CN1738842A - Polymerization curable composition - Google Patents
Polymerization curable composition Download PDFInfo
- Publication number
- CN1738842A CN1738842A CN 200480002200 CN200480002200A CN1738842A CN 1738842 A CN1738842 A CN 1738842A CN 200480002200 CN200480002200 CN 200480002200 CN 200480002200 A CN200480002200 A CN 200480002200A CN 1738842 A CN1738842 A CN 1738842A
- Authority
- CN
- China
- Prior art keywords
- polymerizable monomer
- weight
- bifunctional
- polymerization
- mentioned
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 90
- 238000006116 polymerization reaction Methods 0.000 title abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 162
- 150000001875 compounds Chemical class 0.000 claims abstract description 66
- 238000005562 fading Methods 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims description 82
- 230000001588 bifunctional effect Effects 0.000 claims description 65
- 239000000872 buffer Substances 0.000 claims description 30
- 230000009466 transformation Effects 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 15
- 238000012719 thermal polymerization Methods 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 12
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 43
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 33
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 28
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 19
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- 238000002474 experimental method Methods 0.000 description 17
- 238000007711 solidification Methods 0.000 description 17
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- CVEPFOUZABPRMK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;styrene Chemical compound CC(=C)C(O)=O.C=CC1=CC=CC=C1 CVEPFOUZABPRMK-UHFFFAOYSA-N 0.000 description 5
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 4
- 229940093500 ethoxyquin Drugs 0.000 description 4
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- 239000012530 fluid Substances 0.000 description 4
- 229920001427 mPEG Polymers 0.000 description 4
- 229940059574 pentaerithrityl Drugs 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
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- 238000004528 spin coating Methods 0.000 description 4
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process 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
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229940123457 Free radical scavenger Drugs 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920001213 Polysorbate 20 Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
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- 238000003851 corona treatment Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
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- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 2
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
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- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- LHXNVCCLDTYJGT-UHFFFAOYSA-N 1-(oxiran-2-ylmethoxy)propan-2-ol Chemical compound CC(O)COCC1CO1 LHXNVCCLDTYJGT-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
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- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- OWDBMKZHFCSOOL-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)propoxy]propoxy]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(C)COC(C)COC(=O)C(C)=C OWDBMKZHFCSOOL-UHFFFAOYSA-N 0.000 description 1
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- YJVIKVWFGPLAFS-UHFFFAOYSA-N 9-(2-methylprop-2-enoyloxy)nonyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCOC(=O)C(C)=C YJVIKVWFGPLAFS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- MYQWTPIYZTWWRB-UHFFFAOYSA-N C(C(=C)C)(=O)OCC1CO1.C(CS)(=O)OCCOC(CS)=O Chemical compound C(C(=C)C)(=O)OCC1CO1.C(CS)(=O)OCCOC(CS)=O MYQWTPIYZTWWRB-UHFFFAOYSA-N 0.000 description 1
- MUPIEMDDBGZNRU-UHFFFAOYSA-N C(C)(C)C(=O)O.C(C)(C)(C)OO Chemical compound C(C)(C)C(=O)O.C(C)(C)(C)OO MUPIEMDDBGZNRU-UHFFFAOYSA-N 0.000 description 1
- FVLVWBKHSDWKMM-UHFFFAOYSA-N CC(C)(C)OO.CCCCC(CC)C(O)=O Chemical compound CC(C)(C)OO.CCCCC(CC)C(O)=O FVLVWBKHSDWKMM-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
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- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical class CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
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- 241000218606 Pinus contorta Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
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- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- ZCZFEIZSYJAXKS-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COC(=O)C=C ZCZFEIZSYJAXKS-UHFFFAOYSA-N 0.000 description 1
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- QCCDLTOVEPVEJK-UHFFFAOYSA-N benzyl methyl ketone Natural products CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 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
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000008371 chromenes Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
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- CASPZMCSNJZQMV-UHFFFAOYSA-N ethane;2-methyloxirane Chemical compound CC.CC1CO1 CASPZMCSNJZQMV-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
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- 229920000620 organic polymer Polymers 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
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- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- DSNYFFJTZPIKFZ-UHFFFAOYSA-N propoxybenzene Chemical group CCCOC1=CC=CC=C1 DSNYFFJTZPIKFZ-UHFFFAOYSA-N 0.000 description 1
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
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Landscapes
- Optical Filters (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Eyeglasses (AREA)
Abstract
A polymerization curable composition comprising a specific polyfunctional polymerizable monomer having a hard molecular structure with an L-scale Rockwell hardness of its homopolymer of 60 or more, a specific polyfunctional polymerizable monomer and a photochromic compound, a photochromic lens substrate composed of a cured product of the polymerization curable composition, and a lens comprising the photochromic lens substrate. The substrate and lens show excellent photochromic properties such as high color development density and high fading rate, and the cured product has excellent substrate properties such as hardness, heat resistance and impact resistance as well as strength (toughness) that allows for its use in rimless spectacles.
Description
Technical field
The present invention relates to the photochromic lens base material that constitutes by cured body, contain the polymerization-curable composition and the photochromic lens of this base material with the photochromic property of excellence and excellent intensive property.
Background technology
Described photochromic glasses are to contain the outdoor of ultraviolet light at irradiation sunlight etc., and the lens fast colorizing plays the effect of sun glasses, and is not shining the indoor of these light, fades and plays the effect of transparent common spectacles; In recent years, the demand of photochromic glasses increases just gradually.
The known photochromic compound that makes of method that has the plastic lens of photochromism as a kind of manufacturing is dissolved in the monomer, makes its polymerization and directly obtains the method (below, be called refining and go into method) of photochromic lens.
This method can be given photochromism in forming lens, compare with the method for giving the processing of photochromism behind the molded lens again, has the advantage that obtains the plastic lens of photochromism in a step.
Photochromism is to absorb luminous energy by photochromic compound, producing the reversible structural changes displays, in the photochromism plastic lens that the method for refining obtains, because photochromic compound is distributed in the resinous substrates, so aspect the such photochromic property of colour developing concentration or the speed of fading, can't give full play of the original character that has of photochromic compound mostly.This be since with monomer solution in compare, in this matrix, the absolute of freeboard diminishes, this structural changes is restricted easily.Particularly when the high-molecular weight photochromic compound was disperseed in the high resinous substrates of hardness and thermotolerance, this trend was obvious.For example, making molecular weight is 300 or above photochromic compound when being distributed in the resin combination that is commonly used for plastic lens substrate, the transformation period of fading of photochromic compound elongated significantly (speed of fading postpones significantly), the speed of fading in the resinous substrates be in the monomer solution 50 times of the speed of fading or more than.
In WO01/05854A, disclose a kind of polymerization-curable composition (below, be called existing composition), said composition does not have this problem, just said composition is to have excellent photochromic characteristic, be used to form the solidification compound of the high photochromic cured body of hardness and thermotolerance, its L scale Rockwell hardness that contains the polymkeric substance that (A) obtain when single poly-is 40 or following polymer monomer, the L scale Rockwell hardness of the polymkeric substance that obtains when (B) single poly-is 60 or above 3 functional groups or above polyfunctional group polymerizable monomer, and (C) the L scale Rockwell hardness of the polymkeric substance of gained is 60 or above bifunctional polymerizable monomer and (D) photochromic compound during polymerization.
Feedstock composition when above-mentioned existing composition is gone into manufactured photochromism plastic lens as the use refining is very useful, but the nearest popular no-frame glasses of cured body conduct that said composition curing is obtained, when just directly the support bracket fastened lens substrate that does not have glasses of frame of perforate uses on lens, discovery has following problem: use drill bit to bore a hole on lens substrate and add man-hour, slight crack can appear, even perhaps add and do not have special problem man-hour in perforation, but if apply heavy burden to the fixed framework, the lens of fixed part produce damaged.
Summary of the invention
The object of the present invention is to provide: demonstrate colour developing concentration height, the fast excellent like this photochromic property of the speed of fading, and has the high excellent like this base material character of hardness and thermotolerance, simultaneously also with intensity that is used for no-frame glasses and flexible photochromism lens substrate.
Another object of the present invention is to provides: the polymerization-curable composition that forms the said lens base material.
Another purpose of the present invention is to provide: the photochromic lens that uses lens substrate of the present invention.
