JP4273959B2 - Zirconia particle dispersion, method for producing the same, and photocurable composition - Google Patents
Zirconia particle dispersion, method for producing the same, and photocurable composition Download PDFInfo
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- JP4273959B2 JP4273959B2 JP2003429249A JP2003429249A JP4273959B2 JP 4273959 B2 JP4273959 B2 JP 4273959B2 JP 2003429249 A JP2003429249 A JP 2003429249A JP 2003429249 A JP2003429249 A JP 2003429249A JP 4273959 B2 JP4273959 B2 JP 4273959B2
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- zirconia
- zirconia particle
- particle dispersion
- photocurable composition
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims description 118
- 239000002245 particle Substances 0.000 title claims description 69
- 239000006185 dispersion Substances 0.000 title claims description 62
- 239000000203 mixture Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 24
- 239000002270 dispersing agent Substances 0.000 claims description 19
- 239000002612 dispersion medium Substances 0.000 claims description 13
- -1 polyoxyethylene Polymers 0.000 claims description 13
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 239000011324 bead Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 241000047703 Nonion Species 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- YPEWWOUWRRQBAX-UHFFFAOYSA-N n,n-dimethyl-3-oxobutanamide Chemical compound CN(C)C(=O)CC(C)=O YPEWWOUWRRQBAX-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 101100389975 Mus musculus Ezhip gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002928 artificial marble Substances 0.000 description 1
- RFVHVYKVRGKLNK-UHFFFAOYSA-N bis(4-methoxyphenyl)methanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1 RFVHVYKVRGKLNK-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- JMVIPXWCEHBYAH-UHFFFAOYSA-N cyclohexanone;ethyl acetate Chemical compound CCOC(C)=O.O=C1CCCCC1 JMVIPXWCEHBYAH-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 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
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FSPSELPMWGWDRY-UHFFFAOYSA-N m-Methylacetophenone Chemical compound CC(=O)C1=CC=CC(C)=C1 FSPSELPMWGWDRY-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical class COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Colloid Chemistry (AREA)
Description
本発明は、ジルコニア粒子分散液、その製造方法及び光硬化性組成物に関する。さらに詳しくは、各種基材［例えば、プラスチック（ポリカーボネート、ポリメチルメタクリレート、ポリスチレン、ポリエステル、ポリオレフィン、エポキシ樹脂、メラミン樹脂、トリアセチルセルロース樹脂、ＡＢＳ樹脂、ＡＳ樹脂、ノルボルネン系樹脂等）、金属、木材、紙、ガラス、スレート等］の表面に、高硬度及び高屈折率を有するとともに耐擦傷性並びに基材及び低屈折率層との密着性に優れた塗膜（被膜）を形成し得る光硬化性組成物、及びその光硬化性組成物に用いられるジルコニア粒子分散液及びその製造方法に関する。 The present invention relates to a zirconia particle dispersion, a production method thereof, and a photocurable composition. More specifically, various base materials [for example, plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, etc.), metal, wood , Paper, glass, slate, etc.], photocuring capable of forming a coating film (film) having high hardness and high refractive index and excellent scratch resistance and adhesion to the substrate and the low refractive index layer. The present invention relates to a curable composition, a zirconia particle dispersion used for the photocurable composition, and a method for producing the same.
近年、各種基材表面の傷付き（擦傷）防止や汚染防止のための保護コーティング材；各種基材の接着剤、シーリング材；印刷インクのバインダー材として、優れた塗工性を有し、かつ各種基材の表面に、硬度、耐擦傷性、耐摩耗性、低カール性、密着性、透明性、耐薬品性及び塗膜面の外観のいずれにも優れた硬化膜を形成し得る硬化性組成物が要請されている。
また、フィルム型液晶素子、タッチパネル、プラスチック光学部品等の反射防止膜の用途においては、上記要請に加えて、高屈折率の硬化膜を形成し得る硬化性組成物が要請されている。
このような硬化性組成物に、高屈折率、高硬度及び耐擦傷性を付与するために、ジルコニア粒子分散液が使用されている（例えば、特許文献１）。
In recent years, it has excellent coating properties as a protective coating material for preventing scratches (scratching) on various substrate surfaces and preventing contamination; adhesives and sealing materials for various substrates; and a binder material for printing inks. Curability that can form a cured film with excellent hardness, scratch resistance, abrasion resistance, low curl, adhesion, transparency, chemical resistance, and coating surface appearance on the surface of various substrates. A composition is required.
In addition to the above requirements, curable compositions capable of forming a cured film having a high refractive index are required in addition to the above requirements in applications of antireflection films such as film-type liquid crystal elements, touch panels, and plastic optical components.
