JP5164459B2 - Curable composition - Google Patents
Curable composition Download PDFInfo
- Publication number
- JP5164459B2 JP5164459B2 JP2007182570A JP2007182570A JP5164459B2 JP 5164459 B2 JP5164459 B2 JP 5164459B2 JP 2007182570 A JP2007182570 A JP 2007182570A JP 2007182570 A JP2007182570 A JP 2007182570A JP 5164459 B2 JP5164459 B2 JP 5164459B2
- Authority
- JP
- Japan
- Prior art keywords
- curable composition
- surfactant
- polymerizable monomer
- acid
- liquid
- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 85
- 239000000178 monomer Substances 0.000 claims description 49
- 239000004094 surface-active agent Substances 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000003960 organic solvent Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 20
- 239000000945 filler Substances 0.000 claims description 16
- 239000007870 radical polymerization initiator Substances 0.000 claims description 14
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- -1 4-methacryloyloxydiethoxyphenyl Chemical group 0.000 description 51
- 239000007788 liquid Substances 0.000 description 42
- 239000010410 layer Substances 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 24
- 238000003860 storage Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000003505 polymerization initiator Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 150000001451 organic peroxides Chemical class 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000011256 inorganic filler Substances 0.000 description 7
- 229910003475 inorganic filler Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229910001447 ferric ion Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 239000002563 ionic surfactant Substances 0.000 description 5
- 239000000693 micelle Substances 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- SOFSSZFBVOGIKD-UHFFFAOYSA-N pyrimidine-2,4,5-trione Chemical class O=C1NC(=O)C(=O)C=N1 SOFSSZFBVOGIKD-UHFFFAOYSA-N 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000005548 dental material Substances 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical class OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000012766 organic filler Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000037048 polymerization activity Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- XILIYVSXLSWUAI-UHFFFAOYSA-N 2-(diethylamino)ethyl n'-phenylcarbamimidothioate;dihydrobromide Chemical compound Br.Br.CCN(CC)CCSC(N)=NC1=CC=CC=C1 XILIYVSXLSWUAI-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- JUVSRZCUMWZBFK-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-4-methylanilino]ethanol Chemical compound CC1=CC=C(N(CCO)CCO)C=C1 JUVSRZCUMWZBFK-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical class C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical compound O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 239000003479 dental cement Substances 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 1
- JHQVCQDWGSXTFE-UHFFFAOYSA-N 2-(2-prop-2-enoxycarbonyloxyethoxy)ethyl prop-2-enyl carbonate Chemical compound C=CCOC(=O)OCCOCCOC(=O)OCC=C JHQVCQDWGSXTFE-UHFFFAOYSA-N 0.000 description 1
- ZJIXDTVWANWBLG-UHFFFAOYSA-N 2-[2,3,4,5-tetraethoxy-6-[2-[2,3,4,5-tetraethoxy-6-[2-(2-methylprop-2-enoyloxy)ethoxy]phenyl]propan-2-yl]phenoxy]ethyl 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OCCOC1=C(C(=C(C(=C1OCC)OCC)OCC)OCC)C(C)(C)C1=C(C(=C(C(=C1OCC)OCC)OCC)OCC)OCCOC(C(=C)C)=O ZJIXDTVWANWBLG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NXBXJOWBDCQIHF-UHFFFAOYSA-N 2-[hydroxy-[2-(2-methylprop-2-enoyloxy)ethoxy]phosphoryl]oxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(=O)OCCOC(=O)C(C)=C NXBXJOWBDCQIHF-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- DILXLMRYFWFBGR-UHFFFAOYSA-N 2-formylbenzene-1,4-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(S(O)(=O)=O)C(C=O)=C1 DILXLMRYFWFBGR-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OPZLDVPRAIERSE-UHFFFAOYSA-N 3-[4-[2-[4-[3-(2-methylprop-2-enoyloxy)propoxy]phenyl]propan-2-yl]phenoxy]propyl 2-methylprop-2-enoate Chemical compound C1=CC(OCCCOC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCCCOC(=O)C(C)=C)C=C1 OPZLDVPRAIERSE-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- HTKIZIQFMHVTRJ-UHFFFAOYSA-N 5-butyl-1,3-diazinane-2,4,6-trione Chemical compound CCCCC1C(=O)NC(=O)NC1=O HTKIZIQFMHVTRJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
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- 229930182556 Polyacetal Natural products 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- VSXPEHGZLDNBNU-UHFFFAOYSA-N [2,3,5,6-tetraethoxy-4-[2-[2,3,5,6-tetraethoxy-4-(2-methylprop-2-enoyloxy)phenyl]propan-2-yl]phenyl] 2-methylprop-2-enoate Chemical compound CCOC1=C(OC(=O)C(C)=C)C(OCC)=C(OCC)C(C(C)(C)C=2C(=C(OCC)C(OC(=O)C(C)=C)=C(OCC)C=2OCC)OCC)=C1OCC VSXPEHGZLDNBNU-UHFFFAOYSA-N 0.000 description 1
- FSDJQMOZRWOIRG-UHFFFAOYSA-N [2,3-dipropoxy-4-[2-[2,3,5-triethoxy-4-(2-methylprop-2-enoyloxy)phenyl]propyl]phenyl] 2-methylprop-2-enoate Chemical compound C1=CC(OC(=O)C(C)=C)=C(OCCC)C(OCCC)=C1CC(C)C1=CC(OCC)=C(OC(=O)C(C)=C)C(OCC)=C1OCC FSDJQMOZRWOIRG-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
- NMHJAFPCUXEYFN-UHFFFAOYSA-N [2-[2-[2-(2-methylprop-2-enoyloxy)phenyl]propan-2-yl]phenyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1C(C)(C)C1=CC=CC=C1OC(=O)C(C)=C NMHJAFPCUXEYFN-UHFFFAOYSA-N 0.000 description 1
- SWHLOXLFJPTYTL-UHFFFAOYSA-N [2-methyl-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(COC(=O)C(C)=C)COC(=O)C(C)=C SWHLOXLFJPTYTL-UHFFFAOYSA-N 0.000 description 1
- FOVRCPBDDCLNIG-UHFFFAOYSA-N [3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(COC(=O)C(C)=C)COC(=O)C(C)=C FOVRCPBDDCLNIG-UHFFFAOYSA-N 0.000 description 1
- JNGWKQJZIUZUPR-UHFFFAOYSA-N [3-(dodecanoylamino)propyl](hydroxy)dimethylammonium Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)[O-] JNGWKQJZIUZUPR-UHFFFAOYSA-N 0.000 description 1
- SJSXBTSSSQCODU-UHFFFAOYSA-N [4-[2-[2,3-diethoxy-4-(2-methylprop-2-enoyloxy)phenyl]propan-2-yl]-2,3-diethoxyphenyl] 2-methylprop-2-enoate Chemical compound CCOC1=C(OC(=O)C(C)=C)C=CC(C(C)(C)C=2C(=C(OCC)C(OC(=O)C(C)=C)=CC=2)OCC)=C1OCC SJSXBTSSSQCODU-UHFFFAOYSA-N 0.000 description 1
- NFNKGIYWQDTWKO-UHFFFAOYSA-N [4-[2-[2,3-diethoxy-4-(2-methylprop-2-enoyloxy)phenyl]propyl]-2,3-diethoxyphenyl] 2-methylprop-2-enoate Chemical compound C1=CC(OC(=O)C(C)=C)=C(OCC)C(OCC)=C1CC(C)C1=CC=C(OC(=O)C(C)=C)C(OCC)=C1OCC NFNKGIYWQDTWKO-UHFFFAOYSA-N 0.000 description 1
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- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
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- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 1
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 description 1
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 1
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- 125000000753 cycloalkyl group Chemical group 0.000 description 1
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- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GOJNABIZVJCYFL-UHFFFAOYSA-N dimethylphosphinic acid Chemical compound CP(C)(O)=O GOJNABIZVJCYFL-UHFFFAOYSA-N 0.000 description 1
- WTIFDVLCDRBEJK-VAWYXSNFSA-N diphenyl (e)-but-2-enedioate Chemical compound C=1C=CC=CC=1OC(=O)/C=C/C(=O)OC1=CC=CC=C1 WTIFDVLCDRBEJK-VAWYXSNFSA-N 0.000 description 1
- BEQVQKJCLJBTKZ-UHFFFAOYSA-N diphenylphosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-N 0.000 description 1
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- TWFQJFPTTMIETC-UHFFFAOYSA-N dodecan-1-amine;hydron;chloride Chemical compound [Cl-].CCCCCCCCCCCC[NH3+] TWFQJFPTTMIETC-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
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- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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- 239000003456 ion exchange resin Substances 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- DLAPQHBZCAAVPQ-UHFFFAOYSA-N iron;pentane-2,4-dione Chemical compound [Fe].CC(=O)CC(C)=O DLAPQHBZCAAVPQ-UHFFFAOYSA-N 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229940026210 lauramidopropylamine oxide Drugs 0.000 description 1
- IZWSFJTYBVKZNK-UHFFFAOYSA-N lauryl sulfobetaine Chemical compound CCCCCCCCCCCC[N+](C)(C)CCCS([O-])(=O)=O IZWSFJTYBVKZNK-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 229940005650 monomethyl fumarate Drugs 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- NGDIAZZSCVVCEW-UHFFFAOYSA-M sodium;butyl sulfate Chemical compound [Na+].CCCCOS([O-])(=O)=O NGDIAZZSCVVCEW-UHFFFAOYSA-M 0.000 description 1
- XZTJQQLJJCXOLP-UHFFFAOYSA-M sodium;decyl sulfate Chemical compound [Na+].CCCCCCCCCCOS([O-])(=O)=O XZTJQQLJJCXOLP-UHFFFAOYSA-M 0.000 description 1
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 description 1
- WSVLUYNDHYCZGD-UHFFFAOYSA-M sodium;hexyl sulfate Chemical compound [Na+].CCCCCCOS([O-])(=O)=O WSVLUYNDHYCZGD-UHFFFAOYSA-M 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Landscapes
- Dental Preparations (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は硬化性組成物に関する。更に詳しくは、酸素遮断材の塗布などによる酸素遮断層を設けることなく、硬化時における酸素の影響を低減できる新規な硬化性組成物に関するものである。 The present invention relates to a curable composition. More specifically, the present invention relates to a novel curable composition that can reduce the influence of oxygen at the time of curing without providing an oxygen barrier layer by applying an oxygen barrier material or the like.
