実施される。
上記重縮合反応に用いる触媒は、後述の溶媒に溶解する、又は均一分散する限りにおいては特にその種類は限定されず、必要に応じて適宜選択して用いることができる。
用いることのできる触媒としては、例えば、酸性化合物として、塩酸、硝酸、硫酸などの無機酸、酢酸、シュウ酸などの有機酸;塩基性化合物として、アルカリ金属水酸化物、アルカリ土類金属水酸化物、水酸化アンモニウム、第四級アンモニウム塩、アミン類;フッ化物塩として、NH4F、NR4Fが挙げられる。なお、ここでRは、水素原子、炭素原子数1乃至12の直鎖状アルキル基、炭素原子数3乃至12の分枝状アルキル基、炭素原子数3乃至12の環状アルキル基からなる群から選ばれる一種以上の基である。
これら触媒は、一種単独で、又は複数種を併用することもできる。
触媒の使用量は、前記アルコキシケイ素化合物の総質量に対し、0.01~10質量%、好ましくは0.1~5質量%である。触媒の使用量を0.01質量%以上とすることで反応がより良好に進行する。また、経済性を考慮すれば、10質量%以下の使用で十分である。
上記反応性ポリシロキサン(重縮合物)は、アルコキシケイ素化合物Aの構造が一つの特徴となっており、該アルコキシケイ素化合物Aに含まれる反応性基(重合性二重結合)は、ラジカル又はカチオンによって容易に重合し、重合後(硬化後)は高い耐熱性を示す。
アルコキシケイ素化合物Aの加水分解重縮合反応、あるいはまたアルコキシケイ素化合物Aとアルコキシケイ素化合物Bとの加水分解重縮合反応は、無溶媒下で行うことも可能だが、後述するテトラヒドロフラン(THF)などの、使用するアルコキシケイ素化合物に対して不活性な溶媒を反応溶媒として用いることも可能である。反応溶媒を用いる場合は、反応系を均一にしやすく、より安定した重縮合反応を行えるという利点がある。
このような反応溶媒としては、例えば、アセトン、メチルエチルケトン(MEK)等のケトン類;ベンゼン、トルエン、キシレン等の芳香族炭化水素類;テトラヒドロフラン(THF)、1,4-ジオキサン、ジイソプロピルエーテル、シクロペンチルメチルエーテル(CPME)等のエーテル類;エチレングリコール、プロピレングリコール、ヘキシレングリコール等のグリコール類;エチルセロソルブ、ブチルセロソルブ、エチルカルビトール、ブチルカルビトール、ジエチルセロソルブ、ジエチルカルビトール等のグリコールエーテル類;N-メチル-2-ピロリドン(NMP)、N,N-ジメチルホルムアミド(DMF)等のアミド類が挙げられる。これら溶媒は、一種単独で、又は二種以上を混合して用いてもよい。
反応時間は、重縮合物の分子量増加が終了し、分子量分布が安定するのに必要な時間以上なら、特に制限は受けず、より具体的には数時間から数日間である。
上記塩基並びにその使用量は、上述した塩基性化合物及びフッ化物塩からなる群から選択される一種以上の化合物、またその使用量を採用し得、好ましくは水酸化カリウム、水酸化カルシウム、水酸化バリウム及び水酸化テトラエチルアンモニウムからなる群から選ばれる一種以上のものを塩基として使用できる。
また重縮合反応に用いる反応条件等や反応溶媒等は上述したものを採用できる。
そして反応終了後、塩基の除去に使用する陽イオン交換樹脂としてはスルホ基をイオン基として有するイオン交換樹脂が好ましく用いられる。
中でも、スルホ基をイオン基として有する強酸性陽イオン交換樹脂が好ましく用いられる。
なお、上記反応性ポリシロキサンは、[X(Ar1)SiO]で表されるシロキサン単位を少なくとも有する化合物であり、例えば、[X(Ar1)SiO]と[Ar2SiO3/2]で表されるシロキサン単位を少なくとも有する、架橋構造を持つ化合物である。
上記フルオレン化合物は、下記式[6]で表される化合物である。
上記式[6]中、R5及びR6はそれぞれ独立して、水素原子又はメチル基を表し、L1及びL2はそれぞれ独立して、置換基を有していてもよいフェニレン基、又は置換基を有していてもよいナフタレンジイル基を表し、L3及びL4はそれぞれ独立して、炭素原子数1乃至6のアルキレン基、より好ましくは炭素原子数2又は3のアルキレン基を表し、m及びnはそれぞれ独立して、0≦m+n≦40を満たす0又は正の整数を表す。
また、L1及びL2が表す置換基を有していてもよいナフタレンジイル基としては、例えば、1,2-ナフタレンジイル基、1,4-ナフタレンジイル基、1,5-ナフタレンジイル基、1,8-ナフタレンジイル基、2,3-ナフタレンジイル基、2,6-ナフタレンジイル基が挙げられる。
式[7-1]中、2つのQはそれぞれ同一の基であって、ビニルオキシ基、アリルオキシ基及び(メタ)アクリロイルオキシ基からなる群から選択される基を表し、2つのpはそれぞれ同一に0乃至3の整数を示す。
式[7-2]及び[7-3]中、Ar5及びAr6は、それぞれ独立して、フェニル基、ナフチル基、又はフェナントリル基を表す。