In order to provide such a curable composition with a high refractive index, high hardness, and scratch resistance, a zirconia particle dispersion is used (for example, Patent Document 1).
上記のジルコニア粒子分散液は、分散粒径が小さく分散安定性に優れていることが求められている。
本発明は、上述の課題に鑑みてなされたものであり、分散粒径の小さなジルコニア粒子分散液、その製造方法及び当該ジルコニア分散液を含有する光硬化性組成物を提供することを目的とする。
The above zirconia particle dispersion is required to have a small dispersed particle size and excellent dispersion stability.
This invention is made | formed in view of the above-mentioned subject, and aims at providing the photocurable composition containing the zirconia particle dispersion liquid with a small dispersed particle size, its manufacturing method, and the said zirconia dispersion liquid. .
本発明によれば、以下のジルコニア粒子分散液、その製造方法及び当該ジルコニア分散液を含有する光硬化性組成物を提供できる。
１．ジルコニア粒子、ノニオン型分散剤、分散助剤及び分散媒を含有するジルコニア粒子分散液。
２．前記ノニオン型分散剤が、ポリオキシエチレンアルキル構造を有するリン酸エステル系ノニオン型分散剤である１に記載のジルコニア粒子分散液。
３．前記分散助剤が、アセチルアセトン、Ｎ，Ｎ−ジメチルアセトアセトアミドから選択される少なくとも一種である１又は２に記載のジルコニア粒子分散液。
４．前記分散媒が、メチルエチルケトン、ブタノール、キシレン、エチルベンゼン、トルエンから選択される少なくとも一種である１〜３のいずれか一に記載のジルコニア粒子分散液。
５．反射防止膜の高屈折率膜を形成する組成物に使用される１〜４のいずれか一に記載のジルコニア粒子分散液。
６．分散媒に、ノニオン型分散剤、分散助剤と共に、ジルコニア粒子を分散させる１〜５のいずれか一に記載のジルコニア粒子分散液の製造方法。
７．１〜５のいずれか一に記載のジルコニア粒子分散液、多官能（メタ）アクリレートモノマー及び光重合開始剤を含有する光硬化性組成物。
According to the present invention, the following zirconia particle dispersion, a production method thereof, and a photocurable composition containing the zirconia dispersion can be provided.
1. A zirconia particle dispersion containing zirconia particles, a nonionic dispersant, a dispersion aid, and a dispersion medium.
2. 2. The zirconia particle dispersion according to 1, wherein the nonionic dispersant is a phosphoric ester nonionic dispersant having a polyoxyethylene alkyl structure.
3. The zirconia particle dispersion according to 1 or 2, wherein the dispersion aid is at least one selected from acetylacetone and N, N-dimethylacetoacetamide.
4). The zirconia particle dispersion according to any one of 1 to 3, wherein the dispersion medium is at least one selected from methyl ethyl ketone, butanol, xylene, ethylbenzene, and toluene.
5. The zirconia particle dispersion liquid as described in any one of 1-4 used for the composition which forms the high refractive index film | membrane of an antireflection film.
6). The method for producing a zirconia particle dispersion according to any one of 1 to 5, wherein zirconia particles are dispersed in a dispersion medium together with a nonionic dispersant and a dispersion aid.
The photocurable composition containing the zirconia particle dispersion liquid as described in any one of 7.1-5, a polyfunctional (meth) acrylate monomer, and a photoinitiator.
本発明によれば、分散粒径の小さなジルコニア粒子分散液、その製造方法及び当該ジルコニア分散液を含有する光硬化性組成物が提供できる。 According to the present invention, it is possible to provide a zirconia particle dispersion having a small dispersed particle diameter, a production method thereof, and a photocurable composition containing the zirconia dispersion.
以下、本発明のジルコニア粒子分散液、その製造方法及び光硬化性組成物の実施形態を具体的に説明する。
本発明のジルコニア粒子分散液は、ジルコニア粒子、ノニオン型分散剤、分散助剤及び分散媒を含有してなる。
Hereinafter, embodiments of the zirconia particle dispersion, the production method thereof, and the photocurable composition of the present invention will be specifically described.
The zirconia particle dispersion of the present invention contains zirconia particles, a nonionic dispersant, a dispersion aid, and a dispersion medium.