Other purpose of the present invention and advantage are shown by following explanation.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 1st is to realize that by a kind of photochromic lens base material it is characterized in that: the cured body by a kind of polymerization-curable composition forms, this polymerization-curable composition comprises:
(I) the represented polyfunctional group polymerizable monomer of following formula (1),
In the formula, R
1Be hydrogen atom or methyl, group-R
2-be-CH
2CH
2O-,-CH
2CH (CH
3) O-or-C (=O) CH
2CH
2CH
2CH
2CH
2Group shown in the O-, R
3Be organic residue of 3～6 valencys, a is 0～3 integer, and b is 3～6 integer;
(II) the bifunctional polymerizable monomer shown in the following formula (2),
In the formula, R
4And R
5Be hydrogen atom or methyl independently of one another, R
6And R
7Be the alkyl of hydrogen atom or carbonatoms 1～2 independently of one another, group-X-is-O-,-S-,-S (=O)
2-,-C (=O)-O-,-CH
2-,-CH=CH-or-C (CH
3)
2-shown in group, m and n are that m+n is 0～30 integer;
(III) photochromic compound;
The transformation period of fading of the photochromic compound in this cured body (III) is than 30 times of weak points of the transformation period of the photochromic compound in this polymerization-curable composition (III), and tensile strength be 15Kgf or more than.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 2nd realizes by a kind of polymerization-curable composition (below, be also referred to as the thermopolymerization solidification compound), it is characterized in that: this polymer cure composition comprises,
(I) the polyfunctional group polymerizable monomer shown in the above-mentioned formula (1),
(II) the bifunctional polymerizable monomer shown in the above-mentioned formula (2),
(III) with above-mentioned polymerizable monomer (I) and (II) different other polymerizable monomer,
(IV) photochromic compound and
(V) thermal polymerization;
And be benchmark with whole polymerizable monomers, the content of above-mentioned polyfunctional group polymerizable monomer (I), above-mentioned bifunctional polymer's monomer (II) and other polymerizable monomer (III) is respectively 1～15 weight %, 10～80 weight % and 5～89 weight %.
In addition, according to the present invention, above-mentioned purpose of the present invention and advantage, the 3rd realizes by a kind of polymerization-curable composition (below, be also referred to as the photopolymerization solidification compound), it is characterized in that: this polymer cure composition comprises,
(I) the polyfunctional group polymerizable monomer shown in the above-mentioned formula (1),
(II) the bifunctional polymerizable monomer shown in the above-mentioned formula (2),
(III) according to circumstances, with the above-mentioned polymerizable monomer (I) and (II) polymerizable monomer of different other,
(IV) photochromic compound and
(V) Photoepolymerizationinitiater initiater;
And be benchmark with whole polymerizable monomers, the content of above-mentioned polyfunctional group polymerizable monomer (I), above-mentioned bifunctional polymer's monomer (II) and other polymerizable monomer (III) is respectively 1～60 weight %, 10～90 weight % and 0～89 weight %.
At last, according to the present invention, above-mentioned purpose of the present invention and advantage also realize by a kind of photochromic lens, it is characterized in that: these lens comprise, above-mentioned photochromic lens base material of the present invention, hard coat and be present between these base materials and the hard coat and pencil hardness lower than the pencil hardness of hard coat, be used to engage the buffer layer of this base material and hard coat.
Embodiment
Photochromic lens base material of the present invention is formed by the cured body of the polymerizing curable composition that comprises bifunctional polymerizable monomer shown in the polyfunctional group polymerizable monomer shown in the aforementioned formula (1), the aforementioned formula (2) and photochromic compound.And the transformation period of fading of the photochromic compound in this cured body is than the 30 times shorter of transformation period of fading in this polymerization-curable composition of this photochromic compound, and the tensile strength of this cured body be 15Kgf or more than, be preferably 20Kgf or more than.
Here, described fade the transformation period as described later embodiment define, be meant in rayed and after making photochromic compound be color status, when stopping rayed, the absorbancy of maximum wavelength is reduced to the 1/2 needed time in when colour developing, be as a most important properties in the photochromic property, i.e. the fade finger target value of speed.Photochromic compound in this base material fade the transformation period than 30 times shorter of transformation period of fading of this photochromic compound in the polymerization-curable composition before solidifying, be preferably shorter than 10 times, more preferably shorter than 7 times, be preferably especially than 5 times shorter, this means that it has excellent photochromic property.In addition, the transformation period of fading of cured body itself was preferably in 4 minutes, more suitably was in 2 minutes.
In addition, described tensile strength is the index of endurable hole processing intensity, is meant: for preparing thickness and be 2 ± 0.5mm can crooked discous experiment slice, and the area of its major surfaces is 10～40cm
2By its center of gravity or near the arbitrary line it and 2 intersection points of experiment slice periphery formation, respectively with 2 from this straight line of the inboard 4mm of these 2 intersection points as the center, on experiment slice, pass the hole of 2 diameter 2mm φ by boring processing, then, making diameter is after the rod of the stainless steel manufacturing of 1.6mm φ passes 2 through holes of gained respectively, these 2 rods to be separately fixed in the chuck up and down of tensile testing machine, the tensile strength when stretching with 5mm/ minute speed.It should be noted that, in the tensile strength shown in above-mentioned definition experiment, near the generation hole of bit bore of breaking usually of experiment slice, aspect common glasses lens use, tensile strength is subjected to the influence of the shape of base material hardly.In addition because be processed as before the common user mode and after the eyeglass lens shape and size in the scope of above-mentioned experiment slice, so above-mentioned tensile strength can be just directly as the index of the endurable hole processing intensity of eyeglass lens.But, with above-mentioned tensile strength during as the endurable hole processing intensity index of eyeglass lens, eyeglass lens for the shape that is processed as actual use, in order to become and borderless frame to be installed (just, the arm parts that are connected with pillar) roughly the same position, suitable is to pass 2 holes, carries out stretching experiment.
In order to be used for no-frame glasses, tensile strength be 15Kgf or more than, be preferably 20Kgf or more than.Tensile strength is 15Kgf or above words, in using, the supervision of no-frame glasses demonstrates good result, and pass through boring and process on the optional position of base material with 2, when the revolution of 100rpm is acutely bored a hole into the hole of 2mm φ (is the speed of 1 hole/second as experience), do not have bigger slight crack to occur, the length of slight crack is controlled at below the 0.4mm.
Then, in the present invention, use the polyfunctional group polymerizable monomer shown in the following formula (1),
In the formula, R
1Be hydrogen atom or methyl, group-R
2-be-CH
2CH
2O-,-CH
2CH (CH
3) O-or-C (=O) CH
2CH
2CH
2CH
2CH
2Group shown in the O-, R
3Be organic residue of 3～6 valencys, a is 0～3 integer, and b is 3～6 integer.This monomer is (B) composition in the disclosed existing composition among the aforementioned WO 01/05854A, and the L scale Rockwell hardness of just single polymkeric substance that obtains when poly-is 60 or above 3 functional groups or above polymerizable monomer.By using this monomer can obtain particularly with the cured body of transformation period that fade as the photochromic property excellence of representative.In the polyfunctional group polymerizable monomer, consider the problem of easy acquisition, if illustration is fit to the material of use particularly, can list trimethylolpropane trimethacrylate, Viscoat 295, the tetramethylol methane trimethacrylate, the tetramethylol methane triacrylate, tetramethylol methane tetramethyl-acrylate, the tetramethylol methane tetraacrylate, trimethylolpropane tris glycol trimethacrylate, trimethylolpropane tris glycol triacrylate, the ethoxylation tetramethylol methane tetraacrylate, ethoxyquin tetramethylolmethane tetramethyl-acrylate, pentaerythritol acrylate trimethyl, tetramethylolmethane tetramethyl-acrylate, two-trimethylolpropane tetra-acrylate of hexanolactam modification, two-TriMethylolPropane(TMP) tetramethyl-acrylate of hexanolactam modification, the dipentaerythritol acrylate of hexanolactam modification etc.They can use separately, also can mix 2 kinds or multiple use.
In the present invention, can use the bifunctional polymerizable monomer shown in (II) following formula (2).
In the formula, R
4And R
5Be hydrogen atom or methyl independently of one another, R
6And R
7Be that hydrogen atom or carbonatoms are 1～2 alkyl independently of one another, group-X-is-O-,-S-,-S (=O)
2-,-C (=O)-O-,-CH
2-,-CH=CH-or-C (CH
3)
2-shown in group, m and n are that to make m+n be 0～30 integer.This bifunctional polymerizable monomer is when m+n less than 8, be (C) composition in the disclosed existing composition among the WO01/05854A, the L scale Rockwell hardness of the polymkeric substance that obtains when just single poly-be 60 or above bifunctional polymerizable monomer in the monomer that contains; In addition, be 8 or when above at m+n, be (A) composition in the existing composition, the L scale Rockwell hardness of just single polymkeric substance that obtains when poly-be 40 or following polymerizable monomer in the monomer that contains.Described L scale Rockwell hardness is the value of determining according to JIS K7202, particularly, the pressure head that use is formed by the rigid ball of diameter 6.350mm applies 10Kgf on the surface of cured body experiment slice benchmark bears a heavy burden, the experiment that applies 60Kgf is again born a heavy burden, when getting back to the benchmark heavy burden once more, the pressure head that 2 secondary standards bear a heavy burden from front and back enter depth difference h (mm of unit), the value of trying to achieve according to the calculating formula of 130-500h.
By using aforementioned bifunctional polymerizable monomer, can obtain the particularly cured body of intensity and tenacity excellent.In this bifunctional polymerizable monomer, consider the problem of easy acquisition, if illustration is fit to the material of use particularly, can list 2,2-two [4-(methacryloxy polyethoxye) phenyl] propane (mean value of m+n is 2 material), the same (mean value of m+n is 2.6 material), the same (mean value of m+n is 4 material), the same (mean value of m+n is 10 material), the same (mean value of m+n is 30 material), 2,2-two [4-(acryloxy polyethoxye) phenyl] propane (mean value of m+n is 4 material), 2,2-two [4-(methacryloxy gathers propoxy-) phenyl] propane (mean value of m+n is 4 material), the same (mean value of m+n is 10 material), two [4-(methacryloxy polyethoxye) phenyl] methane (mean value of m+n is 4 material), two [4-(methacryloxy polyethoxye) phenyl] sulfone (mean value of m+n is 4 material) etc.They can use separately, also can mix 2 kinds or the use of multiple back.
