WO2013094738A1 - オリゴマー修飾微粒子とその製造方法および塗料 - Google Patents
オリゴマー修飾微粒子とその製造方法および塗料 Download PDFInfo
- Publication number
- WO2013094738A1 WO2013094738A1 PCT/JP2012/083277 JP2012083277W WO2013094738A1 WO 2013094738 A1 WO2013094738 A1 WO 2013094738A1 JP 2012083277 W JP2012083277 W JP 2012083277W WO 2013094738 A1 WO2013094738 A1 WO 2013094738A1
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- WIPO (PCT)
- Prior art keywords
- oligomer
- fine particles
- oxide fine
- inorganic oxide
- modified
- Prior art date
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- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 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
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000010959 steel 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
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DAVVOFDYOGMLNQ-UHFFFAOYSA-N trimethoxy-[1-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](OC)(OC)C(C)OCC1CO1 DAVVOFDYOGMLNQ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- ZNXDCSVNCSSUNB-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](OC)(OC)CCOCC1CO1 ZNXDCSVNCSSUNB-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3676—Treatment with macro-molecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0096—Compounds of antimony
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3615—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C1/3623—Grinding
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3684—Treatment with organo-silicon compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/041—Grinding
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to oligomer-modified particles, a method for producing the same, and a coating material containing the fine particles.
- Patent Document 1 describes a hard coat film composed of a composite oxide particle composed of an iron oxide component and a titanium oxide component and a matrix. Such a film has a high refractive index, transparency, and scratch resistance. It is described to exert.
- Patent Document 2 describes a coating composition for optical plastic moldings containing titanium oxide composite fine particles whose surface is modified with a silane coupling agent.
- the present invention solves the conventional problems as described above, and has an object to provide surface-treated fine particles that are excellent in reactivity with a matrix component and can exhibit excellent coating performance.
- the present inventors have found that the problems of the present invention can be solved by the following means, and have completed the present invention. That is, the present invention is as follows.
- R n M 1 (OR ') zn (1) M 1 : one or more elements selected from Si, Ti, Zr, and Al R, R ′: one or more groups selected from an alkyl group having 1 to 8 carbon atoms, an aryl group, or a vinyl group n: 0 ⁇ integer z of (z-2): metal alkoxides represented by the valence of M 1 oligomer modified modified with an oligomer derived from the (M 1, R, R 'and n comprises a mixture of different metal alkoxides)
- the inorganic oxide fine particles are oxide fine particles or composite oxide fine particles containing one or more metal elements selected from titanium, zirconium, tin, niobium, tungsten, antimony, indium, and aluminum.
- the unit viscosity value obtained by dividing the viscosity of the methanol dispersion in which the oligomer-modified inorganic oxide fine particles are dispersed in methanol by the solid content concentration of the aqueous dispersion is 0.07 to 0.6565 mPa ⁇ s.
- a paint comprising the oligomer-modified inorganic oxide fine particles according to any one of [1] to [7] or the dispersion according to [8] and a matrix-forming component.
- a method for producing oligomer-modified inorganic oxide fine particles whose surface is modified with an oligomer The following steps (1) to (2); Process (1) following formula (1); R n M 1 (OR ') zn (1) M 1 : one or more elements selected from Si, Ti, Zr, and Al R, R ′: one or more groups selected from an alkyl group having 1 to 8 carbon atoms, an aryl group, or a vinyl group n: 0 ⁇ integer z of (z-2): metal alkoxides represented by the valence of M 1 (M 1, R, comprises a mixture of R 'and n are different metal alkoxide) and / or a hydrolyzate thereof, acid A mixed solution containing a linear metal alkoxide oligomer is obtained by adding a catalyst and water and hydrolyzing and polycondensing the resulting mixed solution at 60 to 120 ° C.
- Step (2) 1 selected from titanium, zirconium, tin, niobium, tungsten, antimony, indium, and aluminum in the mixed solution obtained by removing the acid catalyst from the mixed solution containing the linear metal alkoxide oligomer produced in the step (1).
- a method for producing oligomer-modified inorganic oxide fine particles comprising: [11] The method for producing oligomer-modified inorganic oxide fine particles according to [10], wherein the pH of the mixed solution when hydrolyzing the metal alkoxide in the step (1) is in the range of 2 to 4.