本発明に用いるジルコニア粒子は、強熱減量が０．１〜３％であることが好ましく、０．５〜３％であることがより好ましく、１〜３％であることが特に好ましい。強熱減量がこの範囲にあると、分散液を含んで形成される膜の透明性を高くすることができる。強熱減量は、ジルコニア粒子を１０５℃で２時間加熱した後の重量をＷ１とし、９００℃で２時間加熱した後の重量をＷ２として、（Ｗ１−Ｗ２）÷Ｗ１×１００（％）で表される。 The zirconia particles used in the present invention preferably have a loss on ignition of 0.1 to 3%, more preferably 0.5 to 3%, and particularly preferably 1 to 3%. When the ignition loss is in this range, the transparency of the film formed including the dispersion can be increased. The loss on ignition is expressed as (W1−W2) ÷ W1 × 100 (%), where W1 is the weight after heating the zirconia particles at 105 ° C. for 2 hours and W2 is the weight after heating at 900 ° C. for 2 hours. Is done.
強熱減量と透明性との関係は明確ではないが、強熱減量は残存水酸基量によると考えられることから、ジルコニア粒子を適度に親水性にすることにより透明性が増すと推察される。
強熱減量が０．１〜３％であるジルコニア粒子は、ＵＥＰ（第一稀元素化学工業（株）製）、ＰＣＳ（日本電工（株）製）、ＪＳ−０１、ＪＳ−０３、ＪＳ−０４（日本電工（株）製）、ＵＥＰ−１００（第一稀元素化学工業(株)製）等がある。
The relationship between the loss on ignition and transparency is not clear, but the loss on ignition is considered to be due to the amount of residual hydroxyl groups. Therefore, it is assumed that the transparency is increased by making the zirconia particles appropriately hydrophilic.
Zirconia particles with a loss on ignition of 0.1 to 3% are UEP (Daiichi Rare Element Chemical Co., Ltd.), PCS (Nippon Denko Co., Ltd.), JS-01, JS-03, JS- 04 (Nippon Denko Co., Ltd.), UEP-100 (Daiichi Rare Element Chemical Co., Ltd.) and the like.
ジルコニア粒子の形状は、特に限定されるものではないが、例えば、球状、中空状、多孔質状、棒状、板状、繊維状、又は不定形状であり、好ましくは、球状である。
分散前のジルコニア粒子の一次粒径は、通常、１０ｎｍ〜１００ｎｍのものを使用できる。好ましくは１０〜５０ｎｍである。また、結晶構造も特に限定されないが、単斜晶系等を使用できる。
The shape of the zirconia particles is not particularly limited, but is, for example, spherical, hollow, porous, rod-like, plate-like, fibrous, or indeterminate, and preferably spherical.
The primary particle size of the zirconia particles before dispersion is usually 10 nm to 100 nm. Preferably it is 10-50 nm. The crystal structure is not particularly limited, but a monoclinic system or the like can be used.
ノニオン型分散剤は、好ましくは、ポリオキシエチレンアルキル構造を有するリン酸エステル系ノニオン型分散剤であり、より好ましくは、下記式（１）の分散剤である。
３つのＲは、同一でも異なってもよいが、通常は同一である。
The nonionic dispersant is preferably a phosphate ester nonionic dispersant having a polyoxyethylene alkyl structure, and more preferably a dispersant represented by the following formula (1).
The three Rs may be the same or different, but are usually the same.
分散助剤は、アセト酢酸メチル、アセチルアセトン、Ｎ，Ｎ−ジメチルアセトアセトアミドから選択される一以上のものを好適に使用できる。アセト酢酸メチルは、変異原性物質であるので、特にアセチルアセトン、Ｎ，Ｎ−ジメチルアセトアセトアミドが好ましい。 As the dispersion aid, at least one selected from methyl acetoacetate, acetylacetone, and N, N-dimethylacetoacetamide can be suitably used. Since methyl acetoacetate is a mutagenic substance, acetylacetone and N, N-dimethylacetoacetamide are particularly preferable.
分散媒は、メタノール、エタノール、イソプロパノール、ブタノール、オクタノール等のアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；酢酸エチル、酢酸ブチル、乳酸エチル、γ−ブチロラクトン、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等のエステル類；エチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル等のエーテル類；ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素類；ジメチルフォルムアミド、Ｎ，Ｎ−ジメチルアセトアセトアミド、Ｎ−メチルピロリドン等のアミド類を用いることができる。中でも、メタノール、イソプロパノール、ブタノール、メチルエチルケトン、メチルイソブチルケトン、酢酸エチル、酢酸ブチル、トルエン、キシレン、エチルベンゼンが好ましく、メチルエチルケトン、ブタノール、キシレン、エチルベンゼン、トルエンがより好ましい。分散媒は一種又は二種以上を混合して用いることができる。 Dispersion media: alcohols such as methanol, ethanol, isopropanol, butanol, octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate Esters such as propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; dimethylformamide and N, N-dimethylacetate Amides such as acetamide and N-methylpyrrolidone can be used. Among these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, xylene, and ethylbenzene are preferable, and methyl ethyl ketone, butanol, xylene, ethylbenzene, and toluene are more preferable. A dispersion medium can be used 1 type or in mixture of 2 or more types.