本発明は、前記(a)高屈折率重合性化合物 100質量部と、前記(b)低粘度化剤 10~500質量部を含む、重合性組成物も対象とする。
上記重合性組成物において、(a)高屈折率重合性化合物、及び(b)低粘度化剤のいずれも、それぞれ一種を単独で、或いは二種以上を組み合わせて用いることができる。
当該重合性組成物には、さらに(c)1013.25hPa下、23℃における物質の状態が液体である重合性希釈剤、並びに、(d)重合開始剤を含んでいてもよい。
本発明の重合性組成物に使用可能な重合性希釈剤は、1013.25hPa下、23℃における物質の状態が液体である化合物であり、液状希釈剤ともいう。重合性希釈剤は、1)重合性組成物の粘度を調整するとともに、2)重合性組成物硬化時の架橋密度を調整することを目的として使用され得る。重合性希釈剤の使用より、前述の低粘度化剤の粘度の低減・維持に係る効果をより高めることができる。
本発明の重合性組成物はさらに重合開始剤を含み得る。重合開始剤としては、光重合開始剤及び熱重合開始剤の何れも使用できる。
特に、光開裂型の光ラジカル重合開始剤が好ましい。
市販されている光ラジカル重合開始剤としては、例えば、IRGACURE(登録商標)184、同369、同651、同500、同819、同907、同784、同2959、同CGI1700、同CGI1750、同CGI1850、同CG24-61、同TPO、Darocur(登録商標)1116、同1173[以上、BASFジャパン(株)製]、ESACURE KIP150、同KIP65LT、同KIP100F、同KT37、同KT55、同KTO46、同KIP75[以上、Lamberti社製]を挙げることができる。
市販されているアゾ系熱重合開始剤としては、例えば、V-30、V-40、V-59、V-60、V-65、V-70[以上、和光純薬工業(株)製]を挙げることができる。
また市販されている有機過酸化物系熱重合開始剤としては、例えば、パーカドックス(登録商標)CH、同BC-FF、同14、同16、トリゴノックス(登録商標)22、同23、同121、カヤエステル(登録商標)P、同O、カヤブチル(登録商標)B[以上、化薬アクゾ(株)製]、パーヘキサ(登録商標)HC、パークミル(登録商標)H、パーオクタ(登録商標)O、パーヘキシル(登録商標)O、同Z、パーブチル(登録商標)O、同Z[以上、日油(株)製]を挙げることができるが、これらに限定されるものではない。
さらに本発明の重合性組成物は、本発明の効果を損なわない限りにおいて、必要に応じて、例えば、連鎖移動剤、酸化防止剤、紫外線吸収剤、光安定化剤、レベリング剤、レオロジー調整剤、シランカップリング剤等の接着補助剤、顔料、染料、消泡剤を含有することができる。
フェノール系酸化防止剤としては、例えば、IRGANOX(登録商標)245、同1010、同1035、同1076、同1135[以上、BASFジャパン(株)製]、スミライザー(登録商標)GA-80、同GP、同MDP-S、同BBM-S、同WX-R[以上、住友化学(株)製]、アデカスタブ(登録商標)AO-20、同AO-30、同AO-40、同AO-50、同AO-60、同AO-80、同AO-330[以上、(株)ADEKA製]が挙げられる。
本実施の形態の重合性組成物の調製方法は、特に限定されない。調製法としては、例えば、(a)成分及び(b)成分、及び必要に応じて(c)成分及び(d)成分を所定の割合で混合し、所望によりその他添加剤をさらに添加して混合し、均一な溶液とする方法、これら各成分のうち、例えば(a)成分及び(b)成分の一部を混合して均一な溶液とした後、残りの各成分を加え、所望によりその他添加剤をさらに添加して混合し、均一な溶液とする方法、又はこれらの成分に加えさらに慣用の溶媒を使用する方法が挙げられる。
上記重合性組成物を露光(光硬化)又は加熱(熱硬化)して、硬化物を得ることができ、本発明は上記重合性化合物の硬化物も対象とする。
露光する光線としては、例えば、紫外線、電子線、X線が挙げられる。紫外線照射に用いる光源としては、例えば、太陽光線、ケミカルランプ、低圧水銀灯、高圧水銀灯、メタルハライドランプ、キセノンランプ、UV-LEDが使用できる。また、露光後、硬化物の物性を安定化させるためにポストベークを施してもよい。ポストベークの方法としては、特に限定されないが、通常、ホットプレート、オーブン等を使用して、50~260℃、1~120分間の範囲で行われる。
熱硬化における加熱条件としては、特に限定されないが、通常、50~300℃、1~120分間の範囲から適宜選択される。また、加熱手段としては、特に限定されないが、例えば、ホットプレート、オーブンが挙げられる。
本発明の重合性組成物は、例えば、圧縮成形(インプリント等)、注型、射出成形、ブロー成形などの慣用の成形法を使用することによって、硬化物の形成と並行して各種成形体を容易に製造することができる。こうして得られる成形体も本発明の対象である。