- the oligomer-modified inorganic oxide fine particles according to the present invention are modified with an oligomer having a predetermined degree of polymerization and a molecular weight range, the scratch resistance and film hardness of the coating film obtained from the paint containing the fine particles are improved. In addition, excellent adhesion and transparency can be exhibited. In addition, a coating film excellent in light resistance, weather resistance, chemical resistance, and moisture resistance can be provided.
- Oligomer-modified inorganic oxide fine particles have the following formula (1) on the surface of the inorganic oxide fine particles.
- R n M 1 (OR ') zn (1) M 1 : one or more elements selected from Si, Ti, Zr, and Al R, R ′: one or more groups selected from an alkyl group having 1 to 8 carbon atoms, an aryl group, or a vinyl group n: 0 ⁇ integer z of (z-2): metal alkoxides represented by the valence of M 1 oligomer modification oligomer derived from the (M 1, R, R 'and n comprises a mixture of different metal alkoxides) are modified
- the oligomer is characterized in that the degree of polymerization of the oligomer is 3 or more and the weight average molecular weight of the oligomer is in the range of 1000 to 10,000.
- the oligomer is derived from the metal alkoxide and is a polycondensate of the hydrolyzate and / or partial hydrolyzate of the metal alkoxide, or a polycondensate of these polycondensates, or these It is an oligomer containing a mixture or the like.
- the oligomer preferably includes a linear polycondensed oligomer.
- Such oligomer-modified inorganic oxide fine particles modified with an oligomer are preferable because they are highly stable in an organic solvent and highly reactive with a matrix component, and are excellent in hardness and scratch resistance of the resulting coating film.
- oligomers on the surface of the oligomer-modified inorganic oxide fine particles and the matrix component are combined and integrated so that defects such as coating film cracks are less likely to be formed compared to normal silane coupling agent-treated fine particles. preferable.
- the oligomer according to the present invention has a larger number of OH groups per molecule than a silane coupling agent treated with ordinary silane coupling agent-treated fine particles, it has the same hardness and scratch resistance even with a relatively small modification amount. It is preferable because it is obtained.
- the degree of polymerization of the oligomer is 3 or more, more preferably 6 to 100, more preferably 15 to 90. When the degree of polymerization is less than 3, it is not preferable because the film hardness of the coating film is lowered.
- the weight average molecular weight of the oligomer is preferably in the range of 1000 to 10,000, more preferably 3000 to 9000. When the weight average molecular weight is less than 1000, the film hardness of the coating film is lowered, which is not preferable. When the weight average molecular weight exceeds 10,000, the scratch resistance of the coating film is lowered, which is not preferable.
- R n M 1 (OR ′) zn preferably contains one or more elements selected from Si, Ti, Zr and Al as M 1 .
- Use of a metal alkoxide containing such an element is preferable because the refractive index, film hardness, and scratch resistance of the coating film containing the oligomer-modified inorganic oxide fine particles are improved.
- the M 1 is more preferably Si.
- R and R ′ contained in the formula (1) R n M 1 (OR ′) zn are preferably one or more groups selected from an alkyl group having 1 to 8 carbon atoms, an aryl group or a vinyl group. . Use of such a group is preferable because cracks or pinholes in the coating film are hardly formed.
- alkyl group having 1 to 8 carbon atoms examples include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
- aryl group examples include a phenyl group, a benzyl group, a tolyl group, and an o-xylyl group.
- R n M 1 (OR ′) zn may be an integer from 0 to (z ⁇ 2) (z is the valence of M 1 ). That is, the metal alkoxide only needs to contain at least two hydrolyzable groups.
- the metal alkoxide represented by the formula (1) may be one kind or a mixture of several kinds.
- the oligomer may further contain, as a subcomponent, a component derived from a metal alkoxide in which n is (z-1), that is, a metal alkoxide containing only one hydrolyzable group.
- metal alkoxides examples include silicon alkoxide, zirconium alkoxide, titanium alkoxide, aluminum alkoxide, and the like.
- the inorganic oxide fine particles are preferably oxide fine particles or composite oxide fine particles containing one or more metal elements selected from titanium, zirconium, tin, niobium, tungsten, antimony, indium, and aluminum.
- inorganic oxide fine particles known particles can be used, and the shape of the fine particles may be any shape such as a spherical shape, a rod shape, a confetti shape, and a hollow shape, and is a crystalline fine particle. Alternatively, it may be amorphous fine particles.