As bifunctional polymerizable monomer (II) preferably is that 0～5 the 1st bifunctional polymerizable monomer and the m+n in the above-mentioned formula (2) are 6～30 the 2nd bifunctional polymerizable monomer with the m+n in the above-mentioned formula (2), is that the 3 times of moles or following, as to be preferably 0～2 times of mole ratio of the 1st bifunctional polymerizable monomer used with the 2nd bifunctional polymerizable monomer.
In formula (2), if illustration m+n is 0～5 the 1st bifunctional polymerizable monomer (mainly being the material that is equivalent to the composition C of existing composition) particularly, can list, 2,2-two [4-(methacryloxy) phenyl] propane (mean value of m+n is 0 material), 2,2-two [4-(methacryloxy oxyethyl group) phenyl] propane (mean value of m+n is 2 material), 2,2-two [4-(methacryloxy diethoxy) phenyl] propane (mean value of m+n is 4 material), 2,2-two [4-(acryloyl-oxy base oxethyl) phenyl] propane (mean value of m+n is 2 material), 2,2-two [4-(methacryloxy propoxy-) phenyl] propane (mean value of m+n is 2 material), two [4-(methacryloxy diethoxy) phenyl] methane (mean value of m+n is 4 material), two [4-(methacryloxy oxyethyl group) phenyl] sulfone (mean value of m+n is 2 material) etc.
In formula (2), if illustration m+n is 0～30 the 2nd bifunctional polymerizable monomer particularly, can list 2,2-two [4-(methacryloxy polyethoxye) phenyl] propane (mean value of m+n is 10 material), the same (mean value of m+n is 30 material), 2,2-two [4-(acryloxy polyethoxye) phenyl] propane (mean value of m+n is 10 material), 2,2-two [4-(methacryloxy gathers propoxy-) phenyl] propane (mean value of m+n is 10 material), two [4-(methacryloxy polyethoxye) phenyl] methane (mean value of m+n is 10 material), two [4-(methacryloxy polyethoxye) phenyl] sulfone (mean value of m+n is 10 material) etc.
If the 2nd bifunctional polymerizable monomer surpasses 3 times of moles of the 1st bifunctional polymerizable monomer, then has situation about can not get as the intensity (toughness) of no-frame glasses use.
In polymerization-curable composition, can contain aforementioned composition (I), composition (II) other polymerizable monomer in addition as polymerizable monomer.As other polymerizable monomer so long as L scale Rockwell hardness be 60 or above 3 functional groups or above polyfunctional group polymerizable monomer beyond monomer, just can be without any the known monomer of use that limits.For example, can use suitably as (A) composition that uses in the disclosed solidification compound among the WO01/05854A (existing composition) and (C) the illustrative following monomer of composition (wherein, specific bifunctional monomer except).
As (A) composition, for example can use molecular-weight average is 526 polyethylene glycol methacrylate-styrene polymer, molecular-weight average is 360 polyethylene glycol methacrylate-styrene polymer, molecular-weight average is 475 methyl ether polyethylene glycol methacrylate-styrene polymer, molecular-weight average is 1,000 methyl ether polyethylene glycol methacrylate-styrene polymer, molecular-weight average is 375 polypropylene glycol methacrylic ester, molecular-weight average is 430 polypropylene glycol methacrylic ester, the methacrylic acid stearyl, the methacrylic acid Lauryl Ester, diglycidyl ether of ethylene glycol, the propylene glycol glycidyl ether, Viscoat 335HP and nine glycol diacrylates etc.
As (C) composition, for example can use diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, four propylene glycol dimethacrylates, nine glycol dimethacrylates, nine propylene glycol dimethacrylates, ethylene glycol bisthioglycolate glycidyl methacrylate, 1,4-butylene glycol dimethacrylate, 1,9-nonanediol dimethacrylate, neopentylglycol dimethacrylate etc.
In addition, also can use as (A) composition and (C) the polynary allylic cpds such as diallyl phthalate, diallyl isophthalic acid ester, tartrate diallyl ester of the polymerizable monomer beyond the composition as other polymerizable monomer; Acrylic compound and methacrylate compound such as glycidyl acrylate, glycidyl methacrylate, methyl acrylate, methyl methacrylate, methacrylic acid benzyl ester; Vinyl compounds such as vinylbenzene, chlorostyrene, vinyl toluene, vinyl naphthalene, α-Jia Jibenyixierjuwu, bromostyrene, Vinylstyrene etc.
In addition, also can use urethane oligomer, 2～6 functional group's polymerizability polyester oligomers of 2～6 functional group's polymerizabilitys suitably as other monomer.
Described 2～6 functional group's polymerizability urethane oligomers are on the isocyanate group residual on by various vulcabond, polyvalent alcohol synthetic polyurethane skeleton, the material that addition hydroxyl acrylic or hydroxymethyl vinylformic acid form.Object lesson as vulcabond can list benzyl support vulcabond, 4,4-diphenylmethanediisocyanate, xylylene vulcabond, HDI, isophorone diisocyanate, methylene bis(4-, trimethyl-hexamethylene diisocyanate etc.In addition, the object lesson as polyvalent alcohol can list polypropylene oxide glycol, copolymerization epoxy ethane-epoxy propane glycol, polytetrahydrofuran diol, ethoxyquin dihydroxyphenyl propane, ethoxyquin bisphenol S spiral shell glycol, caprolactone modification glycol, carbonic ether glycol, polyester glycol etc.
2～6 functional group's polymerizability urethane oligomers can use separately, can be with 2 kinds or multiple mixing use.
Described 2～6 functional group's polymerizability polyester oligomers are on the hydroxyl residual on by various polyvalent alcohols and polyprotonic acid synthetic polyester backbone, the material that the acid of condensation acrylic or methacrylic forms.Object lesson as polyvalent alcohol can list glycol ether, triglycol, 1,6-hexylene glycol, TriMethylolPropane(TMP), tetramethylolmethane etc.; Object lesson as polyprotonic acid can be enumerated phthalate anhydride, hexanodioic acid, trihemellitic acid etc.
2～6 functional group's polymerizability polyester oligomers can use separately, also can mix 2 kinds or multiple use.
Bifunctional polymerizable monomer shown in the above-mentioned formula (2) and intensity and the good harmony of flexible that can give the cured body photochromic property and can be used for no-frame glasses as other the combination of 2～6 functional group's polymerizability urethane oligomers of polymerizable monomer are so be preferred.
Rerum natura isostatic viewpoint from the cured body of gained, in polymerization-curable composition, the composition of the whole polymerizable monomers that contain in this cured body is preferably polyfunctional group polymerizable monomer (I), bifunctional polymerizable monomer (II) and other polymerizable monomer (III) and is respectively 1～60 weight %, 10～90 weight % and 0～89 weight %, more preferably is respectively 3～50 weight %, 20～60 weight % and 30～77 weight %.
Photochromic compound as the composition in the polymerization-curable composition (III) can use known photochromic compounds such as chromene, fulgimide, Luo oxazine compound etc., not special the qualification.Wherein, use molecular weight be 200 or above, particularly 500 or during above high molecular photochromic compound, show effect of the present invention, particularly as cured body the time, demonstrating the good photochromic properties, effect is remarkable, is suitable so use this photochromic compound.In these photochromic compounds, the photochromic property of chromene compounds is higher than other serial compound, and the concentration that develops the color, the speed of fading are also excellent, so be particularly suitable for using.If illustration is applicable to photochromic compound of the present invention particularly, can list following material.These compounds can be separately or with 2 kinds or or multiplely use together.Usually, in order to regulate the tone in when colour developing, be mostly to use simultaneously with other photochromic compound (comprising following compound and photochromic compound in addition thereof) more than a kind or 2 kinds.
Molecular weight 376
Molecular weight 515
Molecular weight 522
Molecular weight 547
Molecular weight 561
Molecular weight 568
Molecular weight 673
Molecular weight 681
There is no particular limitation for the amount of the photochromic compound that contains in the solidification compound, from uniformly dispersed viewpoint, with respect to the whole polymerizable monomers of 100 weight parts, is preferably 0.001～5 weight part, is preferably 0.01～2 weight part especially.
In addition, in the scope that does not hinder effect of the present invention, for the weather resistance that improves photochromic compound, improve color speed, improve the speed of fading and improve plasticity, in polymerization-curable composition, can also further add additive.Can list tensio-active agent, oxidation inhibitor, free-radical scavengers, ultra-violet stabilizer, UV light absorber, releasing agent, anti-coloring agent, antistatic agent, fluorescence dye, dyestuff, pigment, spices etc. as the additive that is fit to use.