成形体を製造する方法としては、例えば接し合う支持体と鋳型との間の空間、又は分割可能な鋳型の内部の空間に本発明の重合性組成物を充填する工程、当該充填された組成物を露光して光重合する工程、得られた光重合物を充填された前記空間から取り出して離型する工程、並びに、該光重合物を該離型の前、中途又は後において加熱する工程を含む方法が挙げられる。
上記露光して光重合する工程は、前述の<<硬化物>>に示す条件を適用して実施することができる。
上記加熱工程の条件としては、特に限定されないが、通常、50~260℃、1~120分間の範囲から適宜選択される。また、加熱手段としては、特に限定されないが、例えば、ホットプレート、オーブン等が挙げられる。
このような方法によって製造された成形体は、カメラ用モジュールレンズとして好適に使用することができる。
なお、実施例において、試料の調製及び物性の分析に用いた装置及び条件は、以下の通りである。
装置:Brewer Science社製 Cee(登録商標)200X
(2)UV露光
装置:アイグラフィックス(株)製 バッチ式UV照射装置(高圧水銀灯2kW×1灯)
(3)1H NMRスペクトル
装置:Bruker社製 AVANCE III HD
測定周波数:500MHz
溶媒:CDCl3
内部基準:テトラメチルシラン(δ=0.00ppm)
(4)ゲル浸透クロマトグラフィー(GPC)
装置:(株)島津製作所製 Prominence(登録商標)GPCシステム
カラム:昭和電工(株)製 Shodex(登録商標)GPC KF-804L及びGPC KF-803L
カラム温度:40℃
溶媒:テトラヒドロフラン
検出器:RI
検量線:標準ポリスチレン
(5)アッベ数νD、屈折率nD
装置A(硬化膜測定時):ジェー・エー・ウーラム・ジャパン社製 多入射角分光エリプソメーター VASE
装置B(成形体測定時):メトリコン社製 プリズムカプラ モデル2010/M
測定温度:室温(およそ23℃)
(6)融点
観察装置:(株)ニコン製 偏光顕微鏡 ECLIPSE(登録商標) E600 POL
加熱装置:(株)東海ヒット製 顕微鏡用ステージ自動温度制御システムThermoPlate(登録商標)
昇温速度:0.5℃/秒
測定方法:目視で試料の一部が融解し始めた温度を融点とした
(7)粘度
装置:京都電子工業(株)製 EMS-1000
(8)透過率
装置:日本分光(株)製 紫外可視近赤外分光光度計V-670
リファレンス:空気
NMA:ナフタレン-2-イルメチルアクリレート
VN:2-ビニルナフタレン[新日鐵住金化学(株)製]
SPeDMS:ジメトキシ(フェナントレン-9-イル)(4-ビニルフェニル)シラン
BPOEA:2-([1,1’-ビフェニル]-2-イルオキシ)エチルアクリレート[新中村化学工業(株)製 NKエステルA-LEN-10]
BnA:ベンジルアクリレート[大阪有機化学工業(株)製 ビスコート#160,BZA]
DVB:ジビニルベンゼン[新日鐵住金化学(株)製 DVB-810]
FDA:9,9-ビス(4-(2-アクリロイルオキシエトキシ)フェニル)フルオレン[新中村化学工業(株)製 NKエステルA-BPEF]
PheTMS:トリメトキシ(9-フェナントリル)シラン
STMS:トリメトキシ(4-ビニルフェニル)シラン[信越化学工業(株)製 信越シリコーン(登録商標)KBM-1403]
TMOS:テトラメトキシシラン[東京化成工業(株)製]
TEAH:35質量%水酸化テトラエチルアンモニウム水溶液[アルドリッチ社製]
DDT:n-ドデカンチオール[花王(株)製 チオカルコール20]
I184:1-ヒドロキシシクロヘキシルフェニルケトン[BASFジャパン(株)製 IRGACURE(登録商標)184]
TPO:ジフェニル(2,4,6-トリメチルベンゾイル)ホスフィンオキシド[BASFジャパン(株)製 IRGACURE(登録商標)TPO]
PGMEA:プロピレングリコールモノメチルエーテルアセテート
THF:テトラヒドロフラン
凝縮器を備えた1Lの反応フラスコに、マグネシウム切削片[関東化学(株)製]15.7g(0.65mol)を仕込み、窒素バルーンを用いてフラスコ中の空気を窒素で置換した。ここへ、9-ブロモフェナントレン[東京化成工業(株)製]151.2g(0.58mol)、及びTHF518gの混合物を、室温(およそ23℃)下、1時間で滴下し、さらに1時間撹拌することで、グリニャール試薬を調製した。
2Lの反応フラスコに、STMS131.9g(0.58mol)、及びTHF259gを仕込み、窒素バルーンを用いてフラスコ中の空気を窒素で置換した。ここへ、上記グリニャール試薬を、還流下(およそ66℃)、30分間で滴下し、さらに24時間還流させた。この反応混合物から、エバポレーターを用いてTHFを減圧留去した。得られた残渣にヘキサン1,000gを加え、1時間還流させて可溶物を溶解した後、不溶物をろ別した。この不溶物に再度ヘキサン750gを加え、同様に可溶物を溶解後、不溶物をろ別した。それぞれのろ液を混合し、エバポレーターを用いてヘキサンを減圧留去することで、粗生成物を得た。粗生成物をヘキサン150gで再結晶することで、目的とするSPeDMS102.4g(収率47%)を得た。