- inorganic oxide fine particles crystalline fine particles are particularly preferable. Since the crystalline inorganic oxide fine particles have a high refractive index and high stability, they are suitable for use as a coating liquid for optical substrates.
- the inorganic oxide fine particles may be core-shell type composite oxide fine particles.
- core-shell type complex oxide fine particles known ones can be used.
- the inorganic oxide fine particles are metal elements such as silicon, potassium, sodium, magnesium, calcium, barium, strontium, lithium, lanthanum, cerium, iron, cobalt, nickel, copper, zinc, hafnium, gallium, and selenium as subcomponents. May further be included.
- the unit viscosity value obtained by dividing the viscosity of the methanol dispersion of the oligomer-modified inorganic oxide fine particles by the solid content concentration of the dispersion is 0.07 to 0.65 mPa ⁇ s / (wt%), more preferably It is preferably in the range of 0.10 to 0.50 mPa ⁇ s / (wt%).
- Oligomer-modified inorganic oxide fine particles having such properties are preferable because the viscosity of the coating is high and a coating film having a high film thickness is easily formed.
- the viscosity of the paint is lowered, and the film thickness of the coating film may become thin. If the unit viscosity value exceeds 0.65 mPa ⁇ s / (% by weight), the viscosity of the paint becomes too high and the fluidity is lowered, which is not preferable.
- (A) / (B) is less than 0.05, the hardness of the coating film may be lowered, which is not preferable.
- (A) / (B) exceeds 50, the scratch resistance of the coating film may be lowered, which is not preferable.
- the average particle size of the oligomer-modified inorganic oxide fine particles is preferably in the range of 9 to 65 nm, more preferably 9 to 45 nm.
- the average particle diameter is less than 8 nm, the viscosity of the dispersion may increase, which is not preferable. If the average particle diameter exceeds 60 nm, the transparency of the coating film may be lowered, which is not preferable.
- the average particle diameter of the inorganic oxide fine particles is preferably in the range of 8 to 60 nm, more preferably 8 to 60 nm. When the average particle diameter is less than 8 nm, the viscosity of the dispersion may increase, which is not preferable. If the average particle diameter exceeds 60 nm, the transparency of the coating film may be lowered, which is not preferable.
- Dispersion The dispersion according to the present invention is characterized by containing oligomer-modified inorganic oxide fine particles according to the present invention.
- the dispersion further includes a dispersion solvent, and examples of the dispersion solvent include water, alcohols such as methanol, ethanol, butanol, propanol, and isopropyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and propylene.
- alcohols such as methanol, ethanol, butanol, propanol, and isopropyl alcohol
- ethylene glycol monomethyl ether propylene glycol monomethyl ether
- propylene glycol monomethyl ether propylene.
- At least one organic compound selected from ethers such as glycol monoethyl ether and ketones such as methyl ethyl ketone and ⁇ -butyrolactone can be used.
- the dispersion liquid may contain subcomponents and additives such as a light absorber, a conductive material, and a colorant as required.
- the solid concentration of the dispersion is preferably in the range of 10 to 50% by weight. When the solid content concentration is less than 10% by weight, the solid content concentration of the coating material may decrease, which is not preferable.
- the viscosity of the paint may increase excessively, which is not preferable.
- the dispersion is used for hard coat materials, antireflection materials, reflective materials, catalysts, adhesive materials, primer materials, cross-linking materials, insulating materials, conductive materials, adsorbent materials, cosmetic materials, catalysts, optical path materials, fillers, etc. can do.
- the dispersion according to the present invention contains oligomer-modified inorganic oxide fine particles, pinholes, voids, cracks and other defects are suppressed, adhesion, hardness, scratch resistance, chemical resistance, moisture resistance, transparency, weather resistance Excellent effects such as light resistance and light resistance. Paint The paint according to the present invention is characterized by containing the oligomer-modified inorganic oxide fine particles according to the present invention or the dispersion according to the present invention and a matrix component.
- the coatings are various coatings such as hard coat materials, antireflection materials, reflective materials, catalysts, adhesive materials, primer materials, cross-linking materials, insulating materials, conductive materials, adsorbent materials, decorative materials, catalysts, optical path materials, fillers, etc. It can be used as a coating film-forming coating material, and is particularly suitable as a coating film-forming coating material for optical substrates such as plastic lenses.
- the paint according to the present invention contains the oligomer-modified inorganic oxide fine particles according to the present invention, the film hardness and scratch resistance are high, the adhesion and transparency are excellent, and the light resistance, weather resistance, and chemical resistance are also high. An excellent coating film having a high refractive index can be produced.