硬化性組成物は、重合性単量体と重合開始剤とを含む材料である。硬化性組成物がラジカル重合性である場合、重合工程を空気中で行うと、硬化中の組成物における空気に露出した面に未重合層が生じる。未重合層は以下に示す過程を経て生じる。まず、空気に露出した面で酸素分子がラジカルと結合する。生じた過酸化物ラジカルはラジカル重合性単量体と反応しないので、表面における重合が停止する。重合が停止して重合性単量体が反応せずに残り、硬化性組成物表面に未重合層が生じる。 The curable composition is a material containing a polymerizable monomer and a polymerization initiator. When the curable composition is radically polymerizable, when the polymerization step is performed in air, an unpolymerized layer is formed on the surface of the composition being cured exposed to air. The unpolymerized layer is produced through the following process. First, oxygen molecules bind to radicals on the surface exposed to air. Since the generated peroxide radical does not react with the radical polymerizable monomer, the polymerization on the surface stops. The polymerization is stopped, the polymerizable monomer remains unreacted, and an unpolymerized layer is formed on the surface of the curable composition.
従来、表面に未重合層を有しない硬化体を提供するために幾つかの手法が行われてきた。例えば、窒素雰囲気下や水中での硬化、または酸素遮断材を用いて酸素遮断層を設けるなどして空気との接触を断ち、硬化性組成物をラジカル重合させる方法等である（例えば、特許文献１，２参照）。 Conventionally, several methods have been performed to provide a cured body having no unpolymerized layer on the surface. For example, there is a method of radical polymerization of a curable composition by cutting the contact with air by curing in a nitrogen atmosphere or in water, or providing an oxygen blocking layer using an oxygen blocking material (for example, patent document) 1 and 2).
このうち、（メタ）アクリレート系重合性単量体をラジカル重合で硬化させる手法は、一般工業用途で幅広く利用されており、歯科の分野に於いても利用されている。この手法を採用した歯科材料として、歯科用セメント、歯科用接着材（ボンディング材）、コンポジットレジン、レジン歯科材料表面の滑沢性付与材、歯牙のマニキュア、義歯の補修・裏装用の材料、暫間的なクラウン・ブリッジ等が挙げられる。これらの歯科用修復物の硬化体表面に未重合層が存在すると、表面硬度の低下等の問題が生じる。また、表面に未重合層があると硬化体の研磨・研削を行う際に未重合層が研磨バーに絡みついて、その研磨性が低下する欠点がある。さらに、歯科用途において窒素雰囲気や水中での硬化は現実的でなく、酸素遮断材の塗布は手間が掛かることが問題である。 Among these, the method of curing a (meth) acrylate polymerizable monomer by radical polymerization is widely used in general industrial applications, and is also used in the dental field. Dental materials that employ this method include dental cement, dental adhesives (bonding materials), composite resins, resin surface lubricity imparting materials, tooth nail polish, denture repair and lining materials, Intermittent crowns and bridges. If an unpolymerized layer is present on the surface of the cured body of these dental restorations, problems such as a decrease in surface hardness occur. In addition, when there is an unpolymerized layer on the surface, there is a drawback that the unpolymerized layer is entangled with the polishing bar when the cured body is polished and ground, and the polishability is lowered. Furthermore, in dental applications, curing in a nitrogen atmosphere or in water is not practical, and the problem is that it takes time to apply the oxygen-blocking material.
上記課題に対し、酸素の影響を低減した硬化体を得る技術をさらに検討し、ラジカル重合性単量体、水、界面活性剤、有効量のラジカル重合開始剤を含んでなる硬化性組成物によれば、硬化時に、表面に水と界面活性剤とからなる薄い層が形成され、これが酸素の侵入を防止して、上記未重合の発生を抑制できることが提案されている（特許文献３参照）。 In order to solve the above problems, a technique for obtaining a cured product with reduced influence of oxygen was further studied, and a curable composition comprising a radical polymerizable monomer, water, a surfactant, and an effective amount of a radical polymerization initiator was developed. According to this, it is proposed that a thin layer composed of water and a surfactant is formed on the surface at the time of curing, which can prevent the intrusion of oxygen and suppress the occurrence of unpolymerization (see Patent Document 3). .
しかしながら、本発明者らがさらに検討を進めたところ、この硬化性組成物における、表面未重合の発生を抑制する効果は、組成物の製造直後ではとても優れているものの、その効果は組成物の保存期間が長くなると徐々に低減していくことが発覚した。そして、さらに、このように長期保存した硬化性組成物では、液の透明性が低下し、硬化させた際に硬化時間の遅延の問題も生じ、さらに改良の余地があることが明らかになった。 However, when the present inventors further studied, the effect of suppressing the occurrence of surface unpolymerization in this curable composition is very excellent immediately after the production of the composition, but the effect is It was discovered that the storage period gradually decreased as the storage period increased. Further, in the curable composition stored for a long time in this way, the transparency of the liquid is lowered, and when it is cured, there is a problem of a delay in the curing time, and it becomes clear that there is room for further improvement. .
しかしてこの理由は、上記硬化性組成物の保存中に、組成から水が分離してしまうことが主要因であると考えられる。すなわち、ラジカル重合性単量体、界面活性剤、水、および重合開始剤の組み合わせからなる硬化性組成物では、ミクロサイズで微分散している水の安定性が今一歩十分でなく、保存期間が長くなると、組成物から分離し始める。そして、これに伴って界面活性剤も該組成物から分離し、その結果、この硬化性組成物を長期保存後に硬化させると、得られる硬化体表面に生じる未重合量が増加するようになると考えられる。しかも、このように一旦、相分離してしまった硬化性組成物は、再び、水と界面活性剤がミクロサイズで微分散した状態に戻すのが難しい状態にあり、少々攪拌したとしても、表面未重合の発生抑制効果はほとんど回復できなかった。また、この水と界面活性剤の分離が、前記液の透明性の低下も引き起こしていると考えられる。 However, it is considered that the main reason for this is that water is separated from the composition during storage of the curable composition. In other words, in a curable composition comprising a combination of a radical polymerizable monomer, a surfactant, water, and a polymerization initiator, the stability of water that is finely dispersed in a micro size is not sufficient, and the storage period Begins to separate from the composition. Along with this, the surfactant is also separated from the composition, and as a result, if this curable composition is cured after long-term storage, the amount of unpolymerization generated on the surface of the resulting cured product will increase. It is done. Moreover, the curable composition once phase-separated in this manner is in a state where it is difficult to return the water and the surfactant to a finely dispersed state in a micro size. The effect of suppressing the occurrence of unpolymerization could hardly be recovered. In addition, it is considered that the separation of the water and the surfactant causes a decrease in the transparency of the liquid.
なお、硬化時間の遅延の原因はよく分かっていないが、これは更なる欠点を生む。つまり、硬化のために多くの重合開始剤の添加を必要とし、硬化体の変色の原因になる。 It should be noted that the cause of the delay in curing time is not well understood, but this creates additional drawbacks. That is, the addition of a large amount of polymerization initiator is required for curing, which causes discoloration of the cured product.
一方、ラジカル重合性単量体に界面活性剤を添加することにより、歯牙等の硬組織に対する接着剤として使用した場合、刺激や侵襲の少ない硬化性組成物を得られることが報告されている（特許文献４参照）。該硬化性組成物にはさらに希釈溶媒として水、アルコール等の希釈溶媒を配合し得る。しかし、実施例での具体的使用態様は、上記硬化性組成物を組成分割し、まず、界面活性剤と水やアルコール等の希釈溶媒を含むＩ液を歯牙等に塗布し、それをエアーブローして乾燥させた後に、ラジカル重合性単量体及び重合開始剤を含むII液を塗布、硬化させるという使い方がされている。従って、硬化させる際に前記硬化性組成物の大気に露出している部分は、上記有機溶媒が配合された組成物とはなり得ない。また、同文献には、上記硬化性組成物をプライマーとして使用することも開示されている。しかしながら、プライマーは、親水性のラジカル重合性単量体を歯質に親和させることが目的の材料であるため、その実施例において、上記希釈溶媒は、歯質への親和性を重視して全て水が使用されており、有機溶媒が使用された例は全く開示されていない。 On the other hand, it has been reported that by adding a surfactant to a radical polymerizable monomer, a curable composition with less irritation and invasion can be obtained when used as an adhesive for hard tissues such as teeth ( (See Patent Document 4). The curable composition may further contain a diluent solvent such as water or alcohol as a diluent solvent. However, the specific usage mode in the examples is that the above-mentioned curable composition is divided into components, and first, a liquid I containing a surfactant and a diluting solvent such as water or alcohol is applied to teeth, and then air blown. After being dried, the II liquid containing a radical polymerizable monomer and a polymerization initiator is applied and cured. Accordingly, the portion of the curable composition that is exposed to the atmosphere when cured cannot be a composition containing the organic solvent. The same document also discloses that the curable composition is used as a primer. However, since the primer is a material whose purpose is to make the hydrophilic radical polymerizable monomer compatible with the tooth, in the example, the dilution solvent described above emphasizes the affinity for the tooth. No example is disclosed where water is used and an organic solvent is used.
この他、ラジカル重合性単量体、アセトン、光重合開始剤、フッ素系界面活性剤を含有させた硬化性組成物も知られている（特許文献５参照）。しかし、この硬化性組成物において、フッ素系界面活性剤の配合目的はレベリング性を良くするためであり、この成分により硬化体表面の未重合層低減させることは意図されていない。また、その使用態様は、やはり上記と同じように硬化性組成物を塗布後、アセトンは乾燥除去させてから硬化反応が遂行されている。そしてさらに、後述する比較例で示されるように、斯様に硬化性組成物にフッ素系界面活性剤の配合したのでは、該未重合層低減には顕著な効果は得られないものであった。 In addition, a curable composition containing a radical polymerizable monomer, acetone, a photopolymerization initiator, and a fluorosurfactant is also known (see Patent Document 5). However, in this curable composition, the purpose of blending the fluorosurfactant is to improve leveling, and this component is not intended to reduce the unpolymerized layer on the surface of the cured product. Also, in the usage mode, after the curable composition is applied as in the above, the acetone is dried and removed before the curing reaction is performed. Further, as shown in Comparative Examples described later, when a fluorinated surfactant was blended in such a curable composition, no significant effect was obtained in reducing the unpolymerized layer. .
以上の背景にあって本発明は、酸素の存在する雰囲気下で硬化させた際に、酸素遮断剤を用いなくても、未重合層がほとんど生じない硬化性組成物であって、この未重合層が形成されない効果は、該硬化性組成物を長期に保存しても良好に発揮され、さらに、液の透明性低下、硬化時間の遅延抑制等の問題も解決された硬化性組成物を提供することを目的とする。 In the background described above, the present invention is a curable composition in which an unpolymerized layer is hardly formed even when an oxygen blocking agent is not used when cured in an atmosphere containing oxygen. The effect that the layer is not formed is exhibited satisfactorily even when the curable composition is stored for a long period of time, and further provides a curable composition in which problems such as a decrease in the transparency of the liquid and suppression of a delay in the curing time are solved. The purpose is to do.