本発明の分散液における各成分の配合量は、用途に応じて適宜設定できるが、通常、ジルコニア粒子１〜５０重量％、ノニオン型分散剤０．５〜１０重量％、分散助剤０．５〜１０重量％、分散媒５０〜９０重量％であり、好ましくは、ジルコニア粒子１〜４０重量％、ノニオン型分散剤１〜５重量％、分散助剤２〜６重量％、分散媒６０〜９０重量％である。
分散剤の量が少ないと、粒径分布の大粒径側のテーリングが生じる場合がある。
The amount of each component in the dispersion of the present invention can be appropriately set depending on the application, but is usually 1 to 50% by weight of zirconia particles, 0.5 to 10% by weight of a nonionic dispersant, and a dispersion aid of 0.5 10 to 10% by weight, dispersion medium 50 to 90% by weight, preferably 1 to 40% by weight of zirconia particles, 1 to 5% by weight of nonionic dispersant, 2 to 6% by weight of dispersion aid, and 60 to 90% of dispersion medium. % By weight.
If the amount of the dispersant is small, tailing on the large particle size side of the particle size distribution may occur.
本発明の分散液は、上記の成分の他に、その特性を損なわない範囲において、カップリング剤等を含むことができる。また、後述の多官能（メタ）アクリレートモノマーを含むこともできる。 In addition to the above components, the dispersion of the present invention can contain a coupling agent and the like as long as the characteristics are not impaired. Moreover, the below-mentioned polyfunctional (meth) acrylate monomer can also be included.
本発明の分散液は、分散媒に、ノニオン型分散剤、分散助剤と共に、ジルコニア粒子を分散させて製造する。
分散に先立ち、プレ分散をしてもよい。プレ分散するとさらに小さな粒径に分散できる。プレ分散では、分散媒、分散剤、分散助剤を容器に入れて、ホモジナイザー等を用いて通常８０００〜１００００ｒｐｍで撹拌しながら、ジルコニア粒子を加える。その後、さらに粒子の塊が目視で見られなくなるまで撹拌する。
The dispersion of the present invention is produced by dispersing zirconia particles in a dispersion medium together with a nonionic dispersant and a dispersion aid.
Prior to dispersion, pre-dispersion may be performed. When pre-dispersed, it can be dispersed to a smaller particle size. In pre-dispersion, a dispersion medium, a dispersant, and a dispersion aid are placed in a container, and zirconia particles are added while stirring at 8000 to 10,000 rpm using a homogenizer or the like. Thereafter, the mixture is further stirred until no particle lump is visually observed.
分散は、ＳＣミル、アニュラー型ミル、ピン型ミル等を用いて通常周速５〜１５ｍ／ｓで、粒径の低下が観察されなくなるまで継続する。通常数時間である。分散の際に、ガラスビーズ、ジルコニアビーズ等の分散ビーズを用いることが好ましい。ビーズ径は特に限定されないが、通常０．０５〜１ｍｍ程度である。ビーズ径は、好ましくは０．０５〜０．５ｍｍ、より好ましくは０．０８〜０．５ｍｍ、特に好ましくは０．０８〜０．２ｍｍである。 Dispersion is normally continued at a peripheral speed of 5 to 15 m / s using an SC mill, an annular mill, a pin mill, or the like until no decrease in particle size is observed. Usually several hours. In the dispersion, it is preferable to use dispersed beads such as glass beads and zirconia beads. The bead diameter is not particularly limited, but is usually about 0.05 to 1 mm. The bead diameter is preferably 0.05 to 0.5 mm, more preferably 0.08 to 0.5 mm, and particularly preferably 0.08 to 0.2 mm.
このようにして得られるジルコニア粒子分散液は、分散前には二次凝集をしていたジルコニア粒子がより小さな粒径に分散している。好ましくはジルコニア粒子のメジアン径が１５０ｎｍ以下、さらに好ましくは１００ｎｍ以下である。
また、本発明の均一に分散し分散安定性が高いジルコニア粒子分散液を含んで調製した樹脂組成物を硬化した膜は、ジルコニア粒子が膜内で凝集し難く、透明性が高い。
In the zirconia particle dispersion thus obtained, zirconia particles that have been secondary agglomerated before dispersion are dispersed in a smaller particle size. Preferably, the median diameter of the zirconia particles is 150 nm or less, more preferably 100 nm or less.
Moreover, the film | membrane which hardened | cured the resin composition prepared by including the zirconia particle dispersion liquid which is uniformly disperse | distributed and high dispersion stability of this invention does not aggregate a zirconia particle within a film | membrane, and its transparency is high.