- Examples of the matrix component include organic silicon compounds, thermosetting organic resins, thermoplastic organic resins, and ultraviolet curable organic resins.
- organosilicon compound examples include alkoxysilane compounds, and specific examples include tetraethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glucidoxy.
- organosilicon compounds may be used in a state where at least a part thereof is hydrolyzed.
- Such an organosilicon compound is particularly suitable as a binder component of a coating composition for forming a hard coat film.
- thermosetting organic resin is preferably at least one selected from urethane resins, epoxy resins and melamine resins.
- examples of the urethane resin include a reaction product of a block-type polyisocyanate such as hexamethylene diisocyanate and an active hydrogen-containing compound such as polyester polyol and polyether polyol, and the epoxy resin.
- examples of the resin include a polyalkylene ether-modified epoxy resin and an epoxy group-containing compound in which a flexible skeleton (soft segment) is introduced into a molecular chain.
- examples of the melamine-based resin include a cured product of etherified methylolmelamine, polyester polyol, and polyether polyol.
- a urethane-based resin that is a cured product of a blocked isocyanate and a polyol.
- these thermosetting organic resins may use not only one type but also two or more types.
- the thermoplastic organic resin is preferably at least one selected from an acrylic resin, a urethane resin, and an ester resin, and more preferably a self-emulsifying aqueous emulsion resin.
- a resin is particularly suitable as a binder component of the primer layer-forming coating composition.
- the ultraviolet curable organic resin for example, a compound of an ultraviolet curable compound such as a polyfunctional acrylic compound having an acryloyloxy group can be used.
- the content of the oligomer-modified inorganic oxide fine particles in the coating is not particularly limited, but is preferably in the range of 1 to 35% by weight on the basis of solid content weight conversion.
- Method for producing oligomer-modified inorganic oxide fine particles includes the following steps (1) to (2): Process (1) Following formula (1); R n M 1 (OR ') zn (1) M 1 : one or more elements selected from Si, Ti, Zr, and Al R, R ′: one or more groups selected from an alkyl group having 1 to 8 carbon atoms, an aryl group, or a vinyl group n: 0 ⁇ integer z of (z-2): metal alkoxides represented by the valence of M 1 (M 1, R, comprises a mixture of R 'and n are different metal alkoxide) and / or a hydrolyzate thereof, acid
- Step (2) 1 selected from titanium, zirconium, tin, niobium, tungsten, antimony, indium, and aluminum in the mixed solution obtained by removing the acid catalyst from the mixed solution containing the linear metal alkoxide oligomer produced in the step (1).
- Process (1) a mixed solution containing a metal alkoxide oligomer represented by the formula (1) is produced.
- metal alkoxide examples include silicon alkoxide such as normal ethyl silicate, tetramethoxysilane or a condensate thereof, zirconium alkoxide such as zirconium tetranormal propoxide, zirconium tributoxy monoacetylacetonate or a condensate thereof, titanium tetraisopropoxide.
- titanium alkoxides such as titanium diisopropoxybis (acetylacetonate) or condensates thereof can be used.
- silicate 40, the silicate 45, the silicate 48, the M silicate 51, etc. of Tama Chemical Industry which are these partial hydrolysis or hydrolysates. You may use these in mixture of 2 or more types. These may be dispersed in an organic solvent.
- a metal alkoxide having n of (z-1) may be added as a subcomponent within a range not impairing the effects of the present invention. That is, even if a non-linear oligomer is partially formed by adding a metal alkoxide having n of (z-1), there is a problem if the effect of the present invention is obtained due to the presence of the linear oligomer. There is no.
- the amount may be an amount that is less than 10% by weight of the whole.
- organic solvent examples include alcohols such as methanol, ethanol, butanol, propanol, isopropyl alcohol, ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl ethyl ketone, ⁇ -At least one organic compound selected from ketones such as butyrolactone.
- alcohols such as methanol, ethanol, butanol, propanol, isopropyl alcohol
- ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl ethyl ketone, ⁇ -At least one organic compound selected from ketones such as butyrolactone.
- an organic solvent such as denatured alcohol may be added as a dispersion solvent.
- hydrolysis and polycondensation are carried out at 60 to 120 ° C. for 20 minutes to 24 hours to thereby obtain metal alkoxides and / or hydrolysates thereof. It is possible to obtain an oligomer in which is linearly polymerized.