With respect to whole polymerizable monomer of 100 weight parts, the addition of tensio-active agent is preferably 0～20 weight part.With respect to whole polymerizable monomer of 100 weight parts, the addition of oxidation inhibitor, free-radical scavengers, ultra-violet stabilizer, UV light absorber, releasing agent, anti-coloring agent, antistatic agent, fluorescence dye, dyestuff, pigment and spices etc. is preferably 0～2 weight part respectively.
There is no particular limitation to make above-mentioned polymerization-curable composition solidify the method for making cured body, can take by weighing behind a certain amount of each composition suitably mixed.Also there is no particular limitation for mixed sequential scheduling.Also there is no particular limitation for the solidified method, can pass through heat and/or photocuring, also can use polymerization starter as required.
For example, when making polymerization-curable composition photocuring of the present invention, composition is injected in the mould of maintenances such as using elastomerics packing ring or pad, shine active energy ray with for example metal halide lamp, middle medium pressure mercury lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, sterilizing lamp, xenon lamp, tungsten lamp, luminescent lamp etc. as light source.When the irradiation active energy ray, in order to prevent that photochromic compound assimilating activity energy line (usually, by absorbing the ultraviolet visualization about 380～400nm), be that 400nm or following wavelength use ultraviolet cutoff strainer are suitable for example for cutoff wavelength.
There is no particular limitation for the thermal polymerization that thermofixation is used; can list benzoyl peroxide particularly; peroxidation is to the chlorinated benzene formyl; decanoyl peroxide; lauroyl peroxide; diacyl peroxides such as acetyl peroxide; tert-butyl hydroperoxide-2-ethylhexanoate; tert-butyl hydroperoxide two carbonic ethers; the cumyl new decanoate ester peroxide; tert butyl peroxy benzoate; peroxyesters such as tert-butyl hydroperoxide isobutyrate; diisopropyl peroxydicarbonate; two-2-ethylhexyl peroxy dicarbonate; two-sec-butoxy carbonic ether peroxocarbonates such as (di-sec-butyloxycarbonate); 2; 2 '-Diisopropyl azodicarboxylate; 2; 2 '-azo two (4-methyl pentane nitrile); 2; 2 '-azo two (2-methylbutyronitrile); 1,1 '-azo two azo-compounds such as (hexanaphthenes-1-nitrile) etc.
In addition; there is no particular limitation for the Photoepolymerizationinitiater initiater that photocuring uses; can list benzoin particularly; the benzoin methyl ether; the benzoin butyl ether; benzo phenol (benzophenol); methyl phenyl ketone; 4; 4 '-benzophenone of dichloro; diethoxy acetophenone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; the benzyl methyl ketone acetal; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone; the 1-hydroxycyclohexylphenylketone; the 2-isopropyl thioxanthone; two (2; 4; the 6-trimethylbenzoyl) phenylphosphine oxide; two (2; 6-dimethoxy benzoyl)-2; 4,4-tri-methyl-amyl phosphine oxide etc.
There is no particular limitation for the amount of this polymerization starter, from fully carrying out polymerization and the viewpoint of the polymerization starter of residual surplus not cured body, with respect to the whole polymerizable monomer of 100 weight parts, be preferably 0.001～10 weight part, be preferably 0.01～3 weight part especially.
Above-mentioned polymerization-curable composition is when containing thermal polymerization, the whole polymerizable monomers that contain with polymerization-curable composition are benchmark, and above-mentioned polyfunctional group polymerizable monomer (I) and above-mentioned bifunctional polymerizable monomer (II) contain 1～15 weight % respectively, are preferably 3～10 weight % and 10～80 weight %, are preferably 20～60 weight %; In addition, when containing Photoepolymerizationinitiater initiater, the whole polymerizable monomer that contains with polymerization-curable composition is a benchmark, above-mentioned polyfunctional group polymerizable monomer (I) and above-mentioned bifunctional polymerizable monomer (II) preferably contain 1～60 weight % and 10～90 weight % respectively, especially preferably contain 10～60 weight % and 20～90 weight %.
For the former polymerization-curable composition that contains thermal polymerization, polyfunctional group polymerizable monomer (I) contain quantity not sufficient 1 weight % the time, can't obtain enough photochromic properties, in addition, when surpassing 15 weight %, be difficult to obtain necessary intensity of no-frame glasses and toughness.The preferred content of polyfunctional monomer (I) depends on the content of bifunctional polymerizable monomer (II), when composition (II) less than 40 weight %, polyfunctional monomer (I) is 1～10 weight part, is 40 weight % or when above at the content of composition (II), is 3～15 weight %.So, can obtain the particularly harmonious excellent cured body of photochromic property and intensity.In addition, bifunctional polymerizable monomer (II) contain quantity not sufficient 10 weight % the time, can't obtain necessary intensity of no-frame glasses or toughness, in addition, when surpassing 80 weight %, under the situation as composition, produce the problem that viscosity is too high, the use difficulty is such, under situation as cured body, structure is too upright and outspoken, limited the molecular motion of photochromic compound, generation can't obtain satisfiable photochromic property, slack-off such problem of the transformation period of fading.
Polymerization-curable composition for the latter of containing Photoepolymerizationinitiater initiater, polyfunctional group polymerizable monomer (I) contain quantity not sufficient 1 weight % the time, can't obtain enough photochromic properties, in addition, when surpassing 60 weight %, be difficult to obtain necessary intensity of no-frame glasses and toughness.The preferred content of polyfunctional monomer depends on its structure, for R
1For methyl and a are 0 material, be preferably 10～30 weight %, be preferably 15～25 weight % especially, for the material beyond it, be preferably 30～60 weight %, be preferably 40～60 weight % especially.So, can obtain the particularly harmonious excellent cured body of photochromic property and intensity.In addition, bifunctional polymerizable monomer (II) contain quantity not sufficient 10 weight % the time, can't obtain necessary intensity of no-frame glasses or toughness, in addition, when surpassing 90 weight %, under the situation as composition, produce the problem that viscosity is too high, the use difficulty is such, under situation as cured body, structure is too upright and outspoken, limited the molecular motion of photochromic compound, generation can't obtain satisfiable photochromic property, slack-off such problem of the transformation period of fading.
According to the present invention, as mentioned above,
Polymerization-curable composition is provided, is preferably as follows the photopolymerization solidification compound, it is characterized in that: comprise
(I) the polyfunctional group polymerizable monomer shown in the above-mentioned formula (1),
(II) the bifunctional polymerizable monomer shown in the above-mentioned formula (2),
(III) according to circumstances, with above-mentioned polymerizable monomer (I) and (II) different other polymerizable monomer,
(IV) photochromic compound and
(V) Photoepolymerizationinitiater initiater,
And, with whole polymerizable monomers is benchmark, the content of above-mentioned polyfunctional group polymerizable monomer (I), above-mentioned bifunctional polymerizable monomer (II) and other polymerizable monomer (III) is respectively 1～60 weight %, is preferably 10～60 weight %, 10～90 weight %, is preferably 20～90 weight % and 0～89 weight %, is preferably 0～70 weight %; And
The thermopolymerization solidification compound is characterized in that: comprise
(I) the polyfunctional group polymerizable monomer shown in the above-mentioned formula (1),
(II) the bifunctional polymerizable monomer shown in the above-mentioned formula (2),
(III) with above-mentioned polymerizable monomer (I) and (II) different other polymerizable monomer,
(IV) photochromic compound and
(V) thermal polymerization,
And, with whole polymerizable monomers is benchmark, the content of above-mentioned polyfunctional group polymerizable monomer (I), above-mentioned bifunctional polymerizable monomer (II) and other polymerizable monomer (III) is respectively 1～15 weight %, is preferably 3～10 weight %, 10～80 weight %, is preferably 20～60 weight % and 5～89 weight %, is preferably 30～77 weight %.
In above-mentioned photopolymerization solidification compound and thermopolymerization solidification compound, be that the mean value of 0～5 the 1st bifunctional polymerizable monomer and the m+n in the above-mentioned formula (2) is that 6～30 the 2nd bifunctional polymerizable monomer forms for the mean value of the m+n in the above-mentioned formula (2) more preferably, and the 2nd bifunctional polymerizable monomer is the polymerization-curable composition below 3 times of moles of the 1st bifunctional polymerizable monomer by bifunctional polymerizable monomer (II).
Make polymerization-curable composition solidify the feature that the cured body that obtains has photochromic property, hardness, intensity, the higher such excellence of toughness.Because this cured body has the feature of such excellence, so be especially suitable for use as the photochromism plastic lens substrate that optical article, particularly no-frame glasses are used.When cured body of the present invention is used for this purposes, also moulding, the lens substrate that is processed as suitable shape directly can be used as lens, also can carry out as required using as lens after the surface working.Just, carrying out colloidal sol composition with silane coupling agent and silicon, zirconium, antimony, aluminium, tin, tungsten etc. is that the hard coat agent of principal constituent is handled SiO
2, TiO
2, ZrO
2After antireflection processing of carrying out Deng the coating of the film vapor deposition of metal oxide or organic polymer film etc., as lens.