本発明者らは、上記目的を達成すべく鋭意検討を続けてきた。その結果、前記界面活性剤を含有した硬化性組成物において、水に代えるか、さらに該水に加えるかして親水性有機溶媒を配合することにより、前記の課題が解決できることを見だし、本発明を完成するに至った。 The inventors of the present invention have continually studied to achieve the above object. As a result, in the curable composition containing the surfactant, it was found that the above-mentioned problem can be solved by blending a hydrophilic organic solvent in place of water or by adding to the water. The invention has been completed.
即ち、本発明は、（１）ラジカル重合性単量体１００質量部に対して、（２）親水性有機溶媒を０．１〜３０質量部、（３）非フッ素系界面活性剤を０．１〜１０質量部、（４）ラジカル重合開始剤を有効量で夫々含有してなる硬化性組成物からなることを特徴とする（２）親水性有機溶媒存在下で硬化させて使用される歯科用裏装材である。 That is, the present invention relates to (1) 100 parts by mass of the radically polymerizable monomer, (2) 0.1 to 30 parts by mass of the hydrophilic organic solvent, and (3) 0.03 of the non-fluorinated surfactant. 1-10 parts by weight, is used (4), characterized in that it consists of a radical polymerization initiator effective amount hardening composition Do that contain respectively in (2) is cured in the presence of a hydrophilic organic solvent Dental lining material .
また別の発明は、さらに（５）水を含んでなる硬化性組成物である。 Another invention is a curable composition further comprising (5) water.
また別の発明は、さらに（６）フィラーを含んでなる硬化性組成物である。 Another invention is a curable composition further comprising (6) a filler.
本発明の硬化性組成物は、酸素が存在する環境下で、酸素遮断材を用いるなどの特別の手段を用いなくても、未重合層の生成を高度に抑制することができる。また、保存安定性が高く、上記未重合層の生成抑制効果は、該硬化性組成物を長期に保存しても良好に発揮される。さらに、得られる硬化体の透明性も高く維持され、硬化時間の遅延も生じ難い。 The curable composition of the present invention can highly suppress the formation of an unpolymerized layer without using special means such as using an oxygen blocking material in an environment where oxygen is present. In addition, the storage stability is high, and the effect of suppressing the formation of the unpolymerized layer is satisfactorily exhibited even when the curable composition is stored for a long time. Furthermore, the transparency of the cured product obtained is maintained high, and the curing time is hardly delayed.
本発明の硬化性組成物は、（１）ラジカル重合性単量体、（２）親水性有機溶媒、（３）界面活性剤、（４）重合開始剤を必須成分として含んでなる。このような硬化性組成物において、硬化体表面における未重合の発生が低減できる機構は必ずしも明確でないが、以下に示す機構が考えられる。すなわち、ラジカル重合性単量体が硬化する際に発生する重合熱によって親水性有機溶媒が硬化体から揮発し、親水性有機溶媒の揮発と同時に表面に界面活性剤が運搬され、表面に界面活性剤の薄い層が形成される。この界面活性剤の層が内部への酸素の侵入を防ぎ、結果として未重合が低減するものと考えられる。このようにして、形成される界面活性剤の表面層は従来の酸素遮断剤とは異なり、硬化性組成物に外部から塗布する必要がなく、硬化性組成物に含まれる成分によって、硬化中に自然と硬化体表面に形成される。 The curable composition of the present invention comprises (1) a radical polymerizable monomer, (2) a hydrophilic organic solvent, (3) a surfactant, and (4) a polymerization initiator as essential components. In such a curable composition, the mechanism that can reduce the occurrence of unpolymerization on the surface of the cured body is not necessarily clear, but the following mechanism is conceivable. That is, the hydrophilic organic solvent is volatilized from the cured product by the polymerization heat generated when the radical polymerizable monomer is cured, and the surfactant is transported to the surface simultaneously with the volatilization of the hydrophilic organic solvent. A thin layer of agent is formed. It is believed that this surfactant layer prevents oxygen from entering the interior, resulting in reduced unpolymerization. The surface layer of the surfactant thus formed does not need to be applied to the curable composition from the outside, unlike the conventional oxygen blocking agent, and depending on the components contained in the curable composition, during the curing. Naturally formed on the surface of the cured body.
前記ラジカル重合性単量体／水／界面活性剤の組み合わせからなる硬化性組成物では、長期に保存すると水が分離し、これに伴って界面活性剤も該組成物から分離し、その表面未重合層の形成の抑制効果が低下してしまうが、本発明の硬化性組成物の如くに親水性有機溶媒が配合されていると、その効果が長期に持続する。これは、ラジカル重合性単量体／水／界面活性剤の組み合わせでは、水と界面活性剤とでミセル(逆ミセル)が形成され、保存期間が長期になると、これらが融合し、最終的に水の分離が起こると推察されるところ、親水性有機溶媒が配合されていると、実質上、前記ミセル(逆ミセル)は形成されることがなく、該親水性有機溶媒や界面活性剤はラジカル重合性単量体に溶けるようになり、そのため親水性有機溶媒や界面活性剤が分離しないためと考えられる。そして、このように親水性有機溶媒を用いた系では、ミセルを形成しないため、硬化体の透明性も良好に保持される。さらに、理由は定かではないが、硬化性組成物の硬化時間の遅延も、長期に保存したものであっても、高度に抑制される。 In the curable composition composed of the radical polymerizable monomer / water / surfactant combination, water is separated when stored for a long period of time, and the surfactant is separated from the composition along with this, and the surface is not yet removed. Although the inhibitory effect on the formation of the polymer layer is reduced, the effect lasts for a long time when a hydrophilic organic solvent is blended as in the curable composition of the present invention. This is because in the combination of radical polymerizable monomer / water / surfactant, micelles (reverse micelles) are formed with water and the surfactant, and when the storage period becomes long, these fuse and finally Assuming that water separation occurs, when a hydrophilic organic solvent is blended, the micelle (reverse micelle) is substantially not formed, and the hydrophilic organic solvent and the surfactant are radicals. This is considered to be because it becomes soluble in the polymerizable monomer, so that the hydrophilic organic solvent and the surfactant are not separated. In such a system using a hydrophilic organic solvent, micelles are not formed, so that the transparency of the cured product is also maintained well. Furthermore, although the reason is not clear, the delay of the curing time of the curable composition is also highly suppressed even if it is stored for a long time.
本発明の硬化性組成物に配合されるラジカル重合性単量体は、公知のものが特に制限無く使用することができる。特に、重合性に優れ、室温近辺でも硬化させやすい点で、（メタ）アクリル系の重合性単量体が一般的である。 A well-known thing can be especially used for a radically polymerizable monomer mix | blended with the curable composition of this invention without a restriction | limiting. In particular, (meth) acrylic polymerizable monomers are common in that they are excellent in polymerizability and can be easily cured even near room temperature.
（メタ）アクリル系のものとしては、公知の物が制限なく使用可能であるが、例えば、アクリル酸、メタクリル酸、メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート、イソプロピルメタクリレート、アセトアセトキシエチルメタクリレート、２，２−ビス（メタクリロイルオキシフェニル）プロパン、２，２−ビス〔４−（３−メタクリロイルオキシ）−２−ヒドロキシプロポキシフェニル〕プロパン、２，２−ビス（４−メタクリロイルオキシフェニル）プロパン、２，２−ビス（４−メタクリロイルオキシポリエトキシフェニル）プロパン、２，２−ビス（４−メタクリロイルオキシジエトキシフェニル）プロパン）、２，２−ビス（４−メタクリロイルオキシテトラエトキシフェニル）プロパン、２，２−ビス（４−メタクリロイルオキシペンタエトキシフェニル）プロパン、２，２−ビス（４−メタクリロイルオキシジプロポキシフェニル）プロパン、２（４−メタクリロイルオキシジエトキシフェニル）−２（４−メタクリロイルオキシジエトキシフェニル）プロパン、２（４−メタクリロイルオキシジエトキシフェニル）−２（４−メタクリロイルオキシジトリエトキシフェニル）プロパン、２（４−メタクリロイルオキシジプロポキシフェニル）−２−（４−メタクリロイルオキシトリエトキシフェニル）プロパン、２，２−ビス（４−メタクリロイルオキシプロポキシフェニル）プロパン、２，２−ビス（４−メタクリロイルオキシイソプロポキシフェニル）プロパン、モノエチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、１，３−ブタンジオールジメタクリレート、１，４−ブタンジオールジメタクリレート、１，６−ヘキサンジオールジメタクリレート、ノナメチレンジオールメタクリレート、トリメチロールプロパントリメタクリレート、トリメチロールエタントリメタクリレート、ペンタエリスリトールトリメタクリレート、トリメチロールメタントリメタクリレート、ペンタエリスリトールテトラメタクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルメタクリレート、２−メタクリロイルオキシエチルジハイドロジェンホスフェート、ビス（２−メタクリロイルオキシエチル）ハイドロジェンホスフェート、ポリエチレングリコールジメタクリレート等が挙げられる。 As the (meth) acrylic ones, known ones can be used without limitation. For example, acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isopropyl methacrylate, acetoacetoxyethyl methacrylate, 2, 2 -Bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2- Bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane), 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis ( -Methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxydiethoxyphenyl) propane, 2 ( 4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxyditriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane, 2,2-bis (4-Methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane, monoethylene glycol dimethacrylate, diethylene glycol dimethyl Acrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, nonamethylenediol methacrylate, trimethylolpropane tri Methacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, pentaerythritol tetramethacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-methacryloyloxyethyl dihydrogen phosphate, bis (2-methacryloyloxyethyl) Hydrogen phosphate, polyethylene glycol And dimethacrylate.
なかでも、その分子中にベンゼン環を有する重合性単量体、ポリオキシエチレン鎖を有する重合性単量体、アルキル鎖を有する重合性単量体が好ましく、特に好ましいものを例示するならば、２，２−ビス（４−メタクリロイルオキシポリエトキシフェニル）プロパン、トリエチレングリコールジメタクリレート、平均分子量400のポリエチレングリコールジメタクリレート、１，６−ヘキサンジオールジメタクリレート、ノナメチレンジオールメタクリレート等が挙げられる。 Among them, a polymerizable monomer having a benzene ring in the molecule, a polymerizable monomer having a polyoxyethylene chain, and a polymerizable monomer having an alkyl chain are preferable, and particularly preferable examples are as follows: Examples include 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate having an average molecular weight of 400, 1,6-hexanediol dimethacrylate, and nonamethylenediol methacrylate.