- the acid catalyst for example, hydrochloric acid, nitric acid, sulfuric acid, acetic acid and the like can be used.
- the amount of water added at this time may be any amount that is necessary and sufficient to hydrolyze the metal alkoxide.
- the pH of the mixed solution when the metal alkoxide is hydrolyzed and polycondensed is preferably in the range of 2 to 4.
- the temperature is preferably in the range of 60 to 120 ° C., more preferably 80 to 110 ° C. When the temperature is less than 60 ° C., it is difficult to obtain a desired molecular weight, which is not preferable. If the temperature exceeds 120 ° C., the molecular weight increases excessively, which is not preferable.
- the hydrolysis time is preferably in the range of 20 to 24 hours, more preferably 30 minutes to 12 hours. When the time is less than 20 minutes, the molecular weight decreases, which is not preferable. If the time exceeds 24 hours, the economical efficiency is lowered.
- the degree of polymerization of the oligomer contained in the mixed solution is 3 or more, more preferably 6 to 100, still more preferably 15 to 90, and the average molecular weight is in the range of 1000 to 10,000, more preferably 3000 to 9000. It is preferable that it is such.
- Step (2) In this step, the acid catalyst is removed from the mixed solution produced in the step (1), and then one or more metal elements selected from titanium, zirconium, tin, niobium, tungsten, antimony, indium, and aluminum are included.
- the metal oxide alkoxide oligomer is reacted with the surface of the inorganic oxide fine particles by treating at 5 to 30 ° C. for 0.5 to 24 hours, so that the oligomer-modified inorganic oxide fine particles. This is a step of obtaining a dispersion liquid.
- the oligomer-modified inorganic oxide fine particles having such a structure containing a linear oligomer are stable and excellent in reaction with the matrix component, and the coating film obtained from the paint containing such oligomer-modified inorganic oxide fine particles is Film hardness is very high, and it excels in transparency, scratch resistance and adhesion.
- Inorganic oxide fine particles containing one or more metal elements selected from titanium, zirconium, tin, niobium, tungsten, antimony, indium, and aluminum have a high refractive index and excellent film hardness when blended in a coating film. Therefore, it is preferable.
- Such inorganic oxide fine particles may be single oxide particles, composite oxide fine particles, or core-shell type fine particles.
- the shape can be a known shape such as a spherical shape, a rod shape, a confetti shape, or a hollow shape.
- inorganic oxide fine particles known ones can be used.
- the inorganic oxide fine particles can be produced by, for example, a liquid phase method such as hydrolysis or neutralization reaction or coprecipitation of a metal salt or metal alkoxide, a hydrothermal synthesis method, a solid phase method, or the like. Moreover, you may use what crystallized these by baking etc.
- these inorganic oxide fine particles may further contain other metal element components as subcomponents.
- the dispersion medium is preferably an organic solvent, and in particular, alcohols such as methanol, ethanol, butanol, propanol, isopropyl alcohol, and the like.
- alcohols such as methanol, ethanol, butanol, propanol, isopropyl alcohol, and the like.
- Preferred are at least one organic compound selected from ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ketones such as methyl ethyl ketone and ⁇ -butyrolactone.
- an organic solvent may be added.
- the method described in JP-A-2000-204301, JP-A-2011-132484, JP-A-2011-037659, JP-A-05-2102, or the like can be used. Can do.
- the solid content weight of the mixed solution containing the oligomer is 5 to 50 with respect to the solid content weight of the inorganic oxide fine particles. It may be added as follows.
- the treatment temperature of the mixed solution is preferably 5 to 30 ° C., more preferably 5 to 20 ° C.
- the treatment temperature is less than 5 ° C., the viscosity of the mixed solution increases, so that the stirring efficiency is deteriorated. If the treatment temperature exceeds 30 ° C., the viscosity of the oligomer tends to increase, such being undesirable.
- the treatment time is preferably 0.5 to 24 hours, more preferably 1.0 to 20 hours.
- the treatment time is less than 0.5 hour, the surface treatment of the inorganic fine particles becomes insufficient, which is not preferable. If the treatment time exceeds 24 hours, the economical efficiency is inferior.
- the thus obtained dispersion liquid of oligomer-modified inorganic oxide fine particles may be subjected to a process such as solvent replacement or concentration as necessary.