Particularly, when handling with hard coat agent, hard coat shrinks in curing process, and thus, base material becomes the state of residual stress.The result is, after forming hard coat, the tensile strength of base material with form before compare, about situation of about 30～50% of reduction is arranged, the result has the situation that can't guarantee the intensity used as no-frame glasses that becomes.
In the present invention, in order to address the above problem, be preferably: on base material, directly do not form hard coat, but insertion and base material and aforementioned hard coat have the buffer layer that adaptation and its pencil hardness are lower than the pencil hardness of hard coat on base material, form hard coat again.Engage base material and hard coat by inserting this buffer layer; the stress that in the time of can relaxing hard coat formation base material is applied; can guarantee the tensile strength that base material itself is had; the result is; has excellent photochromic property; when forming hard coat, can also guarantee the intensity that to use as no-frame glasses.
Above-mentioned buffer layer is so long as have adaptation with base material and aforementioned hard coat and than hard coat softish material more, just there is no particular limitation.As the index of above-mentioned pliability, for example can use pencil hardness.The pencil hardness of buffer layer can be lower than the pencil hardness of hard coat, and from the viewpoint of effect, what the pencil hardness of buffer layer was suitable is at 6H or following, and specially suitable is at 4H or following.Can use and to be coated with, to solidify the resin layer that obtains as common plastic lens with the bed material that bed material uses as buffer layer with this pencil hardness; Perhaps make the dura mater that has with hard coat formation usefulness similarly form, contain the coating agent coating of the composition that is useful on softening cured layer, the layer that curing obtains etc. with the coating agent.More specifically, can list the bed material coating of resenes such as polyurethanes, polyester, polyvinyl acetal, epoxies, the resin layer that curing obtains; The dura mater of the colloidal sol composition that contains silane coupling agent and silicon, zirconium, antimony, aluminium, tin, tungsten, titanium etc. that uses in hard coat is with after adding above-mentioned resene bed material in the coating agent, coating, solidifies the resin layer that obtains etc.
In addition, adaptation owing to contain the base material that uses among the present invention to the hard coat of the cured body of existing composition is good, so viewpoint from adaptation, be not on these base materials, to use bed material especially, viewpoint from productivity and cost, if do not need especially, do not use bed material usually.
In order to form aforementioned buffer layer, in being fit to the bed material that uses, relax the higher viewpoint of ability from stress, the suitable polyurethanes material that is to use, from usage period and easy solidified viewpoint, especially preferably use with block type polyisocyanates and polyvalent alcohol Thermocurable urethane bed material as principal constituent.
Can list with various isocyanic ester such as hexamethylene diisocyanate, isophorone diisocyanate, benzyl support group diisocyanate, xylylene vulcabond as the object lesson of block type polyisocyanates is matrix, uses the material of blocks such as phenol, ε-Ji Neixianan, active methylene group, MEK oxime, various amines endways.
In addition, object lesson as polyvalent alcohol can list polypropylene glycol, polyether glycols such as polytetramethylene glycol, the adipic acid ester class polyvalent alcohol that forms by hexanodioic acid and various glycol or polyvalent alcohol, the polycaprolactone polyol that forms by 6-caprolactone and various glycol or polyvalent alcohol, the aromatic polyester polyol that forms by terephthalic acid or m-phthalic acid and various glycol or polyvalent alcohol, the polyester polyols such as polycarbonate diol that form by ethylene carbonate etc. and various glycol, polybutadiene polyol, the hydrogenated butadiene polymer polyvalent alcohol, polyolefins polyvalent alcohols such as hydrogenated isoprene polyvalent alcohol have (methyl) Acrylic Acid Monomer of hydroxyl and (methyl) acrylate, the acrylic polyol that copolymerization such as vinylbenzene obtain etc.
With these blocked isocyanates and polyvalent alcohol is that the thermohardening type urethane bed material of principal constituent uses in the mode that is diluted in all kinds of SOLVENTS usually.Can list N-BUTYL ACETATE, methoxy propyl yl acetate, solvent wet goods as this solvent.
When solidification heat curable urethane bed material, can use known catalyzer such as tertiary amines, organo-tin compound.
There is no particular limitation for the method for formation buffer layer on base material, for example can list methods such as dipping, spin coating, dipping spin coating.Thermohardening type for example can carry out by heating under 70 ℃～130 ℃ temperature in 10～120 minutes; In addition, light-cured type for example can carry out by ultraviolet homenergic line irradiation in 10 seconds～5 minutes.The thickness of the buffer layer that so obtains is preferably 0.1～10 μ m.When thinner than 0.1 μ m, adaptation is low; In addition, when thicker, may damage photochromic property than 10 μ m, not preferred.In addition, before coating bed material liquid, in order to improve adaptation, preferably base material is carried out skimming treatment with organic solvent, carry out chemical treatment by alkalescence or acidic aqueous solution, use the milled processed of abrasive, use the plasma treatment of atmos plasma and low-voltage plasma etc., pre-treatments such as Corona discharge Treatment, flame treating or UV ozonize.
Optical article of the present invention can as above obtain after obtaining hard coat on this buffer layer of the base material that has formed buffer layer like that.The formation of hard coat and existing method are not special to be changed, can be by hard coat be applied on the above-mentioned buffer layer with coating agent (hardening solution), and the method that is cured is carried out.There is no particular limitation for the formation method of the kind of hardening solution, hard coat, can use known material and known method.
For example, as previously mentioned, can use with material such as the colloidal sol composition of silane coupling agent or silicon, zirconium, antimony, aluminium, tin, tungsten etc. as principal constituent as hardening solution.
In addition, there is no particular limitation for the method for formation hard coat on buffer layer, can list methods such as dipping, spin coating, dipping spin coating.Thermohardening type for example can carry out by heating under 70 ℃～130 ℃ temperature in 10～120 minutes; In addition, light-cured type for example can carry out by ultraviolet homenergic line irradiation in 10 seconds～5 minutes.In addition, before the coating hardening solution, in order to improve adaptation, can carry out skimming treatment with organic solvent to base material, carry out chemical treatment by alkalescence or acidic aqueous solution, use the milled processed of abrasive, use the plasma treatment of atmos plasma and low-voltage plasma etc., pre-treatments such as Corona discharge Treatment, flame treating or UV ozonize.
Embodiment
Below, the present invention will be described in more detail according to embodiment, but the present invention limits by these embodiment.
Below, the abbreviation and the title of the compound that uses among the expression embodiment.
1) bifunctional polymerizable monomer
BPE100:2,2-two (4-methacryloxy polyethoxye phenyl) propane (mean value of m+n is 2.6)
BPE200:2,2-two (4-methacryloxy polyethoxye phenyl) propane (mean value of m+n is 4)
BPE500:2,2-two (4-methacryloxy polyethoxye phenyl) propane (mean value of m+n is 10)
PDBP:2,2-two (the 4-methacryloxy gathers the propoxy-phenyl) propane (mean value of m+n is 4)
2) polyfunctional group polymerizable monomer
TMPT: trimethylolpropane trimethacrylate
TMPT3EO: ethoxyquin trimethylolpropane trimethacrylate
AD-TMP-4CL: two-trimethylolpropane tetra-acrylate of hexanolactam modification
3) other polymerizable monomer
4PGX: four propylene glycol dimethacrylates
4G: tetraethylene glycol dimethacrylate
M90G: molecular-weight average is 475 methyl ether polyethylene glycol methacrylate-styrene polymer
A200: Viscoat 335HP
A400: nine glycol diacrylates
APG200: tripropylene glycol diacrylate
PKA5009: methoxy poly (ethylene glycol) allyl ethers (n=11)
GMA: glycidyl methacrylate
α MS: alpha-methyl styrene
MSD: α-Jia Jibenyixierjuwu
U-1084: urethane oligomer tetraacrylate (M/v=440)
EB-1830: polyester oligomer six acrylate (M/v=300).
4) additive
Tween20: single month silicon ester of polyoxyethylene (20) sorbitan
5) photochromic compound
Chromene 1: (the fade transformation period of this compound in solidification compound is 0.4 minute to the compound of following structure.)
Chromene 2: (the fade transformation period of this compound in solidification compound is 0.3 minute to the compound of following structure.)
6) thermal polymerization
パ-Block チ Le ND: tert-butyl hydroperoxide neodecanoic acid ester.
7) Photoepolymerizationinitiater initiater
819: two (2,4, the 6-trimethylbenzoyl) phenylphosphine oxide of イ Le ガ キ ユ ア.
8) intensive property
After the cured body of use gained is configured as the discoid experiment slice of thickness 2mm, diameter 5cm φ, on the line of diameter that is this discoid experiment slice, with the point that is respectively 4mm from the edge is the center, be 2 holes of diameter 2mm φ by boring processing perforation, make rod 2 through holes by gained respectively of the stainless steel of diameter 1.6mm φ, under the state that connects experiment slice, these 2 rods are separately fixed on the chuck up and down of stretching experiment machine the tensile strength when mensuration is carried out stretching experiment with 5mm/ minute speed.Mensuration is carried out 7 samples, and 5 samples beyond 2 points are up and down averaged.