得られた化合物の1H NMRスペクトルを図1に示す。
200mL反応フラスコに、2-ナフタレンメタノール[東京化成工業(株)製]25.0g(0.158mol)、及びTHF158gを仕込み、窒素バルーンを用いてフラスコ中の空気を窒素で置換した後、0℃に冷却した。ここへ、トリエチルアミン[東京化成工業(株)製]17.58g(0.174mol)、及びアクリロイルクロリド[東京化成工業(株)製]15.73g(0.174mol)を加え、室温(およそ23℃)で1時間撹拌した。この反応混合物へ水158gを加え、酢酸エチル158gで生成物を抽出した。有機層からエバポレーターを用いて溶媒を減圧留去することで、粗生成物を得た。粗生成物を、シリカゲルクロマトグラフィー(ヘキサン/酢酸エチル=9/1(質量比))で精製することで、目的物であるナフタレン-2-イルメチルアクリレート21.5g(収率64%)を得た。
得られた化合物の1H NMRスペクトルより、目的の構造であることを確認した。
凝縮器を備えた500mLの反応フラスコに、マグネシウム切削片[関東化学(株)製]10.4g(0.43mol)を仕込み、窒素バルーンを用いてフラスコ中の空気を窒素で置換した。ここへ、9-ブロモフェナントレン[東京化成工業(株)製]100.3g(0.39mol)、及びTHF346gの混合物を、室温(およそ23℃)下、1時間で滴下し、さらに30分間撹拌することで、グリニャール試薬を調製した。
1Lの反応フラスコに、TMOS178.0g(1.17mol)、及びTHF346gを仕込み、窒素バルーンを用いてフラスコ中の空気を窒素で置換した。ここへ、上記グリニャール試薬を、室温(およそ23℃)下、30分間で滴下し、さらに2時間撹拌した。この反応混合物から、エバポレーターを用いてTHFを減圧留去した。得られた残渣に、ヘキサン1,000gを加え、可溶物を溶解した後、不溶物をろ別した。この不溶物に、再度ヘキサン500gを加え、同様に不溶物をろ別した。それぞれのろ液を混合し、エバポレーターを用いてヘキサンを減圧留去することで、粗生成物を得た。粗生成物を減圧蒸留(1mmHg、120~150℃)した後、メタノール389gで再結晶することで、目的とするPheTMS74.6g(収率64%)を得た。
得られた化合物の1H NMRスペクトルを図2に示す。
凝縮器を備えた50mLの反応フラスコに、TEAH1.36g(3.23mmol)、及びTHF12gを仕込み、窒素バルーンを用いてフラスコ中の空気を窒素で置換した。ここへ、製造例1に従って製造したSPeDMS29.9g(80.7mmol)、及びTHF24gの混合物を、室温(およそ23℃)下、10分間で滴下し、40℃で16時間撹拌した。これを室温(およそ23℃)に冷却した。次いで、この反応混合物に、予めTHFで洗浄した陽イオン交換樹脂[ダウ・ケミカル社製 アンバーリスト(登録商標)15JWET]6.0g、及びろ過助剤[日本製紙(株)製 KCフロック W-100GK]1.2gを加え、1時間撹拌して反応を停止させた。その後、孔径0.5μmのメンブレンフィルタで陽イオン交換樹脂及びろ過助剤をろ過し、さらに酢酸エチル30gで洗い流した。このろ液及び洗浄液を併せて、メタノール897gに添加してポリマーを沈殿させた。この沈殿物をろ過、乾燥することで、目的とする高屈折率重合性化合物1(以下、PSPeDMSと略記することもある)18.9gを得た。
GPCによるポリスチレン換算で測定される得られた化合物の重量平均分子量Mwは610、分散度:Mw(重量平均分子量)/Mn(数平均分子量)は1.2であった。
凝縮器を備えた50mLの反応フラスコに、TEAH0.90g(2.14mmol)、イオン交換水0.86g(47.7mmol)、及びTHF7gを仕込み、窒素バルーンを用いてフラスコ中の空気を窒素で置換した。ここへ、製造例1に従って製造したSPeDMS9.9g(26.8mmol)、製造例3に従って製造したPheTMS8.0g(26.8mmol)、及びTHF14gの混合物を、室温(およそ23℃)下、10分間で滴下し、40℃で16時間撹拌した。これを室温(およそ23℃)に冷却した。次いで、この反応混合物に、予めTHFで洗浄した陽イオン交換樹脂[ダウ・ケミカル社製 アンバーリスト(登録商標)15JWET]3.6g、及びろ過助剤[日本製紙(株)製 KCフロック W-100GK]0.72gを加え、1時間撹拌して反応を停止させた。その後、孔径0.5μmのメンブレンフィルタで陽イオン交換樹脂及びろ過助剤をろ過し、さらに酢酸エチル18gで洗い流した。このろ液及び洗浄液を併せて、メタノール538gに添加してポリマーを沈殿させた。この沈殿物をろ過、乾燥することで、目的とする高屈折率重合性化合物2(以下、XPe55と略記することもある)14.8gを得た。