- Manufacturing method of coating material The coating material according to the present invention can be manufactured by mixing the dispersion of oligomer-modified inorganic oxide fine particles obtained in the above-described step and a matrix component.
- Examples of the matrix component include organic silicon compounds, thermosetting organic resins, thermoplastic organic resins, and ultraviolet curable organic resins as described above.
- the organosilicon compound when used as a matrix, the organosilicon compound is used in the presence of an acid or water in the absence of a solvent or in a polar organic solvent such as alcohol. It is preferable to mix with the dispersion liquid of oligomer-modified inorganic oxide fine particles after partial hydrolysis or hydrolysis. Alternatively, after mixing the dispersion of the organosilicon compound and oligomer-modified inorganic oxide fine particles, these may be partially hydrolyzed or hydrolyzed.
- the mixing ratio when the weight of the oligomer-modified inorganic oxide fine particles contained in the dispersion of the oligomer-modified inorganic oxide fine particles is represented by Y, X represents the weight of the organosilicon compound converted to SiO 2 standard, It is preferable that the weight ratio (X / Y) is 30/70 to 90/10, preferably 35/65 to 80/20.
- a coating using a thermosetting organic resin and the thermoplastic resin as a matrix is prepared by mixing the resin and a dispersion of oligomer-modified inorganic oxide fine particles, and the mixing ratio is R based on the weight of the resin.
- the weight of oligomer-modified inorganic oxide fine particles contained in the dispersion of oligomer-modified inorganic oxide fine particles is represented by S
- the weight ratio (R / S) is 90/10 to 30/70, more preferably 80 It is preferable to carry out so as to be / 20 to 35/65.
- the coating composition further contains an ultraviolet absorber.
- the ultraviolet absorber a conventionally known ultraviolet absorber or a currently developed ultraviolet absorber can be used.
- Typical ultraviolet absorbers such as benzophenone series, cinnamic acid series, p-aminobenzoic acid are used.
- organic compounds having optical stability such as a system and salicylic acid, and perovskite structure composite oxides such as calcium titanate, barium titanate, and strontium titanate can be used.
- the particle size distribution was measured.
- the average particle diameter as used in the field of this invention shows the value computed by cumulant analysis of this measurement result.
- (2) Measuring method of specific surface area About 30 ml of powder obtained by drying a dispersion containing inorganic oxide fine particles was collected in a magnetic crucible (type B-2), dried at a temperature of 300 ° C. for 2 hours, Place in a desiccator and cool to room temperature. Next, 1 g of a sample was taken, and the specific surface area (m 2 / g) of the particles was measured by a BET method using a fully automatic surface area measuring device (manufactured by Yuasa Ionics Co., Ltd., Multisorb 12 type).
- Viscosity measurement 20 ml of a methanol dispersion of oligomer-modified inorganic oxide fine particles (solid content concentration 30.5 wt%) was used as a sample, and at room temperature using a viscometer (manufactured by Toki Sangyo Co., Ltd., TV-10M). Viscosity measurement was performed.
- the viscosity meter rotor has a viscosity range of 1.0 to 10.0 mPa ⁇ s at a rotational speed of 60 rpm, a viscosity range of 10.0 to 20.0 mPa ⁇ s at a rotational speed of 30 rpm, and 20.0 to 50.0 mPas at a rotational speed of 12 rpm.
- the viscosity range of s was measured for a viscosity range of 50.0 to 100.0 mPa ⁇ s at a rotation speed of 6 rpm.
- the molecular weight in the repeating unit for each monomer was averaged according to the used weight of the monomer to calculate the unit molecular weight, and the degree of polymerization was determined.
- the oligomer contains a component derived from a metal alkoxide having n of (z-1), the molecular weight derived from the metal alkoxide is not converted as an error.
- About curable coating film (8) Method for measuring film hardness (Bayer value) Created in the preparation examples of the examples using an abrasion tester BTM (manufactured by Colts, USA) and a haze value measuring device (NDH2000 manufactured by NIPPON DENSHOKU). The Bayer value is measured based on the change in haze value between the tested lens and the reference lens.
- a commercially available plastic lens base material CR-39 base material (diethylene glycol bisallyl carbonate, monomer used by PPG, using a base material refractive index of 1.60) is used, and each haze value is first measured.
- the initial haze value of the reference lens is D (std0), and the initial haze value of the lens under test is D (test0).
- Each lens is placed in an abrasion resistance tester pan, filled with 500 g of abrasive (exclusive sand), and vibrated 600 times to the left and right for testing.