本発明の分散液は、保護膜、反射防止膜、接着剤、シーリング材、バインダー材等に用いられる樹脂組成物に含ませて用いることができ、特に反射防止膜の高屈折率膜を形成する樹脂組成物に好適に用いることができる。 The dispersion of the present invention can be used in a resin composition used for a protective film, an antireflection film, an adhesive, a sealing material, a binder material, etc., and particularly forms a high refractive index film as an antireflection film. It can use suitably for a resin composition.
本発明のジルコニア粒子分散液は、以下の表面変性を加えることが好ましい。表面変性を行うことにより、ジルコニア粒子分散液を含有する光硬化性組成物の硬化物の耐擦傷性を改善することができる。 The zirconia particle dispersion of the present invention is preferably subjected to the following surface modification. By performing the surface modification, the scratch resistance of the cured product of the photocurable composition containing the zirconia particle dispersion can be improved.
表面変性は、公知の方法で用いることができる（例えば、特開２００３−１０５０３４号公報参照）。具体的には、ジルコニア粒子を、分子内に、（メタ）アクリロイル基やビニル基等の重合性不飽和基及び下記式（２）
−Ｘ−Ｃ（＝Ｙ）ＮＨ− （２）
［式（２）中、Ｘは、ＮＨ、Ｏ（酸素原子）又はＳ（イオウ原子）を示し、Ｙは、Ｏ又はＳを示す。］
に示す基を有する化合物（以下、「特定有機化合物」という。）と反応させることにより行うことができる。なお、この化合物は、分子内にシラノ−ル基又は加水分解によってシラノ−ル基を生成する基を有する化合物であることが好ましい。
Surface modification can be used by a well-known method (for example, refer Unexamined-Japanese-Patent No. 2003-105034). Specifically, the zirconia particles have a polymerizable unsaturated group such as a (meth) acryloyl group or a vinyl group in the molecule and the following formula (2).
-X-C (= Y) NH- (2)
[In the formula (2), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]
It can carry out by making it react with the compound (henceforth a "specific organic compound") which has group shown. This compound is preferably a compound having a silanol group or a group capable of generating a silanol group by hydrolysis in the molecule.
前記式（２）に示す基は、具体的には、［−Ｏ−Ｃ（＝Ｏ）−ＮＨ−］、［−Ｏ−Ｃ（＝Ｓ）−ＮＨ−］、［−Ｓ−Ｃ（＝Ｏ）−ＮＨ−］、［−ＮＨ−Ｃ（＝Ｏ）−ＮＨ−］、［−ＮＨ−Ｃ（＝Ｓ）−ＮＨ−］、及び［−Ｓ−Ｃ（＝Ｓ）−ＮＨ−］の６種である。これらの基は、１種単独で又は２種以上を組合わせて用いることができる。中でも、熱安定性の観点から、［−Ｏ−Ｃ（＝Ｏ）−ＮＨ−］基を必須とし、［−Ｏ−Ｃ（＝Ｓ）−ＮＨ−］基及び［−Ｓ−Ｃ（＝Ｏ）−ＮＨ−］基の少なくとも１を併用することが好ましい。前記式（２）に示す基［−Ｘ−Ｃ（＝Ｙ）−ＮＨ−］は、分子間において水素結合による適度の凝集力を発生させ、硬化物にした場合、優れた機械的強度、基材との密着性及び耐熱性等の特性を付与せしめるものと考えられる。 Specific examples of the group represented by the formula (2) include [—O—C (═O) —NH—], [—O—C (═S) —NH—], [—S—C (= O) —NH—], [—NH—C (═O) —NH—], [—NH—C (═S) —NH—], and [—S—C (═S) —NH—]. There are six types. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, the [—O—C (═O) —NH—] group is essential, the [—O—C (═S) —NH—] group and the [—S—C (═O). ) -NH-] group is preferably used in combination. The group [—X—C (═Y) —NH—] represented by the formula (2) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when cured. It is considered that it gives properties such as adhesion to the material and heat resistance.
本発明の光硬化性組成物は、ジルコニア粒子分散液の他、多官能（メタ）アクリレートモノマー、光重合開始剤等を含んで調製できる。ここで、表面変性したジルコニア粒子を用いることが好ましい。 The photocurable composition of the present invention can be prepared by including a polyfunctional (meth) acrylate monomer, a photopolymerization initiator and the like in addition to the zirconia particle dispersion. Here, it is preferable to use surface-modified zirconia particles.