GPCによるポリスチレン換算で測定される得られた化合物の重量平均分子量Mwは1,000、分散度:Mw/Mnは1.0であった。
各ワニスを、シリコンウェハー上にスピンコーティング(1,500rpm×30秒間)し、80℃のホットプレートで1分間加熱乾燥した。この塗膜を、窒素雰囲気下、20mW/cm2で250秒間UV露光し、さらに150℃のホットプレートで20分間加熱することで、膜厚1.0μmの硬化膜を作製した。得られた硬化膜の波長589nm(D線)におけるアッベ数νDを測定した。結果を表1に併せて示す。
(b)成分の低粘度化剤としてVN2質量部、(a)成分の高屈折率重合性化合物としてFDA6質量部、及び(c)成分の重合性希釈剤としてBnA2質量部を配合し、40℃で2時間撹拌した。ここへ、(d)成分の重合開始剤としてI184 0.1質量部及びTPO0.07質量部を加え、40℃で1時間撹拌した。さらに、ここへ連鎖移動剤(反応促進剤)としてDDT0.3質量部を加え、室温(およそ23℃)で2時間撹拌することで、重合性組成物1を均一な透明ワニスとして得た。
各配合を表2に記載のように変更した以外は実施例1と同様に操作し、重合性組成物2~16をそれぞれ調製した。なお、表2中、「部」は「質量部」を表す。
各重合性組成物を、1mm厚のシリコーンゴム製スペーサーとともに、離型処理したガラス基板2枚で挟み込んだ。この挟み込んだ重合性組成物を、20mW/cm2で250秒間UV露光した。硬化物をガラス基板から剥離した後、150℃のホットプレートで20分間加熱することで、直径30mm、厚さ1mmの成形体を作製した。
得られた成形体の波長589nm(D線)におけるアッベ数νD、及び屈折率nD、波長400~800nmの平均透過率を測定した。結果を表3に併せて示す。
また従来の液状希釈剤であるBPOEAは、本発明の低粘度化剤と同様に粘度の低下或いは10,000mPa・s以下の粘度を維持することができたものの、アッベ数が上昇した(実施例5と比較例5、実施例7と比較例6、実施例9と比較例7参照)。なお低粘度化剤無配合の例と比べると、BPOEAは配合によって却ってアッベ数の上昇がみられる結果となった(比較例3と5、比較例4と7参照)。
上記FDA、PSPeDMS、XPe55又はBPOEA 100質量部、I184 1質量部、及びPGMEA233質量部を混合した。この溶液を、孔径0.2μmのPTFEシリンジフィルタでろ過し、固形分濃度30質量%のワニスを得た。
各ワニスを、シリコンウェハー上にスピンコーティング(1,500rpm×30秒間)し、80℃のホットプレートで1分間加熱乾燥した。この塗膜を、窒素雰囲気下、20mW/cm2で250秒間UV露光し、さらに150℃のホットプレートで20分間加熱することで、膜厚1.0μmの硬化膜を作製した。得られた硬化膜の波長589nm(D線)における屈折率及びアッベ数νDを測定した。結果を表4に示す。
Claims (17)
- 1013.25hPa下、23℃における物質の状態が固体であり、100℃未満の融点を有する化合物であって、100℃における粘度が10mPa・s以下であり、その硬化物のD線(589.3nm)におけるアッベ数が23以下である化合物を、
重合性二重結合を少なくとも1つ有し、その硬化物のD線(589.3nm)における屈折率が1.60以上である高屈折率重合性化合物の低粘度化剤として使用する方法。 - 前記低粘度化剤が、炭素原子数1乃至6のアルキル基で置換されていてもよいフェニル基又はフェニレン基、複数のベンゼン環構造を有する1価又は2価の縮合環炭化水素基(炭素原子数1乃至6のアルキル基で置換されていてもよい)、及び、複数の芳香環が単結合で直接結合している1価又は2価の炭化水素環集合基(炭素原子数1乃至6のアルキル基で置換されていてもよい)からなる群から選択される芳香族基を少なくとも1つ有し、且つ、
ビニル基、アリル基、(メタ)アリルオキシ基及び(メタ)アクリロイル基からなる群から選択される重合性二重結合を有する基を少なくとも1つ有する化合物である、
請求項1に記載の方法。 - 前記低粘度化剤が、下記式[1]で表される化合物である、請求項2に記載の方法。
(式中、Xは重合性二重結合を有する置換基を少なくとも1つ有するフェニル基、重合性二重結合を有する置換基を少なくとも1つ有するナフチル基、重合性二重結合を有する置換基を少なくとも1つ有するビフェニル基、又は重合性二重結合を有する置換基を少なくとも1つ有するフェナントリル基を表し、Ar1は複数のベンゼン環構造を有する縮合環炭化水素基(炭素原子数1乃至6のアルキル基で置換されていてもよい)、又は複数の芳香環が単結合で直接結合している炭化水素環集合基(炭素原子数1乃至6のアルキル基で置換されていてもよい)を表し、R1はメチル基、エチル基、又はイソプロピル基を表す。) - 重合性二重結合を少なくとも1つ有し、その硬化物のD線(589.3nm)における屈折率が1.60以上である高屈折率重合性化合物の低粘度化剤であって、