- the haze value of the reference lens after the test is D (stdf), and the haze value of the lens under test is D (testf).
- the Bayer test value (R) is calculated from the following equation.
- Example 1 Reference example Preparation of inorganic oxide fine particles (1) (Preparation of core particles) 93.7 kg of titanium tetrachloride aqueous solution containing 7.75% by weight of titanium tetrachloride (manufactured by Osaka Titanium Technologies Co., Ltd.) in terms of TiO 2, and ammonia water containing 15% by weight of ammonia (manufactured by Ube Industries) 36.3 kg) was mixed to prepare a white slurry having a pH of 9.5. Next, this slurry was filtered and then washed with pure water to obtain 72.6 kg of a hydrous titanate cake having a solid content of 10% by weight.
- a cation exchange resin is mixed with 72.9 kg of the aqueous solution of titanic acid titanate, and potassium stannate containing 1 wt% of potassium stannate (manufactured by Showa Kako Co., Ltd.) in terms of SnO 2 conversion. 9.1 kg of aqueous solution was gradually added under stirring.
- a silica sol containing 15% by weight of silica fine particles having an average particle diameter of 7 nm (manufactured by JGC Catalysts & Chemicals Co., Ltd.) 0 .8 kg and 18.0 kg of pure water are mixed and heated in an autoclave (pressure-resistant glass industry, 120 L) at a temperature of 165 ° C. for 18 hours, whereby a composite oxide containing titanium as a main component is obtained.
- An aqueous dispersion (C-1) of fine particles (core particles) was obtained.
- the obtained aqueous dispersion was cooled to room temperature and then concentrated with an ultrafiltration membrane device (ACV-3010, manufactured by Asahi Kasei Co., Ltd.) to give 10.0 kg of an aqueous dispersion having a solid content of 10% by weight. Obtained.
- ACV-3010 manufactured by Asahi Kasei Co., Ltd.
- the core particles contained in the aqueous dispersion has a rutile-type crystal structure, TiO 2 75.2 wt% when the content was measured in the metal element contained in the core particles, SnO 2 9.3 wt % was SiO 2 12.2 wt% and K 2 O3.3% by weight.
- Zirconium oxychloride manufactured by Taiyo Mining Co., Ltd.
- ammonia water containing 15% by weight of ammonia was gradually added with stirring to a pH of 8 .5 slurry was obtained.
- this slurry was filtered and then washed with pure water to obtain 5.26 kg of a cake containing 10% by weight of a zirconium component in terms of ZrO 2 in terms of conversion.
- this mixed solution is put in an autoclave (manufactured by Pressure Glass Industrial Co., Ltd., 50 L), subjected to heat treatment at a temperature of 160 ° C. for 18 hours, cooled to room temperature, and then subjected to ultrafiltration membrane device (Asahi Kasei)
- the surface of the core particles mainly composed of titanium is coated with a shell made of a complex oxide containing zirconium and silicon by concentrating to a solid content of 10% by weight using SIP-1013 manufactured by Co., Ltd.
- An aqueous dispersion (CW-1) of the core-shell type inorganic oxide fine particles thus prepared was prepared.
- the crystal structure of the core-shell type inorganic oxide fine particles was a rutile type.
- the average particle diameter of the core-shell type inorganic oxide fine particles was 21 nm as measured by a dynamic light scattering method, and the BET specific surface area was 224 m 2 / g.
- the core-shell type fine particles were used as the inorganic oxide fine particles of this example. While stirring 2000 g of the core-shell inorganic oxide fine particle aqueous dispersion (CW-1) obtained in the above step, 204 g of cation exchange resin was added and stirred for 1 hour at room temperature, and then the resin was separated. Subsequently, the dispersion solvent of the obtained aqueous dispersion was changed from water to methanol (manufactured by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9) using an ultrafiltration membrane device (filtration membrane manufactured by Asahi Kasei Corporation, SIP-1013). % By weight).
- CM-1 core-shell inorganic oxide fine particle methanol dispersion
- CM-1 had a water content of about 0.5 wt% and a solid content concentration of 10 wt%.
- the average particle diameter of the core-shell type inorganic oxide fine particles contained in the methanol dispersion was 21 nm.