多官能（メタ）アクリレートモノマーは、ジルコニア分散液に硬化性を付与するために用いる。ここで多官能とは、１分子中に２個以上の（メタ）アクリロイル基を有することをいい、製膜性の観点から、３官能以上の（メタ）アクリレートモノマーが好ましく、５官能以上の（メタ）アクリレートモノマーがさらに好ましい。または２種以上の多官能（メタ）アクリレートモノマーの混合物を用いることができる。 The polyfunctional (meth) acrylate monomer is used for imparting curability to the zirconia dispersion. Here, polyfunctional means having two or more (meth) acryloyl groups in one molecule, and from the viewpoint of film forming property, a trifunctional or higher (meth) acrylate monomer is preferable, and a pentafunctional or higher ( More preferred are meth) acrylate monomers. Alternatively, a mixture of two or more polyfunctional (meth) acrylate monomers can be used.
多官能（メタ）アクリレートモノマーの好ましい具体例としては、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレート等を挙げることができる。
多官能（メタ）アクリレートモノマーの市販品としては、ＫＡＹＡＲＡＤ ＤＰＨＡ（日本化薬（株）製）等を挙げることができる。
Preferable specific examples of the polyfunctional (meth) acrylate monomer include dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and the like.
Examples of commercially available polyfunctional (meth) acrylate monomers include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.).
光重合開始剤としては、光照射により分解してラジカルを発生して重合を開始せしめるものであれば特に制限はなく、例えば、アセトフェノン、アセトフェノンベンジルケタール、１−ヒドロキシシクロヘキシルフェニルケトン、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、３−メチルアセトフェノン、４−クロロベンゾフェノン、４，４’−ジメトキシベンゾフェノン、ベンジルジメチルケタール、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−プロパン−１−オン、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス−（２，６−ジメトキシベンゾイル）−２，４，４−トリメチルペンチルフォスフィンオキシド、オリゴ（２−ヒドロキシ−２−メチル−１−（４−（１−メチルビニル）フェニル）プロパノン）等を挙げることができる。 The photopolymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2- Dimethoxy-1,2-diphenylethane-1-one, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, Su- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), etc. Can be mentioned.
放射線（光）重合開始剤の市販品としては、例えば、チバスペシャルティケミカルズ（株）製 商品名：イルガキュア １８４、３６９、６５１、５００、８１９、９０７、７８４、２９５９、ＣＧＩ１７００、ＣＧＩ１７５０、ＣＧＩ１８５０、ＣＧ２４−６１、ダロキュア １１１６、１１７３、ＢＡＳＦ社製 商品名：ルシリン ＴＰＯ、ＵＣＢ社製 商品名：ユベクリル Ｐ３６、フラテツリ・ランベルティ社製 商品名：エザキュアー ＫＩＰ１５０、ＫＩＰ６５ＬＴ、ＫＩＰ１００Ｆ、ＫＴ３７、ＫＴ５５、ＫＴＯ４６、ＫＩＰ７５／Ｂ等を挙げることができる。 As a commercial item of a radiation (photo) polymerization initiator, for example, Ciba Specialty Chemicals Co., Ltd. trade name: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24- 61, Darocur 1116, 1173, manufactured by BASF, Inc. Product name: Lucillin TPO, manufactured by UCB, Inc. Product name: Ubekrill P36, manufactured by Fratteri Lamberti, Inc. Product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B Etc.
本発明の光硬化性組成物中に含まれる各成分の配合量は、用途に応じて適宜設定できるが、通常、ジルコニア粒子分散液中に含まれるジルコニア粒子（表面変性をした場合には、表面変性後のジルコニア粒子）１００重量部に対して、多官能（メタ）アクリレートモノマー１０〜２０００重量部、光重合開始剤０．０１〜１００重量部であり、好ましくは、多官能（メタ）アクリレートモノマー２０〜１０００重量％、光重合開始剤０．１〜６０重量％である。 The amount of each component contained in the photocurable composition of the present invention can be appropriately set depending on the application, but usually the zirconia particles contained in the zirconia particle dispersion (if the surface is modified, the surface 10 to 2000 parts by weight of a polyfunctional (meth) acrylate monomer and 0.01 to 100 parts by weight of a photopolymerization initiator with respect to 100 parts by weight of the modified zirconia particles), preferably a polyfunctional (meth) acrylate monomer It is 20 to 1000% by weight, and the photopolymerization initiator is 0.1 to 60% by weight.
本発明の光硬化性組成物は、上記の成分の他に、その特性を損なわない範囲において、単官能（メタ）アクリレート化合物の他、メチルイソブチルケトン等の溶媒、その他レベリング剤等を含むこともできる。 In addition to the above components, the photocurable composition of the present invention may contain a monofunctional (meth) acrylate compound, a solvent such as methyl isobutyl ketone, other leveling agents, etc., as long as the properties are not impaired. it can.