1013.25hPa下、23℃における物質の状態が固体であり、100℃未満の融点を有する化合物であって、100℃における粘度が10mPa・s以下であり、その硬化物のD線(589.3nm)におけるアッベ数が23以下である化合物からなる、低粘度化剤。 - (a)重合性二重結合を少なくとも1つ有し、その硬化物のD線(589.3nm)における屈折率が1.60以上である高屈折率重合性化合物100質量部、及び
(b)1013.25hPa下、23℃における物質の状態が固体であり、100℃未満の融点を有する化合物であって、100℃における粘度が10mPa・s以下であり、その硬化物のD線(589.3nm)におけるアッベ数が23以下である化合物からなる、低粘度化剤10~500質量部
を含む、重合性組成物。 - 前記(a)高屈折率重合性化合物が、式[4]で表されるアルコキシケイ素化合物Aの重縮合物、及び式[4]で表されるアルコキシケイ素化合物Aと式[5]で表されるアルコキシケイ素化合物Bとの重縮合物の少なくとも一方を含む、反応性ポリシロキサンを含む、請求項7に記載の重合性組成物。
(式中、Xは重合性二重結合を有する置換基を少なくとも1つ有するフェニル基、重合性二重結合を有する置換基を少なくとも1つ有するナフチル基、重合性二重結合を有する置換基を少なくとも1つ有するビフェニル基、又は重合性二重結合を有する置換基を少なくとも1つ有するフェナントリル基を表し、Ar3は炭素原子数1乃至6のアルキル基で置換されていてもよいフェニル基、複数のベンゼン環構造を有する縮合環炭化水素基(炭素原子数1乃至6のアルキル基で置換されていてもよい)、又は複数の芳香環が単結合で直接結合している炭化水素環集合基(炭素原子数1乃至6のアルキル基で置換されていてもよい)を表し、R3はメチル基、エチル基、又はイソプロピル基を表す。)
(式中、Ar4は炭素原子数1乃至6のアルキル基で置換されていてもよいフェニル基、複数のベンゼン環構造を有する縮合環炭化水素基(炭素原子数1乃至6のアルキル基で置換されていてもよい)、又は複数の芳香環が単結合で直接結合している炭化水素環集合基(炭素原子数1乃至6のアルキル基で置換されていてもよい)を表し、R4はメチル基、エチル基、又はイソプロピル基を表す。) - (c)1013.25hPa下、23℃における物質の状態が液体である重合性希釈剤をさらに含む、請求項7乃至請求項10のうち何れか一項に記載の重合性組成物。
- 請求項7乃至請求項11の何れか一項に記載の重合性組成物の硬化物。
- 請求項7乃至請求項11の何れか一項に記載の重合性組成物からなる高屈折率樹脂レンズ用材料。
- 請求項7乃至請求項11の何れか一項に記載の重合性組成物から作製された、樹脂レンズ。
- 請求項7乃至請求項11の何れか一項に記載の重合性組成物を、接し合う支持体と鋳型との間の空間、又は分割可能な鋳型の内部の空間に充填する工程、及び当該充填された組成物を露光して光重合する工程、を含む成形体の製造方法。
- さらに、得られた光重合物を充填された前記空間から取り出して離型する工程、並びに、該光重合物を該離型の前、中途又は後において加熱する工程、を含む請求項15に記載の製造方法。
- 前記成形体がカメラモジュール用レンズである、請求項15又は請求項16に記載の製造方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020187033485A KR102165729B1 (ko) | 2016-05-30 | 2017-05-26 | 고굴절률 중합성 화합물의 저점도화제 및 이것을 포함하는 중합성 조성물 |
CN201780030853.1A CN109154677B (zh) | 2016-05-30 | 2017-05-26 | 高折射率聚合性化合物的低粘度化剂及包含该低粘度化剂的聚合性组合物 |
JP2018520874A JP6555499B2 (ja) | 2016-05-30 | 2017-05-26 | 高屈折率重合性化合物の低粘度化剤及びそれを含む重合性組成物 |
SG11201810721RA SG11201810721RA (en) | 2016-05-30 | 2017-05-26 | Viscosity lowering agent for high-refractive index polymerizable compound and polymerizable composition comprising same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016107986 | 2016-05-30 | ||