これらのラジカル重合性単量体はそれぞれ単独で用いるだけでなく、必要な物性に応じて２種類以上の種類を組み合わせて使用することもできる。 These radically polymerizable monomers can be used not only alone but also in combination of two or more kinds depending on the required physical properties.
さらに、本発明の硬化性組成物においては、前記（メタ）アクリル系重合性単量体に加えて、重合の容易さ、粘度の調節、あるいはその他の物性の調節のために、上記例示したような（メタ）アクリル系重合性単量体以外の他のラジカル重合性単量体を混合して用いることも可能である。例示すると、フマル酸モノメチル、フマル酸ジエチル、フマル酸ジフェニル等のフマル酸エステル類；スチレン、ジビニルベンゼン、α−メチルスチレン、α−メチルスチレン等のスチレンあるいはα−メチルスチレン誘導体；ジアリルテレフタレート、ジアリルフタレート、ジアリルジグリコールカーボネート等のアリル化合物等を挙げることができる。これら他の重合性単量体もまた単独でまたは二種以上を一緒に使用することができる。 Further, in the curable composition of the present invention, in addition to the (meth) acrylic polymerizable monomer, as exemplified above, for ease of polymerization, adjustment of viscosity, or adjustment of other physical properties. It is also possible to use a mixture of other radical polymerizable monomers other than the (meth) acrylic polymerizable monomer. For example, fumaric acid esters such as monomethyl fumarate, diethyl fumarate and diphenyl fumarate; styrene such as styrene, divinylbenzene, α-methylstyrene, α-methylstyrene, and α-methylstyrene derivatives; diallyl terephthalate, diallyl phthalate And allyl compounds such as diallyl diglycol carbonate. These other polymerizable monomers can also be used alone or in combination of two or more.
本発明において親水性有機溶媒は、静電的相互作用や水素結合などによって水分子と弱い結合を作る官能基を有する有機溶媒で、具体的には水酸基、カルボニル基、カルボキシル基、アミノ基、シアノ基等の親水基を含む有機溶媒で、公知のものが特に制限無く使用することができる。 In the present invention, the hydrophilic organic solvent is an organic solvent having a functional group that forms a weak bond with a water molecule by electrostatic interaction or hydrogen bond, specifically, a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, a cyano group. A known organic solvent containing a hydrophilic group such as a group can be used without particular limitation.
通常は、２５℃における誘電率が１０〜４０のものが挙げられ、この２５℃における誘電率が１５〜３５のものがより好ましい。入手のしやすさ、匂い、環境に対する安全性から、アルコール類、ケトン類が好ましい。アルコール類は、その分子の持つ水酸基数によって、水酸基数が1つの一価アルコール、2つ以上の多価アルコールがある。一価アルコールとして、メタノール、エタノール、n-プロパノール、イソプロパノール、1-ブタノール、2-ブタノール、iso-ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール等が挙げられる。また、メトキシエタノール、エトキシエタノールといったアルコキシアルコールも使用することができる。 Usually, the thing whose dielectric constant in 25 degreeC is 10-40 is mentioned, The thing whose dielectric constant in this 25 degreeC is 15-35 is more preferable. Alcohols and ketones are preferred from the standpoint of availability, odor, and environmental safety. Alcohols include monohydric alcohols with one hydroxyl group and two or more polyhydric alcohols, depending on the number of hydroxyl groups in the molecule. Examples of the monohydric alcohol include methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, iso-butanol, pentanol, hexanol, heptanol, octanol and the like. Also, alkoxy alcohols such as methoxyethanol and ethoxyethanol can be used.
ケトン類は、アセトン、エチルメチルケトン、メチルプロピルケトン、ジエチルケトン等が挙が例示できる。 Examples of ketones include acetone, ethyl methyl ketone, methyl propyl ketone, diethyl ketone and the like.
なかでも、親水性有機溶媒の粘度が低い方が表面に界面活性剤を運搬する速度が速いと考えられ、その観点から、２０℃における粘性率が１５ｃＰ以下のものが好ましく、さらには０〜３のものが特に好ましい。さらに、親水性有機溶媒の揮発により上記界面活性剤が運搬されることを勘案すれば、該親水性有機溶媒は適度な揮発性を有することが望ましく、２０℃における蒸気圧が1ｍｍHg〜５００ｍｍHgが好ましく、特に蒸気圧が１０ｍｍHg〜３００ｍｍHgであるのが好ましい。これらの好適条件を満足する親水性有機溶媒としては、具体的には、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、アセトン、メチルエチルケトン、メチルプロピルケトン、ジエチルケトン、メトキシエタノール等である。 Of these, the lower the viscosity of the hydrophilic organic solvent, the faster the rate of transport of the surfactant to the surface is considered, and from that viewpoint, the viscosity at 20 ° C. is preferably 15 cP or less, and more preferably 0-3. Are particularly preferred. Furthermore, considering that the surfactant is transported by volatilization of the hydrophilic organic solvent, the hydrophilic organic solvent desirably has an appropriate volatility, and the vapor pressure at 20 ° C. is preferably 1 mmHg to 500 mmHg. In particular, the vapor pressure is preferably 10 mmHg to 300 mmHg. Specific examples of the hydrophilic organic solvent that satisfies these preferable conditions include methanol, ethanol, n-propanol, isopropanol, acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methoxyethanol, and the like.
なお、以上に示す親水性有機溶媒は１種または２種以上を混合して使用することができる。 In addition, the hydrophilic organic solvent shown above can be used 1 type or in mixture of 2 or more types.
硬化性組成物中において親水性有機溶媒は、その配合量が多いほうが表面への界面活性剤の運搬量が増加して未重合層形成の低減効果が向上すると考えられる。ただし、この配合量があまりに多くなると、重合性単量体およびラジカル重合開始剤の濃度低下を来たし、重合発熱の温度も低くなり、こうなると、親水性有機溶媒が揮発し難くなり、上記未重合層形成の低減効果は逆に十分に発揮されなくなる。したがって、親水性有機溶媒の配合量は、界面活性剤の運搬効果と重合熱の発熱効果の両方が相乗するように、ラジカル重合性単量体１００質量部に対し０．０１〜３０質量部の範囲であるのが好ましい。中でも、２〜２０質量部の範囲が最適である。 It is considered that the hydrophilic organic solvent in the curable composition increases the amount of surfactant transported to the surface and increases the effect of reducing the formation of the unpolymerized layer as the amount of the hydrophilic organic solvent increases. However, if this amount is too large, the concentration of the polymerizable monomer and radical polymerization initiator will decrease, and the temperature of the polymerization exotherm will also decrease. On the contrary, the effect of reducing the layer formation is not sufficiently exhibited. Therefore, the blending amount of the hydrophilic organic solvent is 0.01 to 30 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer so that both the carrying effect of the surfactant and the exothermic effect of the polymerization heat are synergistic. A range is preferred. Especially, the range of 2-20 mass parts is optimal.
本発明において界面活性剤は、非フッ素系のものが使用され、これらはイオン型界面活性剤、非イオン型界面活性剤のいずれであってもよく、ＨＬＢ値(親水親油バランス)も特に限定されるものではないが、表面未重合低減効果の点から、ＨＬＢ値が２０以上、好適には３０〜５０のものを使用するのが好ましい。イオン型界面活性剤としては、アニオン性界面活性剤、カチオン性界面活性剤、両性イオン界面活性剤のいずれも制限なく使用できる。ここで、非フッ素系界面活性剤とは、分子内にフッ素原子を一つも含有しない界面活性剤であり、言い換えれば、分子内にフッ素分子を一つ以上含有する、パーフルオロアルキルスルホン酸のアンモニウム塩、パーフルオロアルキルスルホン酸のカリウム塩、パーフルオロアルキルカルボン酸のカリウム塩、パーフルオロアルキル第四級アンモニウムヨウ化物、パーフルオロアルキルポリオキシエチレンエタノール、フッ素化アルキルエステル等の界面活性剤は該当しない。ここで、フッ素系界面活性剤を用いたのでは、十分な未重合層低減の効果が発揮されない理由は、必ずしも明らかではないが、該フッ素系界面活性剤は分子の運動性が高く、このため硬化性組成物の表面に形成されるこのものの表面層を酸素が透過し易くなるためではないかと推察される。 In the present invention, a non-fluorine type surfactant is used, and these may be either an ionic surfactant or a nonionic surfactant, and the HLB value (hydrophilic / lipophilic balance) is also particularly limited. However, from the viewpoint of the effect of reducing surface unpolymerization, it is preferable to use those having an HLB value of 20 or more, preferably 30 to 50. As the ionic surfactant, any of an anionic surfactant, a cationic surfactant, and an amphoteric ionic surfactant can be used without limitation. Here, the non-fluorinated surfactant is a surfactant that does not contain any fluorine atom in the molecule, in other words, an ammonium perfluoroalkylsulfonic acid that contains one or more fluorine molecules in the molecule. Surfactants such as salt, potassium salt of perfluoroalkyl sulfonic acid, potassium salt of perfluoroalkyl carboxylic acid, perfluoroalkyl quaternary ammonium iodide, perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester are not applicable. . Here, the reason why a sufficient effect of reducing the unpolymerized layer is not exhibited when a fluorosurfactant is used is not necessarily clear, but the fluorosurfactant has high molecular mobility, and therefore It is presumed that oxygen may easily permeate through the surface layer formed on the surface of the curable composition.
本発明に好適に使用される非フッ素系界面活性剤を具体的に例示すると、アニオン性界面活性剤としては、公知のものが特に制限なく使用できるが、こうしたアニオン性界面活性剤を具体的に例示すると、デシル硫酸ナトリウム、ドデシル硫酸ナトリウムなどのアルキル硫酸塩、ドデシルベンゼンスルホン酸ナトリウムなどのアルキルベンゼンスルホン酸塩、ラウリン酸ナトリウム、ステアリン酸ナトリウム、オレイン酸ナトリウムなどの脂肪族カルボン酸金属塩、ラウリルアルコールとエチレンオキサイドの付加物を硫酸化したラウリルエーテル硫酸エステルナトリウムなどの高級アルキルエーテル硫酸エステルの金属塩、スルホコハク酸ナトリウムなどのスルホコハク酸ジエステル、高級アルコールエチレンオキサイド付加物のリン酸エステル塩などを挙げることができる。 Specific examples of the non-fluorinated surfactant suitably used in the present invention include known anionic surfactants with no particular limitation, and these anionic surfactants are specifically exemplified. Illustrative examples include alkyl sulfates such as sodium decyl sulfate and sodium dodecyl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, aliphatic carboxylic acid metal salts such as sodium laurate, sodium stearate and sodium oleate, lauryl alcohol Metal salts of higher alkyl ether sulfates such as sodium lauryl ether sulfate, which is a sulfated adduct of ethylene oxide and ethylene oxide, sulfosuccinic acid diesters such as sodium sulfosuccinate, and phosphates of higher alcohol ethylene oxide adducts Or the like can be mentioned ether salt.