実施例１
ノニオン型分散剤として楠本化成（株）製、ＰＬＡＤＤ ＥＤ１５１（上記式（１）（ｍ＝約９，ｎ＝約１３）のポリオキシエチレンアルキルリン酸エステル）１．８０ｇ（ドライ）、アセト酢酸メチル（分散助剤）１．５６ｇ、多官能（メタ）アクリレートモノマーとして日本化薬（株）製、商品名：ＫＡＹＡＲＡＤ ＤＰＨＡ（ジペンタエリスリトールヘキサアクリレートとジペンタエリスリトールペンタアクリレートとの重量比６０対４０の混合物）４．２０ｇ、メチルエチルケトン５６．３２ｇ及び２−ブタノール４．１７ｇを混合し、ホモジナイザーで撹拌しながらジルコニア粒子（第一稀元素科学工業（株）製、ＵＥＰ、一次粒径２０〜３０ｎｍ、強熱減量０．４％）３０．００ｇを約１０分間にわたって加えた。粒子添加後約１５分間撹拌した（プレ分散）。得られたスラリーを、以下の条件で、三井鉱山（株）製ＳＣミルを用いて２．５時間分散した。
機器 ：三井鉱山（株）製 ＳＣミル
周波数：６０Ｈｚ（回転数３６００ｒｐｍに相当）
ケーシング容量：５９ｍｌ
スラリー量：４００ｇ
分散ビーズ充填量：ガラスビーズ（ＴＯＳＨＩＮＲＩＫＯ製、ＢＺ−０１）
（ビーズ径０．１ｍｍ）４６ｇ 体積充填率３１%
分散時間：経時で粒径を測定し、粒径の低下が観察されなくなった時点を分散の終点とした。
Example 1
1.80 g (dry) of PLADD ED151 (polyoxyethylene alkyl phosphate ester of the above formula (1) (m = about 9, n = about 13)) manufactured by Enomoto Kasei Co., Ltd. as a nonionic dispersant, methyl acetoacetate (Dispersion aid) 1.56 g, manufactured by Nippon Kayaku Co., Ltd. as a polyfunctional (meth) acrylate monomer, trade name: KAYARAD DPHA (weight ratio 60:40 of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) (Mixture) 4.20 g, methyl ethyl ketone 56.32 g and 2-butanol 4.17 g were mixed and stirred with a homogenizer, zirconia particles (manufactured by Daiichi Rare Elemental Sciences, UEP, primary particle size 20-30 nm, strong) 30.00 g) (heat loss 0.4%) was added over about 10 minutes. It stirred for about 15 minutes after particle | grain addition (pre-dispersion). The obtained slurry was dispersed for 2.5 hours using an SC mill manufactured by Mitsui Mining Co., Ltd. under the following conditions.
Equipment: Mitsui Mining Co., Ltd. SC mill frequency: 60 Hz (equivalent to 3600 rpm)
Casing capacity: 59ml
Amount of slurry: 400g
Dispersed bead filling amount: Glass beads (manufactured by TOSHINRIKO, BZ-01)
(Bead diameter 0.1mm) 46g Volume filling rate 31%
Dispersion time: The particle size was measured over time, and the point at which no decrease in particle size was observed was taken as the end point of dispersion.
このジルコニア分散ゾルに分散しているジルコニア粒子のメジアン径を以下の条件で測定した。結果を表１に示す。
機器：（株）堀場製作所製 動的光散乱式粒径分布測定装置
測定条件： 温度 ２５℃
試料 サンプルを原液のまま測定
データ解析条件：粒子径基準 体積基準
分散粒子 ＺｒＯ２ 屈折率２．０５０
分散媒 メチルエチルケトン 屈折率１．３７９
The median diameter of the zirconia particles dispersed in the zirconia dispersion sol was measured under the following conditions. The results are shown in Table 1.
Equipment: Dynamic light scattering type particle size distribution measuring device manufactured by HORIBA, Ltd. Measurement conditions: Temperature 25 ° C
Sample Analytical condition of measurement data as sample solution: Particle size standard Volume standard
Dispersed particles ZrO 2 Refractive index 2.050
Dispersion medium Methyl ethyl ketone Refractive index 1.379
実施例２
実施例１で用いたＰＬＡＤＤ ＥＤ１５１の代わりに、ノニオン型分散剤として、楠本化成（株）製、ディスパロンＰＷ３６（上記式（１）（ｍ＝約１０，ｎ＝約１６）のポリオキシエチレンアルキルリン酸エステル）を用いた他は、実施例１と同様にしてジルコニア分散ゾルを得て、ジルコニア粒子のメジアン径を測定した。結果を表１に示す。
Example 2
Instead of PLAD ED151 used in Example 1, polyoxyethylene alkyl phosphorus of Disparon PW36 (formula (1) (m = about 10, n = about 16) manufactured by Enomoto Kasei Co., Ltd.) was used as a nonionic dispersant. A zirconia dispersed sol was obtained in the same manner as in Example 1 except that the acid ester was used, and the median diameter of the zirconia particles was measured. The results are shown in Table 1.