9) photochromic property
Xenon lamp L-2480 (300W) SHL-100 that uses shore pine ホ ト ニ Network ス to make is by Air quality strainer (aeromassfilter, コ-ニ Application グ corporate system), at 20 ℃ ± 1 ℃, the beam intensity 365nm=2.4mW/cm of polymer surfaces
2, 245nm=24 μ W/cm
2To 120 seconds of cured body (thickness 2mm, diameter 5cm's is discoid) irradiation of gained, develop the color down, measure the photochromic property of aforementioned sample.Each photochromic property is according to following method evaluation.
1. maximum absorption wavelength (λ max): be by (the maximum absorption wavelength after the colour developing of trying to achieve of the spectrophotometer (moment multichannel light detector MCPD1000) made of strain) Da mound electronic industry.The tone in this maximum absorption wavelength and when colour developing is relevant.
2. the concentration that develops the color { ε (120)-ε (0) }: the rayed in the aforementioned maximum absorption wavelength after 120 seconds absorbancy { ε (120) } and absorbancy ε (0) poor before the rayed.Can think that this value is high more, photochromism is excellent more.
3. [t fades the transformation period
1/2(min)]: rayed is after 120 seconds, when stopping rayed, and the absorbancy of the aforementioned maximum wavelength of sample is reduced to the 1/2 needed time of { ε (120)-ε (0) }.Can think that this time is short more, the speed of fading is fast more, and photochromism is excellent more.
10) pencil hardness
Fined away in the top of pencil, vertically push with the heavy burden of 1kg.Applying the state of heavy burden, the stretching pencil, hardness is judged in the experiment that makes buffer layer produce cut.If the pencil with 5H can add cut, then pencil hardness is 4H.
11) Rockwell hardness
It is the value of determining according to JIS K7202, the pressure head of using the rigid ball by diameter 6.350mm to form specifically applies 10Kgf on the surface of cured body experiment slice benchmark bears a heavy burden, the experiment that applies 60Kgf is again born a heavy burden, when getting back to the benchmark heavy burden once more, the pressure head that 2 secondary standards bear a heavy burden from front and back enter depth difference h (mm of unit), according to the calculating formula of 130-500h, the value of trying to achieve.
Embodiment 1
With 50 weight part BPE100,5 weight part TMPT, 5 weight part A200,24 weight part 4G, 10 weight part GMA, 5 weight part α MS, 1 weight part MSD thorough mixing.After adding the パ-Block チ Le ND of 0.03 weight part chromene, 1,1 weight part therein as thermal polymerization, thorough mixing.This mixed solution is injected in the mold that is made of the glass mold packing ring, and its middle washer is formed by ethylene-vinyl acetate copolymer.After 5 hours, from the glass model of mold, take out cured body 90 ℃ of following thermopolymerizations.Then, estimate the photochromic property and the intensive property of the cured body of gained.The result is as shown in table 1.
Embodiment 2
With 15 weight part BPE100,10 weight part BPE500,5 weight part TMPT, 49 weight part 4G, 5 weight part A200,10 weight part GMA, 5 weight part α MS, 1 weight part MSD thorough mixing.After adding the パ-Block チ Le ND of 0.03 weight part chromene, 1,1 weight part therein as thermal polymerization, thorough mixing.This mixed solution is injected in the mold that is made of glass mold and packing ring, and its middle washer is formed by ethylene-vinyl acetate copolymer.After 5 hours, from the glass model of mold, take out cured body 90 ℃ of following thermopolymerizations.Then, estimate the photochromic property and the intensive property of the cured body of gained.The result merges to shown in the table 1.
Embodiment 3～10
Similarly to Example 1, the polymerization-curable composition polymerization with table 1 record obtains cured body, estimates the photochromic property and the intensive property of the cured body of gained.The result is as shown in table 1.
Comparative example 1
With 50 weight part BPE100,20 weight part TMPT, 9 weight part 4G, 5 weight part A200,10 weight part GMA, 5 weight part α MS, 1 weight part MSD thorough mixing.After adding the パ-Block チ Le ND of 0.03 weight part chromene, 1,1 weight part therein as thermal polymerization, thorough mixing.This mixed solution is injected in the mold that is made of glass mold and packing ring, and its middle washer is formed by ethylene-vinyl acetate copolymer.After 5 hours, from the glass model of mold, take out cured body 90 ℃ of following thermopolymerizations.Then, estimate the photochromic property and the intensive property of the cured body of gained.The result is as shown in table 1.
Comparative example 2,3
With comparative example 1 similarly, the polymerization-curable composition polymerization with table 1 record obtains cured body.The photochromic property of the cured body of gained and the evaluation result of intensive property are as shown in table 1.
Table 1
| No. | Polymerization-curable composition | ||||
| Bifunctional polymerizable monomer (weight part) | Polyfunctional group polymerizable monomer (weight part) | Other polymerizable monomer (weight part) | Additive (weight part) | Photochromic compound (weight part) | |
| Embodiment 1 | BPE100 50 | TMPT 5 | 4G/A200/GMA/αMS/MSD 24/5/10/5/1 | - | Chromene 1 0.03 |
| Embodiment 2 | BPE100/BPE500 15/10 | TMPT 5 | 4G/A200/GMA/αMS/MSD 49/5/10/5/1 | - | Chromene 1 0.03 |
| Embodiment 3 | BPE100 50 | TMPT 10 | 4G/A200/GMA/αMS/MSD 22/2/10/5/1 | - | Chromene 1 0.03 |
| Embodiment 4 | BPE100 20 | TMPT 5 | 4G/A200/GMA/αMS/MSD 54/5/10/5/1 | - | Chromene 1 0.03 |
| Embodiment 5 | BPE100/BPE500 5/30 | TMPT 5 | 4G/A200/GMA/αMS/MSD 39/5/10/5/1 | - | Chromene 1 0.03 |
| Embodiment 6 | BPE100 50 | TMPT3EO 15 | 4G/A200/GMA/αMS/MSD 9/10/10/5/1 | - | Chromene 1 0.03 |
| Embodiment 7 | PDBP 50 | TMPT 5 | 4PGX/APG200/GMA/αMS/MSD 24/5/10/5/1 | - | Chromene 2 0.03 |
| Embodiment 8 | BPE100 50 | TMPT 2 | 4G/A400/GMA/αMS/MSD 24/8/10/5/1 | - | Chromene 2 0.03 |
| Embodiment 9 | BPE200 20 | TMPT 5 | 4G/M90G/GMA/αMS/MSD 44/15/10/5/1 | - | Chromene 2 0.03 |
| Embodiment 10 | BPE100 60 | TMPT 15 | 4G/PKA5009/GMA/αMS/MSD 7/2/10/5/1 | Tween20 1 | Chromene 2 0.03 |
| Comparative example 1 | BPE100 50 | TMPT 20 | 4G/A200/GMA/αMS/MSD 9/5/10/5/1 | - | Chromene 1 0.03 |
| Comparative example 2 | BPE100 50 | - | 4G/A200/GMA/αMS/MSD 32/2/10/5/1 | - | Chromene 2 0.03 |
| Comparative example 3 | - | TMPT 15 | 4G/A200/GMA/αMS/MSD 64/5/10/5/1 | - | Chromene 2 0.03 |
Table 1 (continuous table)
| No. | Intensive property | Photochromic property | |||
| Tensile strength (Kgf) | λ max(nm) | Colour developing concentration | Fading the transformation period in the cured body (branch) | Fading the transformation period in the solidification compound (branch) | |
| Embodiment 1 | 33 | 588 | 1.3 | 2.0 | 0.4 |
| Embodiment 2 | 27 | 588 | 1.3 | 2.0 | 0.4 |
| Embodiment 3 | 20 | 588 | 1.4 | 1.9 | 0.4 |
| Embodiment 4 | 27 | 588 | 1.3 | 2.0 | 0.4 |
| Embodiment 5 | 25 | 588 | 1.3 | 2.0 | 0.4 |
| Embodiment 6 | 34 | 588 | 1.3 | 2.2 | 0.4 |
| Embodiment 7 | 30 | 592 | 1.0 | 1.7 | 0.3 |
| Embodiment 8 | 35 | 592 | 0.8 | 1.8 | 0.3 |
| Embodiment 9 | 25 | 592 | 0.9 | 1.7 | 0.3 |
| Embodiment 10 | 17 | 592 | 0.9 | 1.7 | 0.3 |
| Comparative example 1 | 11 | 588 | 1.4 | 1.9 | 0.4 |
| Comparative example 2 | 35 | 592 | 0.6 | 4.2 | 0.3 |
| Comparative example 3 | 12 | 592 | 0.7 | 1.7 | 0.3 |
Can know from table 1, by having excellent photochromic property, and cured body with the intensity that can be used for no-frame glasses, with specific mixed bifunctional polymerizable monomer and polyfunctional group polymerizable monomer, can obtain the cured body that has excellent photochromic property and can guarantee to be used for the intensity of no-frame glasses.
Embodiment 11
With 30 weight part TMPT, 60 weight part BPE500,10 weight part GMA thorough mixing.After adding the イ Le ガ キ ユ ア 819 of 0.04 weight part chromene, 1,0.01 weight part therein as Photoepolymerizationinitiater initiater, thorough mixing under shading.This mixed solution is injected in the mold that is made of glass mold and packing ring, and its middle washer is formed by ethylene-vinyl acetate copolymer.By metal halide lamp it was shone 2 minutes.Irradiation is taken out cured body after finishing from the glass model of mold.