カチオン性界面活性剤としては、ドデシルアンモニウムクロリドなどのアルキルアミン塩類及びトリメチルドデシルアンモニウムブロミドなどの４級アンモニウム塩類などを挙げることができる。 Examples of the cationic surfactant include alkylamine salts such as dodecyl ammonium chloride and quaternary ammonium salts such as trimethyldodecyl ammonium bromide.
両性イオン界面活性剤としては、ドデシルジメチルアミンオキシドなどのアルキルジメチルアミンオキシド類、ドデシルカルボキシベタインなどのアルキルカルボキシベタイン類、ドデシルスルホベタインなどのアルキルスルホベタイン類、ラウラミドプロピルアミンオキシドなどのアミドアミノ酸塩などが挙げられる。 Zwitterionic surfactants include alkyldimethylamine oxides such as dodecyldimethylamine oxide, alkylcarboxybetaines such as dodecylcarboxybetaine, alkylsulfobetaines such as dodecylsulfobetaine, and amide amino acid salts such as lauramidopropylamine oxide. Etc.
非イオン性界面活性剤としては、ポリオキシエチレンラウリルエーテルなどのポリオキシエチレンアルキルエーテル類、ポリオキシエチレンラウリルフェニルエーテルなどのポリオキシエチレンアルキルフェニルエーテル類、脂肪酸ポリオキシエチレンラウリルエステルなどの脂肪酸ポリオキシエチレンエステル類、ポリオキシエチレンソルビタンラウリルエステルなどのポリオキシエチレンソルビタンエステル類などが挙げられる。 Nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene lauryl phenyl ether, and fatty acid polyoxy such as fatty acid polyoxyethylene lauryl ester. And polyoxyethylene sorbitan esters such as ethylene esters and polyoxyethylene sorbitan lauryl esters.
これら非フッ素系界面活性剤の中でも、表面に生じる二重膜が電気的なエネルギーで安定化し、より強固な界面活性剤による表面層を形成しやすいイオン性界面活性剤が好ましく、イオン性界面活性剤の中でも、より分子のイオン性の高い構造を有するものの多いアニオン性界面活性剤を使用するの効果が顕著であることから好ましい。さらには、この中でもアルキル硫酸塩、アルキルベンゼンスルホン酸塩がより好ましく、特に、アルキル基の炭素鎖が６〜１６の物がより好ましい。 Among these non-fluorine-based surfactants, ionic surfactants that can form a surface layer with a stronger surfactant are preferable because the double film formed on the surface is stabilized by electrical energy, and ionic surfactants are preferred. Among the agents, the effect of using an anionic surfactant having a lot of molecules having a highly ionic structure is preferable because it is remarkable. Furthermore, among these, alkyl sulfates and alkylbenzene sulfonates are more preferable, and those having an alkyl group with 6 to 16 carbon chains are more preferable.
また、非フッ素系界面活性剤は、それぞれ単独で使用するだけでなく、必要に応じて複数の種類を組み合わせて使用しても良い。このように複数の種類を組み合わせて使用することにより、相乗的に作用して、未重合層形成の低減効果が高まることがあるため好適である。 Further, the non-fluorinated surfactants are not only used alone, but may be used in combination of a plurality of types as required. By using a combination of a plurality of types in this way, it is preferable because it may act synergistically and increase the effect of reducing the formation of the unpolymerized layer.
硬化性組成物中において非フッ素系界面活性剤は、その配合量が多いほど、未重合の発生が抑制されて好ましい。ただし、その配合量があまりに多くなると、硬化体の物性が低下する虞がある。これらを勘案して、界面活性剤の配合量は、ラジカル重合性単量体１００質量部に対して０．１〜１０質量部の範囲であるのが好ましい。なかでもラジカル重合性単量体成分１００質量部に対して０．３〜３質量部の範囲が最適である。 In the curable composition, the non-fluorinated surfactant is more preferable as the blending amount is larger because the occurrence of unpolymerization is suppressed. However, if the amount is too large, the physical properties of the cured product may be reduced. Considering these, the amount of the surfactant is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer. Especially, the range of 0.3-3 mass parts is optimal with respect to 100 mass parts of radically polymerizable monomer components.
本発明の硬化性組成物には、前記ラジカル重合性単量体を重合させるためのラジカル重合開始剤が配合される。当該ラジカル重合開始剤としては、用いるラジカル重合性単量体を重合、硬化させることができるものであれば何ら制限なく使用可能であり、公知のものが使用可能である。一般に知られているラジカル重合開始剤としては、化学重合開始剤（常温重合開始剤）、光重合開始剤、熱重合開始剤等が存在し、いずれも適用できるし、これらを組合せて用いても良い。 In the curable composition of the present invention, a radical polymerization initiator for polymerizing the radical polymerizable monomer is blended. The radical polymerization initiator can be used without any limitation as long as it can polymerize and cure the radical polymerizable monomer to be used, and a known one can be used. Generally known radical polymerization initiators include chemical polymerization initiators (room temperature polymerization initiators), photopolymerization initiators, thermal polymerization initiators, etc., all of which can be applied, or a combination thereof can be used. good.
化学重合開始剤は、一般に、２成分以上からなり、使用直前に全成分が混合されることにより室温近辺で重合活性種を生じる形態である。このような化学重合開始剤としては、アミン化合物／有機過酸化物系、アリールボレート化合物／酸性化合物系、ピリミジントリオン誘導体／ハロゲンイオン形成化合物／第二銅形成化合物又は第二鉄イオン形成化合物系が代表的で、なかでもアミン化合物／有機過酸化物系が好ましい。 The chemical polymerization initiator is generally composed of two or more components, and forms a polymerization active species near room temperature by mixing all the components immediately before use. Such chemical polymerization initiators include amine compounds / organic peroxide systems, aryl borate compounds / acidic compound systems, pyrimidinetrione derivatives / halogen ion forming compounds / cupric copper forming compounds or ferric ion forming compound systems. Typical is an amine compound / organic peroxide system.
該アミン化合物を具体的に例示すると、Ｎ，Ｎ−ジメチル−ｐ−トルイジン、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジエタノール−ｐ−トルイジンなどの芳香族アミン化合物が例示される。 Specific examples of the amine compound include aromatic amine compounds such as N, N-dimethyl-p-toluidine, N, N-dimethylaniline, and N, N-diethanol-p-toluidine.
代表的な有機過酸化物としては、公知のケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアリールパーオキサイド、パーオキシエステル、ジアシルパーオキサイド、パーオキシジカーボネートに分類されるベンゾイルパーオキサイドなどの有機過酸化物が好ましい。 Typical organic peroxides include organic compounds such as known ketone peroxides, peroxyketals, hydroperoxides, diaryl peroxides, peroxyesters, diacyl peroxides, and benzoyl peroxides classified into peroxydicarbonates. Peroxides are preferred.
使用する有機過酸化物は、適宜選択して使用すればよく、単独又は２種以上を組み合わせて用いても何等構わないが、中でもハイドロパーオキサイド類、ケトンパーオキサイド類、パーオキシエステル類及びジアシルパーオキサイド類が重合活性の点から特に好ましい。さらにこの中でも、硬化性組成物としたときの保存安定性の点から１０時間半減期温度が６０℃以上の有機過酸化物を用いるのが好ましい。 The organic peroxide to be used may be appropriately selected and used, and it may be used alone or in combination of two or more. Among them, hydroperoxides, ketone peroxides, peroxyesters and diacyl Peroxides are particularly preferred from the viewpoint of polymerization activity. Furthermore, among these, it is preferable to use an organic peroxide having a 10-hour half-life temperature of 60 ° C. or higher from the viewpoint of storage stability when a curable composition is used.
該有機過酸化物と該アミン化合物からなる開始剤系にさらに、ベンゼンスルフィン酸やｐ−トルエンスルフィン酸及びその塩などのスルフィン酸を加えた系、５−ブチルバルビツール酸などのピリミジントリオン系開始剤を配合しても何ら問題なく使用できる。 An initiator system composed of the organic peroxide and the amine compound and a sulfinic acid such as benzenesulfinic acid, p-toluenesulfinic acid and its salt, and a pyrimidinetrione system such as 5-butylbarbituric acid. Even if an agent is blended, it can be used without any problems.
また、アリールボレート化合物が酸により分解してラジカルを生じることを利用した、アリールボレート化合物／酸性化合物系の重合開始剤を用いることもできる。 An aryl borate compound / acidic compound polymerization initiator that utilizes the fact that an aryl borate compound is decomposed by an acid to generate a radical can also be used.
アリールボレート化合物は、分子中に少なくとも１個のホウ素−アリール結合を有する化合物であれば特に限定されず公知の化合物が使用できるが、その中でも、保存安定性を考慮すると、１分子中に３個または４個のホウ素−アリール結合を有するアリールボレート化合物を用いることが好ましく、さらには取り扱いや合成・入手の容易さから４個のホウ素−アリール結合を有するアリールボレート化合物がより好ましい。 The aryl borate compound is not particularly limited as long as it is a compound having at least one boron-aryl bond in the molecule, and known compounds can be used, but among them, three in one molecule are considered in view of storage stability. Alternatively, an aryl borate compound having four boron-aryl bonds is preferably used, and an aryl borate compound having four boron-aryl bonds is more preferable from the viewpoint of easy handling, synthesis, and availability.
これらアリールボレート化合物は２種以上を併用しても良い。 Two or more of these aryl borate compounds may be used in combination.