JP2016-107986 | 2016-05-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017209004A1 true WO2017209004A1 (ja) | 2017-12-07 |
Family
ID=60477758
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/019752 WO2017209004A1 (ja) | 2016-05-30 | 2017-05-26 | 高屈折率重合性化合物の低粘度化剤及びそれを含む重合性組成物 |
Country Status (6)
Country | Link |
---|---|
JP (1) | JP6555499B2 (ja) |
KR (1) | KR102165729B1 (ja) |
CN (1) | CN109154677B (ja) |
SG (1) | SG11201810721RA (ja) |
TW (1) | TWI725190B (ja) |
WO (1) | WO2017209004A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2022530116A (ja) * | 2019-04-26 | 2022-06-27 | キヤノン株式会社 | 光硬化性組成物 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01118802A (ja) * | 1987-11-02 | 1989-05-11 | Nippon Oil & Fats Co Ltd | 光学用樹脂 |
JP2012233118A (ja) * | 2011-05-06 | 2012-11-29 | Kaneka Corp | 硬化性組成物 |
WO2013146346A1 (ja) * | 2012-03-29 | 2013-10-03 | 富士フイルム株式会社 | 半硬化物、硬化物およびそれらの製造方法、光学部品、硬化樹脂組成物 |
WO2017047547A1 (ja) * | 2015-09-16 | 2017-03-23 | 大阪ガスケミカル株式会社 | 硬化性組成物及びその硬化物 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000044866A (ja) * | 1998-07-29 | 2000-02-15 | Toyota Motor Corp | 塗料用ポリマー組成物 |
JP5641253B2 (ja) * | 2009-06-19 | 2014-12-17 | 日産化学工業株式会社 | カルバゾールノボラック樹脂 |
JP4859998B2 (ja) * | 2010-01-07 | 2012-01-25 | 日本合成化学工業株式会社 | 活性エネルギー線硬化性組成物及びその用途 |
CN103562271B (zh) * | 2011-04-28 | 2015-08-12 | 三菱瓦斯化学株式会社 | 固化性组合物及光学用粘接剂 |
JP2012255914A (ja) | 2011-06-09 | 2012-12-27 | Jsr Corp | レンズ材用硬化性組成物、レンズの製造方法、及びレンズ |
CN103080162B (zh) * | 2011-06-13 | 2013-11-13 | Dic株式会社 | 自由基聚合性组合物、固化物和塑料透镜 |
WO2013001463A1 (en) * | 2011-06-27 | 2013-01-03 | University Of Cape Town | An endoprosthesis |
JP5940496B2 (ja) * | 2012-09-26 | 2016-06-29 | 富士フイルム株式会社 | 半硬化物、硬化物およびそれらの製造方法、光学部品、硬化樹脂組成物ならびに化合物 |
JP2016180017A (ja) * | 2013-08-15 | 2016-10-13 | 日産化学工業株式会社 | 反応性シリコーン化合物を含む重合性組成物 |
JP6470620B2 (ja) | 2014-04-01 | 2019-02-13 | 大阪ガスケミカル株式会社 | フルオレン骨格を有する(メタ)アクリレート化合物及びその製造方法 |
CN105085779B (zh) * | 2014-05-09 | 2019-03-01 | 武汉强力荷新材料有限公司 | 以双可聚合乳化剂制备的高固含量低粘度高稳定性聚丙烯酸酯乳液及方法 |
-
2017
- 2017-05-26 TW TW106118006A patent/TWI725190B/zh active
- 2017-05-26 KR KR1020187033485A patent/KR102165729B1/ko active IP Right Grant