The photochromic property of the cured body of gained and the evaluation result of intensive property are as shown in table 2.In addition, the transformation period of fading of the monomer solution described in the table 2 is meant and solidifies fading the transformation period of preceding mixing solutions (solidification compound).
Embodiment 12
With 25 weight part TMPT, 45 weight part BPE500,20 weight part U-1084,10 weight part GMA thorough mixing.After adding the イ Le ガ キ ユ ア 819 of 0.04 weight part chromene, 1,0.01 weight part therein as Photoepolymerizationinitiater initiater, thorough mixing under shading.This mixed solution is injected in the mold that is made of glass mold and packing ring, and its middle washer is formed by ethylene-vinyl acetate copolymer.By metal halide lamp it was shone 2 minutes.Irradiation is taken out cured body after finishing from the glass model of mold.
The photochromic property of the cured body of gained and the evaluation result of intensive property are as shown in table 2.
Embodiment 13
With 25 weight part TMPT, 45 weight part BPE500,20 weight part EB-1830,10 weight part GMA thorough mixing.After adding the イ Le ガ キ ユ ア 819 of 0.04 weight part chromene, 1,0.01 weight part therein as Photoepolymerizationinitiater initiater, thorough mixing under shading.This mixed solution is injected in the mold that is made of glass mold and packing ring, and its middle washer is formed by ethylene-vinyl acetate copolymer.By metal halide lamp it was shone 2 minutes.Irradiation is taken out cured body after finishing from the glass model of mold.
The photochromic property of the cured body of gained and the evaluation result of intensive property are as shown in table 2.
Embodiment 14
With 20 weight part TMPT, 30 weight part BPE100,40 weight part BPE500 (ratio of the mole number (a2) of the mole number of BPE100 (a1) and BPE500 is 1.26), 10 weight part GMA thorough mixing.After adding the パ-Block チ Le IB of イ Le ガ キ ユ ア 819,0.5 weight part as thermal polymerization of 0.04 weight part chromene, 1,0.01 weight part therein as Photoepolymerizationinitiater initiater, thorough mixing under shading.This mixed solution is injected in the mold that is made of glass mold and packing ring, and its middle washer is formed by ethylene-vinyl acetate copolymer.By metal halide lamp it was shone 2 minutes.Irradiation after 5 hours, is taken out cured body 90 ℃ of following thermopolymerizations after finishing from the glass model of mold.
The photochromic property of the cured body of gained and the evaluation result of intensive property are as shown in table 2.
Embodiment 15
With 50 weight part AD-TMP-4CL, 40 weight part BPE500,10 weight part GMA thorough mixing.After adding the パ-Block チ Le IB of イ Le ガ キ ユ ア 819,0.5 weight part as thermal polymerization of 0.04 weight part chromene, 1,0.01 weight part therein as Photoepolymerizationinitiater initiater, thorough mixing under shading.This mixed solution is injected in the mold that is made of glass mold and packing ring, and its middle washer is formed by ethylene-vinyl acetate copolymer.By metal halide lamp it was shone 2 minutes.Irradiation after 5 hours, is taken out cured body 90 ℃ of following thermopolymerizations after finishing from the glass model of mold.
The photochromic property of the cured body of gained and the evaluation result of intensive property are as shown in table 2.
Comparative example 4
With 70 weight part TMPT, 20 weight part BPE, 500,10 weight part GMA thorough mixing.After adding the イ Le ガ キ ユ ア 819 of 0.04 weight part chromene, 1,0.01 weight part therein as Photoepolymerizationinitiater initiater, thorough mixing under shading.This mixed solution is injected in the mold that is made of glass mold and packing ring, and its middle washer is formed by ethylene-vinyl acetate copolymer.By metal halide lamp it was shone 2 minutes.Irradiation is taken out cured body after finishing from the glass model of mold.
The photochromic property of the cured body of gained and the evaluation result of intensive property are as shown in table 2.
Table 2
| No. | Photochromic property | Intensive property | |||
| λ max/nm | Colour developing concentration | Fade the transformation period/minute | Tensile strength/Kgf | ||
| Cured body | Monomer solution | ||||
| Embodiment 11 | 588 | 1.5 | 1.8 | 0.4 | 30 |
| Embodiment 12 | 588 | 1.4 | 1.9 | 0.4 | 35 |
| Embodiment 13 | 588 | 1.3 | 2.0 | 0.4 | 27 |
| Embodiment 14 | 588 | 1.5 | 1.8 | 0.4 | 32 |
| Embodiment 15 | 588 | 1.3 | 2.0 | 0.4 | 30 |
| Comparative example 4 | 588 | 1.4 | 1.8 | 0.3 | 11 |
Embodiment 16
With 10 weight part TMPT, 60 weight part BPE100,20 weight part A400,10 weight part GMA thorough mixing.After adding the パ-Block チ Le ND of 0.04 weight part chromene, 1,1 weight part therein as thermal polymerization, thorough mixing.This mixed solution is injected in the mold that is made of glass mold and packing ring, and its middle washer is formed by ethylene-vinyl acetate copolymer.After 5 hours, from the glass model of mold, take out cured body 90 ℃ of following thermopolymerizations.
The evaluation result of the intensive property of the cured body of gained is as shown in table 3.
The transformation period of fading in the solidification compound in the table 3 is measured after being the solidification compound of preparation same concentrations in addition.
Then, with デ ス モ ジ ユ-Le BL3475 (obtain with the isocyanate group of active methylene group block hexamethylene diisocyanate, firmly change バ イ エ Le ウ レ Application company and make) and デ ス モ Off エ Application 670BA (polyester polyol; Same companies is made) with 1: 1 mixed, mix the buffer layer coating fluid that obtains by dip coated, solidified 30 minutes down at 110 ℃.Then, by dip coated hardening solution TS-56H (silicone based colloidal sol; (strain) moral mountain system), solidified 3 hours down at 120 ℃.In addition, the thickness of the buffer layer in the dura mater product of gained is 3 μ m, and measuring its pencil hardness is H.In addition, the pencil hardness of the dura mater face of mensuration dura mater product is 8H.
Having formed the intensive property of cured body of buffer layer and hard coat and the evaluation result of photochromic property merges to shown in the table 3.
Embodiment 17
In bisphenol A type epoxy resin, add 5 weight % triethylamines, form the buffer layer coating fluid, this coating fluid is applied on the cured body (material before buffer layer and hard coat form) that embodiment 16 obtains, 110 ℃ of curing 30 minutes down by dipping.Then, by dip coated hardening solution TS-56H, solidified 3 hours down at 120 ℃.In addition, the buffer layer thickness of the dura mater product of gained is 3 μ m, and measuring its pencil hardness is 2H.
Having formed the intensive property of cured body of buffer layer and hard coat and the evaluation result of photochromic property merges to shown in the table 3.
Embodiment 18
By being immersed in last coating of cured body (material before buffer layer and hard coat form) that embodiment 16 obtains by the KS (organosilicon that contains titanium dioxide; Network レ Ha レ Application テ Star Network (strain) manufacturing) the buffer layer coating fluid that forms solidified 30 minutes down at 110 ℃.Then, by dip coated hardening solution TS-56H, solidified 3 hours down at 120 ℃.In addition, the thickness of the buffer layer in the dura mater product of gained is 3 μ m, and measuring its pencil hardness is 6H.
Having formed the intensive property of cured body of buffer layer and hard coat and the evaluation result of photochromic property merges to shown in the table 3.
Comparative example 5
The cured body that embodiment 16 is obtained (material before buffer layer and hard coat form) etching after 10 minutes in 60 ℃ 10% aqueous sodium hydroxide solution, by dip coated hardening solution TS-56H (the silicone based colloidal sol that make on the moral mountain), solidified 3 hours down at 120 ℃.
The formation of gained the intensive property of cured body of hard coat and the evaluation result of photochromic property merge to shown in the table 3.
Table 3
| Intensive property | Photochromic property | Other character | |||||
| Tensile strength/Kgf | λ max/nm | Colour developing concentration | Fade the transformation period/minute | The Rockwell hardness of base material | |||
| Cured body | In the solidification compound | ||||||
| Embodiment 16 | Before hard coat forms | 22 | 588 | 1.4 | 1.9 | 0.4 | 90 |
| After hard coat forms | 22 | 588 | 1.4 | 1.9 | 0.4 | 90 | |
| Embodiment 17 | Before hard coat forms | 22 | 588 | 1.4 | 1.9 | 0.4 | 90 |
| After hard coat forms | 22 | 588 | 1.4 | 1.9 | 0.4 | 90 | |
| Embodiment 18 | Before hard coat forms | 22 | 588 | 1.4 | 1.9 | 0.4 | 90 |
| After hard coat forms | 22 | 588 | 1.4 | 1.9 | 0.4 | 90 | |
| Comparative example 5 | Before hard coat forms | 22 | 588 | 1.4 | 1.9 | 0.4 | 90 |
| After hard coat forms | 15 | 588 | 1.4 | 1.9 | 0.4 | 90 | |
Can know from table 3, by having excellent photochromic property, and the cured body with the intensity that can be used for no-frame glasses inserts buffer layer and forms hard coat, and the hard coat that can obtain having excellent photochromic property and can guarantee to be used for the intensity of no-frame glasses forms cured body.On the other hand, if do not insert buffer layer, form hard coat, find that then intensity is low, the result is to be used for no-frame glasses.