酸性化合物は、一般的にブレンステッド酸として知られている無機酸、有機酸が何等制限なく用いられる。代表的な無機酸を例示すれば、塩酸、硫酸、硝酸、リン酸等が挙げられる。また、代表的な有機酸としては、酢酸、プロピオン酸、マレイン酸、フマル酸、フタル酸、安息香酸、トリクロロ酢酸、トリフルオロ酢酸、クエン酸およびトリメリット酸等のカルボン酸類、ｐ−トルエンスルホン酸、ベンゼンスルホン酸、メタンスルホン酸およびトリフルオロメタンスルホン酸等のスルホン酸類、メチルホスホン酸、フェニルホスホン酸、ジメチルホスフィン酸、ジフェニルホスフィン酸等のリン酸類等が挙げられる。また、フェノール類、チオール類の他、酸性イオン交換樹脂、酸性アルミナ等の固体酸も好適な酸として例示される。さらに、酸性化合物としては、それ自身が重合可能な基を含有する酸性基含有重合性単量体を使用してもよく、この場合には、酸性化合物自身が重合性単量体でもあり、重合硬化によって、酸性成分の溶出等の心配がないため好ましい。 As the acidic compound, an inorganic acid or an organic acid generally known as a Bronsted acid is used without any limitation. Examples of typical inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like. Representative organic acids include acetic acid, propionic acid, maleic acid, fumaric acid, phthalic acid, benzoic acid, trichloroacetic acid, trifluoroacetic acid, citric acid, trimellitic acid and other carboxylic acids, p-toluenesulfonic acid And sulfonic acids such as benzenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid, and phosphoric acids such as methylphosphonic acid, phenylphosphonic acid, dimethylphosphinic acid and diphenylphosphinic acid. In addition to phenols and thiols, solid acids such as acidic ion exchange resins and acidic alumina are also exemplified as suitable acids. Furthermore, as the acidic compound, an acidic group-containing polymerizable monomer containing a group capable of being polymerized itself may be used. In this case, the acidic compound itself is also a polymerizable monomer, The curing is preferable because there is no concern about elution of acidic components.
また、このようなアリールボレート化合物／酸性化合物系の重合開始剤に更に、有機過酸化物及び／又は遷移金属化合物を組み合わせて用いることも好適である。有機過酸化物としては前記した通りである。遷移金属化合物としては＋ＩＶ価及び／又は＋Ｖ価のバナジウム化合物が好適である。 Further, it is also preferable to use a combination of an organic peroxide and / or a transition metal compound in addition to such an aryl borate compound / acidic compound polymerization initiator. The organic peroxide is as described above. The transition metal compound is preferably a + IV and / or + V vanadium compound.
さらに、ピリミジントリオン誘導体／ハロゲンイオン形成化合物／第二銅形成化合物又は第二鉄イオン形成化合物系の開始剤として、ピリミジントリオン誘導体、ハロゲンイオン形成化合物及び第二銅形成化合物又は第二鉄イオン形成化合物との組み合わせを挙げることができる。この化学重合触媒系は、硬化後の変色が起こりにくく、本発明の硬化性組成物を歯科修復材料の目的に使用した場合の触媒系として特に好ましい。 Further, as an initiator of a pyrimidinetrione derivative / halogen ion forming compound / cupric copper forming compound or ferric ion forming compound system, a pyrimidinetrione derivative, a halogen ion forming compound and a cupric ion forming compound or a ferric ion forming compound are used. Can be mentioned. This chemical polymerization catalyst system is not particularly susceptible to discoloration after curing, and is particularly preferred as a catalyst system when the curable composition of the present invention is used for the purpose of a dental restorative material.
ピリミジントリオンの中でも、重合性単量体への溶解性及びラジカル重合の活性の点から、窒素原子に結合した水素をアルキル基又はシクロアルキル基で置換したピリミジントリオン誘導体が特に好ましい。 Among pyrimidinetriones, a pyrimidinetrione derivative in which hydrogen bonded to a nitrogen atom is substituted with an alkyl group or a cycloalkyl group is particularly preferable from the viewpoint of solubility in a polymerizable monomer and radical polymerization activity.
ハロゲンイオン形成化合物としては、溶液中でハロゲン化物イオンを形成させる化合物であれば特に限定されず公知の化合物が使用でき、これらは１種又は２種以上を混合して使用してもよい。 The halogen ion-forming compound is not particularly limited as long as it is a compound that forms halide ions in a solution, and known compounds can be used, and these may be used alone or in combination of two or more.
また、第二銅形成化合物又は第二鉄イオン形成化合物としては、溶液中で２価の銅イオン又は３価の鉄イオンを形成する化合物であれば特に限定されない。好適な第二銅又は第二鉄イオン形成化合物としては、アセチルアセトン銅、酢酸第二銅、オレイン酸銅、アセチルアセトン鉄等があり、これらは１種又は２種以上混合して使用してもよい。 The cupric-forming compound or ferric ion-forming compound is not particularly limited as long as it is a compound that forms divalent copper ions or trivalent iron ions in the solution. Suitable cupric or ferric ion forming compounds include acetylacetone copper, cupric acetate, copper oleate, acetylacetone iron and the like, and these may be used alone or in combination.
また、ハロゲンイオン形成化合物と第２銅又は第２鉄イオン形成化合物とは必ずしも別の化合物である必要はなく、ハロゲン化物イオンと２価の銅イオン又は３価の鉄イオンの両方を同時に形成する化合物であってもよい。このような化合物として、例えば、ハロゲン化第２銅又はハロゲン化第２鉄を使用することも可能であり、具体的な例としては、塩化第二銅、臭化第二銅等のハロゲン化第二銅、塩化第二鉄、臭化第二鉄等のハロゲン化第２鉄等を挙げることができる。 Further, the halogen ion forming compound and the cupric or ferric ion forming compound do not necessarily need to be different compounds, and both a halide ion and a divalent copper ion or a trivalent iron ion are formed simultaneously. It may be a compound. As such a compound, for example, it is possible to use cupric halide or ferric halide. Specific examples include cupric halides such as cupric chloride and cupric bromide. Examples thereof include ferric halides such as dicopper, ferric chloride, and ferric bromide.
光重合開始剤を使用する場合においても、該光重合開始剤は公知のものが制限なく使用でき、１種あるいは２種以上を混合して用いても差し支えない。光重合開始剤の中でも、重合活性の良さ、生体への為害性の少なさ等の点からα−ジケトン類が好ましい。また、α−ジケトンを用いる場合には、第３級アミン化合物と組み合わせて用いることが好ましい。 Even in the case of using a photopolymerization initiator, known photopolymerization initiators can be used without limitation, and one kind or a mixture of two or more kinds may be used. Among the photopolymerization initiators, α-diketones are preferred from the viewpoints of good polymerization activity and low harm to living organisms. When α-diketone is used, it is preferably used in combination with a tertiary amine compound.
本発明において上記ラジカル重合開始剤の配合量は、ラジカル重合性単量体が十分に重合する有効量であれば良いが、十分な機械的物性を得るために、具体的には、ラジカル重合性単量体１００質量部に対して０．００１〜１０質量部が好ましく、更に好ましくは０．０１〜５質量部が好ましい。なお、重合開始剤として、前記アリールボレート化合物／酸性化合物系のものを用いる場合、該ラジカル重合開始剤の配合量には、酸性化合物の質量は含めないものとする。 In the present invention, the amount of the radical polymerization initiator may be an effective amount that allows the radical polymerizable monomer to be sufficiently polymerized. In order to obtain sufficient mechanical properties, specifically, the radical polymerization initiator is used. 0.001-10 mass parts is preferable with respect to 100 mass parts of monomers, More preferably, 0.01-5 mass parts is preferable. In addition, when using the said aryl borate compound / acidic compound type thing as a polymerization initiator, the mass of an acidic compound shall not be included in the compounding quantity of this radical polymerization initiator.
本発明の構成組成物は、上記組成により、硬化時に未重合層の形成が抑制され、さらに硬化体の透明性低下、硬化時間の遅延抑制等の問題も生じ難い優れたものになるが、さらに、水を配合することにより、上記未重合層の形成能力が一層に高まり好適である。すなわち、水は、界面活性剤のラジカル重合性単量体への溶解性をさらに高める等して、表面により多くの界面活性剤を運搬できるようになると考えられる。このように表面により多くの界面活性剤が運搬されるようになることにより、硬化の際に硬化性組成物の表面に析出する界面活性剤の量も増加し、その結果、未重合量が更に低下すると推察される。 The composition of the present invention is excellent in that the composition prevents the formation of an unpolymerized layer at the time of curing, and further hardly causes problems such as a decrease in transparency of a cured product and a delay in curing time. By adding water, the formation ability of the unpolymerized layer is further enhanced, which is preferable. That is, water is considered to be able to carry more surfactant to the surface, for example, by further increasing the solubility of the surfactant in the radical polymerizable monomer. Since more surfactant is transported to the surface in this way, the amount of surfactant that precipitates on the surface of the curable composition during curing also increases, and as a result, the unpolymerized amount further increases. Presumed to decline.
使用する水としては、不純物を実質的に含まないことが好ましく、例としては脱イオン水、蒸留水等が挙げられる。 The water to be used is preferably substantially free of impurities, and examples thereof include deionized water and distilled water.
本発明において水の配合量は、上記未重合層の形成の抑制効果の向上を考えれば、より多いほうが効果的であるが、あまり多くても硬化体の強度が低下するため、好ましくはラジカル重合性単量体１００質量部に対して０．１〜１０質量部である。より好ましくはラジカル重合性単量体１００質量部に対して０．５〜５質量部である。 In the present invention, the amount of water added is more effective in consideration of improvement in the effect of suppressing the formation of the unpolymerized layer. However, if it is too much, the strength of the cured product is reduced, and therefore preferably radical polymerization is performed. It is 0.1-10 mass parts with respect to 100 mass parts of an ionic monomer. More preferably, it is 0.5-5 mass parts with respect to 100 mass parts of radically polymerizable monomers.
本発明の硬化性組成物は、フィラーと組み合わることにより、より広範な用途に用いることができる。フィラーには無機フィラー、有機フィラー、有機−無機複合フィラーがあり、公知のものが制限なく使用可能である。 The curable composition of the present invention can be used in a wider range of applications by combining with a filler. Fillers include inorganic fillers, organic fillers, and organic-inorganic composite fillers, and known ones can be used without limitation.
無機フィラーは公知のものが制限なく使用可能であるが、代表的な無機フィラーを具体的に例示すれば、石英、シリカ、アルミナ、シリカチタニア、シリカジルコニア、ランタンガラス、バリウムガラス、ストロンチウムガラス等が挙げられる。さらに無機フィラーの内、カチオン溶出性フィラーとしては、水酸化カルシウム、水酸化ストロンチウム等の水酸化物、酸化亜鉛、ケイ酸塩ガラス、フルオロアルミノシリケートガラス等の酸化物が挙げられる。いずれも、一種または二種以上を混合して用いても何等差し支えない。 Known inorganic fillers can be used without limitation, but specific examples of typical inorganic fillers include quartz, silica, alumina, silica titania, silica zirconia, lanthanum glass, barium glass, and strontium glass. Can be mentioned. Further, among the inorganic fillers, examples of the cation-eluting filler include hydroxides such as calcium hydroxide and strontium hydroxide, and oxides such as zinc oxide, silicate glass, and fluoroaluminosilicate glass. Any of them may be used alone or in combination of two or more.