比較例１〜６
実施例１で用いたＰＬＡＤＤ ＥＤ１５１の代わりに、下記に示す分散剤を用いた他は、実施例１と同様にしてジルコニア分散ゾルを得て、ジルコニア粒子のメジアン径を測定した。ただし、プレ分散において、粒子の沈降、増粘が起きた分散剤については、その時点で調整を中止した。結果を表１に示す。
Comparative Examples 1-6
A zirconia-dispersed sol was obtained in the same manner as in Example 1 except that the following dispersant was used instead of the PLAADD ED151 used in Example 1, and the median diameter of the zirconia particles was measured. However, in the pre-dispersion, the adjustment for the dispersant in which sedimentation or thickening of the particles occurred was stopped at that time. The results are shown in Table 1.
比較例１
ノニオン型：花王（株）製、エマルゲン１０４Ｐ、
ポリオキシエチレンラウリルエーテル
比較例２
ノニオン型：花王（株）製、レオドールスーパーＳＰ−Ｌ１０、
ソルビタンモノラウレート
比較例３
ノニオン型：花王（株）製、レオドールＭＯ−６０、
グリセロールモノオレエート
比較例４
アニオン型：花王（株）製、ネオペレックスＮｏ.６、
ドデシルベンゼンスルホン酸ナトリウム
比較例５
カチオン型：日本油脂（株）製、エレガン２６４、
変性脂肪族ジメチルエチルアンモニウムエトサルフェート
比較例６
高分子量型：花王（株）製、デモールＥＰ、
特殊ポリカルボン酸高分子界面活性剤
Comparative Example 1
Nonion type: manufactured by Kao Corporation, Emulgen 104P,
Polyoxyethylene lauryl ether comparative example 2
Nonion type: manufactured by Kao Corporation, Rheodor Super SP-L10,
Sorbitan monolaurate comparative example 3
Nonion type: manufactured by Kao Corporation, Rheodor MO-60,
Glycerol monooleate comparative example 4
Anion type: manufactured by Kao Corporation, Neo-Perex No. 6,
Comparative example 5 of sodium dodecylbenzenesulfonate
Cationic type: Nippon Oil & Fats Co., Ltd., Elegan 264,
Modified Aliphatic Dimethylethylammonium Ethosulphate Comparative Example 6
High molecular weight type: Kao Corporation, Demole EP,
Special polycarboxylic acid polymer surfactant
△：１日後、沈降、増粘有り
×：撹拌直後に沈降、増粘有り
本発明の光硬化性組成物は、例えば、プラスチック光学部品、タッチパネル、フィルム型液晶素子、プラスチック容器、建築内装材としての床材、壁材、人工大理石等の傷付き（擦傷）防止や汚染防止のための保護コーティング材；フィルム型液晶素子、タッチパネル、プラスチック光学部品等の反射防止膜；各種基材の接着剤、シーリング材；印刷インクのバインダー材等に用いられ、特に反射防止膜の高屈折率膜を形成する樹脂組成物として好適に用いることができる。また、本発明のジルコニア粒子分散液は、上記の光硬化性組成物に含ませて用いることができる。 The photocurable composition of the present invention can be used to prevent, for example, plastic optical parts, touch panels, film-type liquid crystal elements, plastic containers, floor materials as building interior materials, wall materials, artificial marble, etc. and prevent contamination. Protective coating material for coatings; antireflection films for film-type liquid crystal elements, touch panels, plastic optical parts, etc .; adhesives and sealing materials for various substrates; binders for printing inks, etc. It can be suitably used as a resin composition for forming a rate film. Moreover, the zirconia particle dispersion liquid of the present invention can be used by being included in the above-mentioned photocurable composition.
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| JP4817254B2 (en) * | 2006-12-01 | 2011-11-16 | 大日本塗料株式会社 | Zirconium oxide particle dispersion, photocurable composition containing zirconium oxide particles, and cured film |
| JP2008201634A (en) * | 2007-02-21 | 2008-09-04 | Fujifilm Corp | Zirconia particle dispersion, organic and inorganic composite material produced from the dispersion and optical member |
| JP5500910B2 (en) * | 2009-08-03 | 2014-05-21 | 第一稀元素化学工業株式会社 | Zirconia sol and method for producing the same |
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| WO2016093014A1 (en) | 2014-12-12 | 2016-06-16 | Dic株式会社 | Process for producing dispersion of fine inorganic particles, curable composition containing said dispersion, and cured object obtained therefrom |
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