- 2017-05-26 SG SG11201810721RA patent/SG11201810721RA/en unknown
- 2017-05-26 CN CN201780030853.1A patent/CN109154677B/zh active Active
- 2017-05-26 JP JP2018520874A patent/JP6555499B2/ja active Active
- 2017-05-26 WO PCT/JP2017/019752 patent/WO2017209004A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01118802A (ja) * | 1987-11-02 | 1989-05-11 | Nippon Oil & Fats Co Ltd | 光学用樹脂 |
JP2012233118A (ja) * | 2011-05-06 | 2012-11-29 | Kaneka Corp | 硬化性組成物 |
WO2013146346A1 (ja) * | 2012-03-29 | 2013-10-03 | 富士フイルム株式会社 | 半硬化物、硬化物およびそれらの製造方法、光学部品、硬化樹脂組成物 |
WO2017047547A1 (ja) * | 2015-09-16 | 2017-03-23 | 大阪ガスケミカル株式会社 | 硬化性組成物及びその硬化物 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2022530116A (ja) * | 2019-04-26 | 2022-06-27 | キヤノン株式会社 | 光硬化性組成物 |
JP7423658B2 (ja) | 2019-04-26 | 2024-01-29 | キヤノン株式会社 | 光硬化性組成物 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2017209004A1 (ja) | 2019-03-28 |
TWI725190B (zh) | 2021-04-21 |
CN109154677B (zh) | 2022-07-05 |
SG11201810721RA (en) | 2018-12-28 |
KR102165729B1 (ko) | 2020-10-14 |
KR20190013754A (ko) | 2019-02-11 |
TW201819431A (zh) | 2018-06-01 |
CN109154677A (zh) | 2019-01-04 |
JP6555499B2 (ja) | 2019-08-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10703863B2 (en) | Polymerizable composition comprising silsesquioxane compound having acrylic group | |
EP3327049B1 (en) | Reactive silsesquioxane compound and polymerizable composition containing aromatic vinyl compound | |
EP3466956B1 (en) | Polymerizable silane compound | |
US10899891B2 (en) | Reactive polysiloxane and polymerizable composition comprising same | |
JP6555499B2 (ja) | 高屈折率重合性化合物の低粘度化剤及びそれを含む重合性組成物 | |
JP6674157B2 (ja) | フェナントレン環含有反応性シルセスキオキサン化合物を含む重合性組成物 | |
WO2022211070A1 (ja) | 反応性シルセスキオキサン化合物を含有した光導波路用の重合性組成物 | |
KR102676480B1 (ko) | 아크릴기를 갖는 실세스퀴옥산 화합물을 포함하는 중합성 조성물 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2018520874 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20187033485 Country of ref document: KR Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17806559 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17806559 Country of ref document: EP Kind code of ref document: A1 |