上記した無機フィラーは、シランカップリング剤に代表される表面処理剤で処理することが、重合性単量体とのなじみをよくし、機械的強度や耐水性を向上させる上で望ましい。表面処理の方法は公知の方法で行えばよい。 It is desirable to treat the above-mentioned inorganic filler with a surface treating agent typified by a silane coupling agent in order to improve the compatibility with the polymerizable monomer and improve the mechanical strength and water resistance. The surface treatment method may be performed by a known method.
代表的な有機フィラーを具体的に例示すれば、ポリメタクリル酸メチル、ポリメタクリル酸エチル、メタクリル酸メチル−メタクリル酸エチル共重合体、架橋型ポリメタクリル酸メチル、架橋型ポリメタクリル酸エチル、エチレン−酢酸ビニル共重合体、スチレン−ブタジエン共重合体、アクリロニトリル−スチレン共重合体、アクリロニトリル−スチレン−ブタジエン共重合体が挙げられ、これらは一種または二種以上の混合物として用いることができる。 Specific examples of typical organic fillers include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, ethylene- A vinyl acetate copolymer, a styrene-butadiene copolymer, an acrylonitrile-styrene copolymer, and an acrylonitrile-styrene-butadiene copolymer can be used, and these can be used as one kind or a mixture of two or more kinds.
有機フィラーと組み合わせた場合には、例えば裏装用の材料として好適に使用される。 When combined with the organic filler it is suitably used as a material of the back wear, for example.
また、前述の無機フィラーに重合性単量体を予め添加し、ペースト状にした後、重合させ、粉砕して得られる粒状の有機−無機複合フィラーを用いる場合もある。 In some cases, a granular organic-inorganic composite filler obtained by adding a polymerizable monomer to the above-described inorganic filler in advance, forming a paste, polymerizing, and pulverizing is used.
これらフィラーの粒径は特に限定されず、例えば一般的な歯科用材料として使用する場合は０．００１μｍ〜１００μｍの平均粒子径のフィラーが目的に応じて適宜使用できる。また、フィラーの屈折率も特に限定されないが、例えば一般的な歯科材料として使用する場合は１．４〜１．７の範囲のものが好ましく使用できる。 The particle size of these fillers is not particularly limited. For example, when used as a general dental material, a filler having an average particle size of 0.001 μm to 100 μm can be appropriately used according to the purpose. Also, the refractive index of the filler is not particularly limited, but for example, when used as a general dental material, a filler in the range of 1.4 to 1.7 can be preferably used.
さらに、上記したフィラーの中でもとりわけ球状の無機フィラーを用いると、得られる硬化体の表面滑沢性が増し、優れた修復材料となり得る硬化性組成物が得られる。この特長は特に歯科用途において優れた性質である。 Furthermore, when a spherical inorganic filler is used among the above-mentioned fillers, the surface smoothness of the resulting cured product is increased, and a curable composition that can be an excellent restoration material is obtained. This feature is an excellent property especially in dental applications.
これらのフィラーの割合は、使用目的に応じて、ラジカル重合性単量体と混合した時の粘度（操作性）や硬化体の機械的物性を考慮して適宜決定すればよいが、一般的には、ラジカル重合性単量体１００質量部に対して１〜１５００質量部が好ましい。より好ましくは７０〜１０００質量部の範囲で用いられる。 The proportion of these fillers may be appropriately determined in consideration of the viscosity (operability) when mixed with the radical polymerizable monomer and the mechanical properties of the cured product, depending on the purpose of use. Is preferably 1 to 1500 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer. More preferably, it is used in the range of 70 to 1000 parts by mass.
本発明の硬化性組成物には、例えば歯科材料として使用する場合はさらに歯牙や歯肉の色調に合わせるため、顔料、蛍光顔料等の着色材料を配合したり、紫外線に対する変色防止のため紫外線吸収剤を添加したりしてもよい。また、保存安定性を向上させるために、重合禁止剤を配合することも好ましい。 For example, when used as a dental material, the curable composition of the present invention is further blended with a coloring material such as a pigment or a fluorescent pigment to match the color tone of a tooth or gum, or an ultraviolet absorber for preventing discoloration to ultraviolet rays. May be added. Moreover, in order to improve storage stability, it is also preferable to mix | blend a polymerization inhibitor.
このような硬化性組成物は、公知の方法に従って製造されたものが制限なく使用できる。また、重合が開始しないように成分をいくつかに分けて包装・保存し、使用時にそれらを混合して用いる態様としても良い。この場合でも、（１）ラジカル重合性単量体、（２）親水性有機溶媒、および（３）非フッ素系界面活性剤が共存する包装があれば、このものでは、保存中に、組成から水が分離してしまう問題が良好に抑制される。したがって、こうした分割された形態で長期に保存させた後に、各包装を混合し重合硬化させても、表面未重合は良好に抑制され、硬化時間遅延の問題も生じ難い。さらに、上記組成の包装液において、透明性も維持される。 As such a curable composition, those produced according to a known method can be used without limitation. Moreover, it is good also as an aspect which divides and divides a component into several so that superposition | polymerization may not start, and mix and use them at the time of use. Even in this case, if there is a package in which (1) a radically polymerizable monomer, (2) a hydrophilic organic solvent, and (3) a non-fluorinated surfactant coexist, this can be removed from the composition during storage. The problem of water separation is satisfactorily suppressed. Therefore, even if each package is mixed and polymerized and cured after being stored in such a divided form for a long period of time, surface unpolymerization is satisfactorily suppressed, and the problem of curing time delay hardly occurs. Furthermore, transparency is maintained in the packaging liquid having the above composition.
使用するラジカル重合開始剤が、２成分の混合によりラジカルが発生するタイプ（多くの化学重合型等）のものである場合には、硬化性組成物は、保存中に重合が進行しないように、該ラジカル重合開始剤の構成成分ごとに分割して、前記２包装以上にする必要性がある。例えば、ラジカル重合開始剤が、アミン化合物／有機過酸化物系のものであれば、アミンを含む包装と、有機過酸化物を含む包装とに、それぞれ別の容器に収容することになる。また、熱や光の照射によってラジカルが発生し、重合が開始されてしまうラジカル重合開始剤を用いるのであれば、該成分が含有される包装は外部からの熱や光を遮断するような容器を用いるのが好適である。 When the radical polymerization initiator to be used is of a type that generates radicals by mixing two components (many chemical polymerization types, etc.), the curable composition should not be polymerized during storage. It is necessary to divide into each component of the radical polymerization initiator to make the two or more packages. For example, if the radical polymerization initiator is an amine compound / organic peroxide type, the amine-containing package and the organic peroxide-containing package are stored in separate containers. In addition, if a radical polymerization initiator is used that generates radicals upon irradiation with heat or light and polymerization is initiated, the packaging containing the component should be a container that blocks heat and light from the outside. It is preferred to use.
本発明の硬化性組成物は、前記したとおり表面未重合層の形成抑制効果が極めて高いものであり、そのため、該表面未重合層の形成が許容できない場合に必要であった、硬化雰囲気を窒素環境にするための設備等を特に設ける必要がなく、酸素遮断材の塗布等の操作も特に行う必要が無い。したがって、このような利点から、一般工業用途において、幅広く使用できる。 The curable composition of the present invention has an extremely high effect of suppressing the formation of the surface unpolymerized layer as described above. Therefore, the curing atmosphere required for the case where the formation of the surface unpolymerized layer is unacceptable is used as the nitrogen. There is no particular need to provide facilities or the like for making the environment, and it is not particularly necessary to perform an operation such as application of an oxygen shielding material. Therefore, from such advantages, it can be widely used in general industrial applications.
特に、空気との接触を回避するのが困難な状態で、硬化させなければならない歯科用の硬化性組成物に適用するのが好ましく、具体的には、裏装材として用いることができる。
In particular, in difficult conditions to avoid contact with air, it is preferable to apply the curable composition for dental must be cured, specifically, can be used as a relining material .
以下、実施例を挙げて本発明を具体的に示すが、本発明はこれら実施例によって何等制限されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is shown concretely, this invention is not restrict | limited at all by these Examples.
尚、実施例および比較例で使用した化合物とその略称を以下に示す。
〔界面活性剤〕
・非フッ素系界面活性剤
（アニオン性界面活性剤）
ＳＤＳ；ドデシル硫酸ナトリウム ＨＬＢ:４０
ＳＣ4Ｓ；ブチル硫酸ナトリウム ＨＬＢ：４４
ＳＣ6Ｓ；ヘキシル硫酸ナトリウム ＨＬＢ：４２
ＳＣ16Ｓ；ヘキサデシル硫酸ナトリウム ＨＬＢ：３８
ＳＣ20Ｓ；エイコシルシル硫酸ナトリウム ＨＬＢ：３６
（カチオン性界面活性剤）
ＬＴＭＡＣｌ；ラウリルトリメチルアンモニウムクロリド
（ノニオン性界面活性剤）
ＰＯＥ４Ｌ；ポリオキシエチレン（４）ラウリルエーテル
・フッ素系界面活性剤
ＦＣ−９８（３Ｍ Ｆｌｕｏｒａｄ）
ＦＣ−４３１（３Ｍ Ｆｌｕｏｒａｄ）
［ラジカル重合性単量体］
Ｄ２．６Ｅ；２，２−ビス（４−メタクリロイルオキシポリエトキシフェニル）プロパン
３Ｇ；トリエチレングリコールジメタクリレート
［重合開始剤］
（アミン化合物）
ＤＥＰＴ；p-トリルジエタノールアミン
（有機過酸化物）
ＢＰＯ；ベンゾイルパーオキサイド
[フィラー]
不定形シリカ−ジルコニア、γ−メタクリロイルオキシプロピルトリメトキシシラン表面処理物（平均粒径：３μｍ）を用いた。
The compounds used in Examples and Comparative Examples and their abbreviations are shown below.