Claims (12)
1. photochromic lens base material, it is characterized in that: the cured body by polymerization-curable composition forms, and this polymerization-curable composition comprises:
(I) the represented polyfunctional group polymerizable monomer of following formula (1),
In the formula, R
1Be hydrogen atom or methyl, group-R
2-be-CH
2CH
2O-,-CH
2CH (CH
3) O-or-C (=O) CH
2CH
2CH
2CH
2CH
2Group shown in the O-, R
3Be organic residue of 3～6 valencys, a is 0～3 integer, and b is 3～6 integer;
(II) the bifunctional polymerizable monomer shown in the following formula (2),
In the formula, R
4And R
5Be hydrogen atom or methyl independently of one another, R
6And R
7Be that hydrogen atom or carbonatoms are 1～2 alkyl independently of one another, group-X-is-O-,-S-,-S (=O)
2-,-C (=O)-O-,-CH
2-,-CH=CH-or-C (CH
3)
2-shown in group, m and n are that m+n is 0～30 integer;
(III) photochromic compound;
The transformation period of fading of the photochromic compound in this cured body (III) is than 30 times of weak points of the transformation period of the photochromic compound in this polymerization-curable composition (III), and tensile strength be 15Kgf or more than.
2. the lens substrate of putting down in writing according to claim 1, wherein bifunctional polymerizable monomer (II) is that 0～5 the 1st bifunctional polymerizable monomer and the m+n in the above-mentioned formula (2) are that 6～30 the 2nd bifunctional polymerizable monomer constitutes by the m+n in the above-mentioned formula (2), and the 2nd bifunctional polymerizable monomer be the 1st bifunctional polymerizable monomer 3 times of moles or below.
3. the lens substrate of putting down in writing according to claim 1, wherein polymerization-curable composition further contains thermal polymerization, and be benchmark with the whole polymerizable monomer that contains in the polymerization-curable composition, above-mentioned polyfunctional group polymerizable monomer (I) and above-mentioned bifunctional polymerizable monomer (II) contain 1～15 weight % and 10～80 weight % respectively.
4. the lens substrate of putting down in writing according to claim 1, wherein polymerization-curable composition further contains Photoepolymerizationinitiater initiater, and be benchmark with the whole polymerizable monomer that contains in the polymerization-curable composition, above-mentioned polyfunctional group polymerizable monomer (I) and above-mentioned bifunctional polymerizable monomer (II) contain 1～60 weight % and 10～90 weight % respectively.
5. the lens substrate of putting down in writing according to claim 4, wherein polymerization-curable composition further contains at least a kind of oligopolymer that is selected from 2～6 functional group's polymerizability urethane oligomers and 2～6 functional group's polyester oligomers.
6. polymerization-curable composition is characterized in that: this polymer cure composition comprises,
(I) the polyfunctional group polymerizable monomer shown in the above-mentioned formula (1),
(II) the bifunctional polymerizable monomer shown in the above-mentioned formula (2),
(III) with above-mentioned polymerizable monomer (I) and (II) different other polymerizable monomer,
(IV) photochromic compound and
(V) thermal polymerization;
And be benchmark with whole polymerizable monomers, the content of above-mentioned polyfunctional group polymerizable monomer (I), above-mentioned bifunctional polymer's monomer (II) and other polymerizable monomer (III) is respectively 1～15 weight %, 10～80 weight % and 5～89 weight %.
7. the composition of putting down in writing according to claim 6, wherein the content of polyfunctional group polymerizable monomer (I), bifunctional polymerizable monomer (II) and other polymerizable monomer (III) is respectively 3～10 weight %, 20～60 weight % and 30～77 weight %.
8. the composition of putting down in writing according to claim 6, wherein bifunctional polymerizable monomer (II) is that 0～5 the 1st bifunctional polymerizable monomer and the m+n in the above-mentioned formula (2) are that 6～30 the 2nd bifunctional polymerizable monomer constitutes by the m+n in the above-mentioned formula (2), and the 2nd bifunctional polymerizable monomer be the 1st bifunctional polymerizable monomer 3 times of moles or below.
9. polymerization-curable composition is characterized in that: this polymer cure composition comprises,
(I) the polyfunctional group polymerizable monomer shown in the above-mentioned formula (1),
(II) the bifunctional polymerizable monomer shown in the above-mentioned formula (2),
(III) according to situation and above-mentioned polymerizable monomer (I) and (II) polymerizable monomer of different other,
(IV) photochromic compound and
(V) Photoepolymerizationinitiater initiater;
And be benchmark with whole polymerizable monomers, the content of above-mentioned polyfunctional group polymerizable monomer (I), above-mentioned bifunctional polymer's monomer (II) and other polymerizable monomer (III) is respectively 1～60 weight %, 10～90 weight % and 0～89 weight %.
10. the composition of putting down in writing according to claim 9, wherein the content of polyfunctional group polymerizable monomer (I), bifunctional polymerizable monomer (II) and other polymerizable monomer (III) is respectively 10～60 weight %, 20～90 weight % and 0～70 weight %.
11. the composition of putting down in writing according to claim 9, wherein bifunctional polymerizable monomer (II) is that 0～5 the 1st bifunctional polymerizable monomer and the m+n in the above-mentioned formula (2) are that 6～30 the 2nd bifunctional polymerizable monomer constitutes by the m+n in the above-mentioned formula (2), and the 2nd bifunctional polymerizable monomer be the 1st bifunctional polymerizable monomer 3 times of moles or below.
12. photochromic lens, it is characterized in that: these lens comprise, the photochromic lens base material of record in the claim 1, hard coat and be present between these base materials and the hard coat and pencil hardness lower than the pencil hardness of hard coat, be used to engage the buffer layer of this base material and hard coat.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003077114A JP4200032B2 (en) | 2003-03-20 | 2003-03-20 | Polymerization curable composition |
| JP77114/2003 | 2003-03-20 | ||
| JP208784/2003 | 2003-08-26 |
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|---|---|
| CN1738842A true CN1738842A (en) | 2006-02-22 |
| CN100357332C CN100357332C (en) | 2007-12-26 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101935376A (en) * | 2009-06-29 | 2011-01-05 | 富士胶片株式会社 | Photocurable composition for embossing and method for producing cured products |
| CN101889036B (en) * | 2007-12-13 | 2013-01-02 | 株式会社德山 | Photochromic curable composition |
| CN108424482A (en) * | 2018-02-27 | 2018-08-21 | 同济大学 | A kind of dendritic of multiple response and preparation method thereof containing spiro-pyrans |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4261656A (en) * | 1979-03-12 | 1981-04-14 | Corning Glass Works | Optically clear articles incorporating protective plastic coatings |
| US5200483A (en) * | 1991-11-07 | 1993-04-06 | Ppg Industries, Inc. | Polyol(allyl carbonate) composiitons and articles prepared there from |
| JPH11209750A (en) * | 1998-01-26 | 1999-08-03 | Tokuyama Corp | Photochromic curable composition |
| JP3681534B2 (en) * | 1998-03-13 | 2005-08-10 | 株式会社トクヤマ | Polymerization curable composition for optical lens |
| JP3922873B2 (en) * | 2000-09-29 | 2007-05-30 | 株式会社トクヤマ | Curable composition |
| JP4305594B2 (en) * | 2000-11-28 | 2009-07-29 | 株式会社トクヤマ | Dental bonding kit |
| JP4726026B2 (en) * | 2001-03-13 | 2011-07-20 | 株式会社トクヤマ | Dental primer composition |
-
2003
- 2003-03-20 JP JP2003077114A patent/JP4200032B2/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101889036B (en) * | 2007-12-13 | 2013-01-02 | 株式会社德山 | Photochromic curable composition |
| CN101935376A (en) * | 2009-06-29 | 2011-01-05 | 富士胶片株式会社 | Photocurable composition for embossing and method for producing cured products |
| CN108424482A (en) * | 2018-02-27 | 2018-08-21 | 同济大学 | A kind of dendritic of multiple response and preparation method thereof containing spiro-pyrans |
| CN108424482B (en) * | 2018-02-27 | 2020-06-02 | 同济大学 | Spiropyran-containing multi-responsiveness dendritic polymer and preparation method thereof |
| CN113614622A (en) * | 2019-03-29 | 2021-11-05 | 豪雅镜片泰国有限公司 | Spectacle lens and spectacles |
| CN113614622B (en) * | 2019-03-29 | 2023-09-22 | 豪雅镜片泰国有限公司 | Spectacle lens and spectacles |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004285141A (en) | 2004-10-14 |
| JP4200032B2 (en) | 2008-12-24 |
| CN100357332C (en) | 2007-12-26 |
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