[Surfactant]
・ Non-fluorine surfactant (anionic surfactant)
SDS; sodium dodecyl sulfate HLB: 40
SC4S; sodium butyl sulfate HLB: 44
SC6S; sodium hexyl sulfate HLB: 42
SC16S; sodium hexadecyl sulfate HLB: 38
SC20S; sodium eicosylsil sulfate HLB: 36
(Cationic surfactant)
LTMACl; Lauryltrimethylammonium chloride (nonionic surfactant)
POE4L: Polyoxyethylene (4) lauryl ether / fluorine surfactant FC-98 (3M Fluorad)
FC-431 (3M Fluorad)
[Radically polymerizable monomer]
D2.6E; 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane 3G; triethylene glycol dimethacrylate [polymerization initiator]
(Amine compound)
DEPT; p-tolyldiethanolamine (organic peroxide)
BPO; Benzoyl peroxide
[Filler]
An amorphous silica-zirconia, γ-methacryloyloxypropyltrimethoxysilane surface-treated product (average particle size: 3 μm) was used.
実施例１
ラジカル重合性単量体としてＤ２．６Ｅを１００質量部、エタノールを１０質量部、ＳＤＳを１質量部、ＤＥＰＴを１．５質量部混合して得たＡ液、それと同じくラジカル重合性単量体としてＤ２．６Ｅを１００質量部、エタノールを１０質量部、ＳＤＳを１質量部、ＢＰＯを１．５質量部混合して得たＢ液を調整した。このＡ液とＢ液を質量比で１：１となるように量り取って混合することにより、硬化性組成物を調製する使用態様で、以下の評価を行った。
Example 1
As a radically polymerizable monomer, a liquid A obtained by mixing 100 parts by mass of D2.6E, 10 parts by mass of ethanol, 1 part by mass of SDS, and 1.5 parts by mass of DEPT, and radically polymerizable monomers as well The liquid B obtained by mixing 100 parts by mass of D2.6E, 10 parts by mass of ethanol, 1 part by mass of SDS, and 1.5 parts by mass of BPO was prepared. The following evaluation was performed by the use aspect which prepares a curable composition by measuring and mixing this A liquid and B liquid so that it may become 1: 1 by mass ratio.
〔未重合量測定方法〕
直径５ｍｍ、厚さ１ｍｍの孔を有するポリアセタール製の型に、硬化性組成物を填入し、２３℃恒温室中で１５分間放置することにより硬化を行った。硬化後重量を測定し、その後エタノールで未重合層を除去し、重量変化を表面積で割り、単位面積あたりの未重合量を求めた。
[Measurement method of unpolymerized amount]
The curable composition was filled in a mold made of polyacetal having a hole with a diameter of 5 mm and a thickness of 1 mm, and cured by leaving it in a constant temperature room at 23 ° C. for 15 minutes. After curing, the weight was measured, and then the unpolymerized layer was removed with ethanol, and the change in weight was divided by the surface area to determine the amount of unpolymerized per unit area.
〔硬化時間測定方法〕
Ａ液とＢ液とを混合した。混合開始時間を０秒とし、１５秒間混合した。このサンプルを直径６ｍｍ、深さ１２ｍｍの穴の開いたアセタール製モールドに流し込み、熱電対を差し込み、発熱ピークの時間を測定した。発熱ピークの時間は厳密には硬化時間とは異なるが、硬化過程における硬化時間の目安となる物性であり（硬化時間が短いと発熱ピーク時間も短く、硬化時間が長いと発熱ピーク時間も長くなり、発熱ピーク時間は硬化時間と相関がある）、一方、硬化時間そのものの測定は困難であるため、上記発熱ピーク時間を硬化時間として評価した。
[Curing time measurement method]
A liquid and B liquid were mixed. The mixing start time was 0 second and mixing was performed for 15 seconds. This sample was poured into an acetal mold having a hole with a diameter of 6 mm and a depth of 12 mm, a thermocouple was inserted, and the time of exothermic peak was measured. Strictly speaking, the exothermic peak time is different from the curing time, but it is a physical property that can be used as a guide for the curing time in the curing process (the shorter the curing time, the shorter the exothermic peak time; The exothermic peak time has a correlation with the curing time). On the other hand, since the measurement of the curing time itself is difficult, the exothermic peak time was evaluated as the curing time.
〔保存安定性〕
混合前のＡ液およびＢ液をガラス製サンプル管に入れ密栓し、４℃で３０日保存し、保存前と３０日経過時に、それぞれの液について、溶媒の分離状態、透明性、さらに白濁等が無いかどうかを目視で観察し、Ａ液、Ｂ液の状態について以下の三段階で評価した。なお、すべての実施例および比較例において、Ａ液およびＢ液ともに同じ挙動を示したため、以下に示す実施例ではＡ液とＢ液の結果に区別をつけず、同一の結果として表記した。
[Storage stability]
Liquid A and liquid B before mixing are sealed in a glass sample tube and stored at 4 ° C. for 30 days. Before storage and when 30 days have elapsed, the solvent separation state, transparency, white turbidity, etc. The liquid A and the liquid B were evaluated in the following three stages. In all of the examples and comparative examples, both the liquid A and the liquid B showed the same behavior. Therefore, in the examples shown below, the results of the liquid A and the liquid B were not distinguished, and were expressed as the same result.
液は透明で均一な状態 ○
液が白濁している △
有機溶媒(または水)の相分離がある ×
更に、３０日経過したＡ液とＢ液を混合して硬化させ、未重合量の測定および硬化時間の測定を行った。
The liquid is transparent and uniform ○
The liquid is cloudy △
There is phase separation of organic solvent (or water) ×
Furthermore, the A liquid and B liquid which passed for 30 days were mixed and hardened, and the unpolymerized amount and the curing time were measured.
以上の測定の結果を表１に示した。硬化性組成物は、調製時において未重合量は５μg/mm2、硬化時間は１３５秒であり、これは４℃で３０日保存後においても保存安定性は○で、未重合量、硬化時間ともに変化は無かった。 The results of the above measurement are shown in Table 1. The curable composition has an unpolymerized amount of 5 μg / mm 2 at the time of preparation and a curing time of 135 seconds, and the storage stability is ○ even after storage at 4 ° C. for 30 days. There was no change in both.
実施例２〜４
実施例１のＡ液、Ｂ液に水２質量部をそれぞれ加えた場合、実施例１のＡ液、Ｂ液にフィラー（不定形シリカ−ジルコニアのγ−メタクリロイルオキシプロピルトリメトキシシラン表面処理物）１１２．５質量部をそれぞれ加えた場合、および実施例１のＡ液、Ｂ液に水２質量部と上記フィラー１１４．５質量部をそれぞれ加えた場合で、得られる各硬化性組成物について、該実施例１と同様の評価を実施した。結果を表１に示した。
Examples 2-4
When 2 parts by mass of water were added to the A liquid and the B liquid of Example 1, respectively, the filler (liquid surface treatment product of γ-methacryloyloxypropyltrimethoxysilane of amorphous silica-zirconia) was added to the A liquid and B liquid of Example 1. About each curable composition obtained when 112.5 parts by mass are added and when 2 parts by mass of water and 114.5 parts by mass of the filler are added to the A liquid and the B liquid of Example 1, respectively. The same evaluation as in Example 1 was performed. The results are shown in Table 1.
実施例５〜４２
実施例１において、組成を表１および表２に示したものに変えた場合で、得られる各硬化性組成物について、該実施例１と同様の評価を実施した。結果を表１〜３に示した。
Examples 5-42
In Example 1, when the composition was changed to those shown in Table 1 and Table 2, each curable composition obtained was evaluated in the same manner as in Example 1. The results are shown in Tables 1-3.
比較例１，２
実施例１のＡ液、Ｂ液においてエタノールを配合しなかった場合、および実施例１のＡ液、Ｂ液において界面活性剤（ＳＤＳ）を配合しなかった場合で、得られる各硬化性組成物について、該実施例１と同様の評価を実施した。結果を表４に示した。
Comparative Examples 1 and 2
Each curable composition obtained in the case where ethanol was not blended in the liquid A and liquid B of Example 1 and in the case where the surfactant (SDS) was not blended in the liquid A and liquid B of Example 1. The same evaluation as in Example 1 was performed. The results are shown in Table 4.
エタノールが配合されていなくても、および界面活性剤が配合されていなくても、未重合量は調製時から６００μg/mm2以上の多量に生じるものであった。 Even if ethanol was not blended and no surfactant was blended, the unpolymerized amount was a large amount of 600 μg / mm 2 or more from the time of preparation.
比較例３
実施例２のＡ液、Ｂ液においてエタノールを配合しなかった場合で、得られる硬化性組成物について、該実施例２と同様の評価を実施した。結果を表４に示した。
Comparative Example 3
In the case where ethanol was not blended in the liquid A and liquid B of Example 2, the same evaluation as in Example 2 was performed on the curable composition obtained. The results are shown in Table 4.
硬化性組成物は、調製直後では未重合量が少ないものの、４℃で３０日保存後は保存安定性は×で、未重合量は４８１μg/mm2に増加し、硬化前の液は水の相分離が生じていた。 Although the curable composition has a small amount of unpolymerized immediately after preparation, the storage stability is x after storage at 4 ° C. for 30 days, the unpolymerized amount increases to 481 μg / mm 2, and the liquid before curing is water. Phase separation occurred.
比較例４
実施例２のＡ液、Ｂ液において界面活性剤を配合しなかった場合で、得られる硬化性組成物について、該実施例２と同様の評価を実施した。結果を表４に示した。
Comparative Example 4
In the case where the surfactant was not blended in the liquid A and liquid B of Example 2, the same evaluation as in Example 2 was performed on the resulting curable composition. The results are shown in Table 4.
未重合量は調製時から７００μg/mm2以上と多量に生じるものであった。 The unpolymerized amount was a large amount of 700 μg / mm 2 or more from the time of preparation.
比較例５，６
実施例１のＡ液、Ｂ液において、界面活性剤としてＳＤＳに代えて、フッ素系界面活性剤ＦＣ−９８（３Ｍ Ｆｌｕｏｒａｄ）またはＦＣ−４３１（３Ｍ Ｆｌｕｏｒａｄ）を用いた場合で、得られる各硬化性組成物について、該実施例１と同様の評価を実施した。結果を表４に示した。
Comparative Examples 5 and 6
In the liquid A and liquid B of Example 1, each curing obtained when a fluorosurfactant FC-98 (3M Fluorad) or FC-431 (3M Fluorad) is used instead of SDS as the surfactant. The same evaluation as in Example 1 was performed on the composition. The results are shown in Table 4.
ＦＣ−９８を用いた時の未重合量は調製時から５２９μg/mm2であり、ＦＣ−４３１を用いた時も未重合量は調製時から６２４μg/mm2で、いずれも多量であった。 The amount of unpolymerized when FC-98 was used was 529 μg / mm 2 from the time of preparation, and the amount of unpolymerized when FC-431 was used was 624 μg / mm 2 from the time of preparation, both of which were large.
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