- Preparation of oligomer-modified inorganic oxide fine particles (1) Process (1) Preparation of mixed solution containing oligomer (1) Mixing of 17.6 kg of methyl polysilicate (manufactured by Tama Chemical Co., Ltd., M silicate 51; degree of polymerization 3-5, average molecular weight 470) and 61.5 kg of denatured alcohol (produced by Nippon Alcohol Sales Co., Ltd., Echinen F-1) While stirring, 10.9 kg of 0.15% hydrochloric acid aqueous solution was added to the liquid.
- methyl polysilicate manufactured by Tama Chemical Co., Ltd., M silicate 51; degree of polymerization 3-5, average molecular weight 470
- denatured alcohol produced by Nippon Alcohol Sales Co., Ltd., Echinen F-1
- the resulting mixed solution had a solid content of 10.0% by weight and a pH of 3.3.
- the average molecular weight of the oligomer contained in the mixed solution is 3600, and the average degree of polymerization is 34 when the molecular weight of the repeating unit of the metal alkoxide is 106 (the structural formula of the repeating unit ⁇ —SiO (OCH 3 ) 2 — ⁇ ).
- Step (2) The mixed solution (P-1) 0.5 kg obtained above was mixed with 150 g of an amphoteric ion exchange resin and stirred at room temperature for 3 hours, and then the resin was separated to obtain a mixed solution from which hydrochloric acid as an acid catalyst had been removed. It was.
- the average particle size of the oligomer-modified inorganic oxide fine particles by dynamic light scattering was 23 nm. Further, this oligomer-modified fine particle dispersion had a pH of 4.5 and a viscosity of 3.3 mPa ⁇ s. Further, the solid content concentration of the methanol dispersion of the oligomer-modified fine particles was 30.5% by weight, and the unit viscosity value was 0.11 mPa ⁇ s / (% by weight).
- oligomer-modified inorganic oxide fine particles in methanol 402.1 g, propylene glycol monomethyl ether (manufactured by Dow Chemical) 40.6 g, tris (2,4-pentanedionato) aluminum III (Tokyo Kasei) Kogyo Co., Ltd.) (7.1 g) and 1.1 g of a silicone surfactant (Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added, and the mixture was stirred at room temperature all day and night to form a coating film for forming a hard coat layer film Composition (H1) was prepared.
- CP-1 402.1 g
- propylene glycol monomethyl ether manufactured by Dow Chemical
- tris (2,4-pentanedionato) aluminum III Tokyo Kasei) Kogyo Co., Ltd.
- a silicone surfactant Toray Dow Corning Co., Ltd., L-7604
- primer layer film-forming coating composition 161.0 g of polyurethane emulsion “Superflex 150” (Daiichi Kogyo Seiyaku, water-dispersed urethane elastomer solid content 30%), which is a commercially available thermoplastic resin, A container was prepared, and 205.9 g of a methanol dispersion (CP-1) of oligomer-modified fine particles prepared in this example and 97.1 g of ion-exchanged water were added, and the mixture was stirred for 1 hour.
- CP-1 methanol dispersion
- Example 2 Preparation of oligomer-modified inorganic oxide fine particles (2) Process (1) Preparation of mixed solution containing oligomer (2) Methyl polysilicate (manufactured by Tama Chemical Co., Ltd., M silicate 51; mainly composed of Si n O (n-1) (OCH 3 ) 2 (n + 1) .
- Methyl polysilicate manufactured by Tama Chemical Co., Ltd., M silicate 51; mainly composed of Si n O (n-1) (OCH 3 ) 2 (n + 1) .
- the resulting mixed solution had a solid content of 10.0% by weight and a pH of 3.3.
- the molecular weight of the oligomer contained in this mixed solution is 5000, and the molecular weight of the repeating unit is ⁇ —SiO (OCH 3 ) 2 — ⁇ (molecular weight 106) and [—ZrO (OC 4 H 9 ) (C 5 H 7 O 2 )-] (molecular weight 279) is included at a weight ratio of 9: 1.
- the polymerization degree is 40.4 when the average molecular weight of the repeating unit determined from the weight ratio calculated from this weight ratio is 123.3. 6.
- Step (2) In this step of “preparation of methanol dispersion of oligomer-modified inorganic oxide fine particles” described in Example 1, this example was used instead of using 0.5 kg of the silicon-based polymer dispersion (P-1) prepared in Example 1.
- Inorganic oxidation mainly composed of titanium by the same method as “Preparation of methanol dispersion of oligomer-modified fine particles” in Example 1 except that 0.5 kg of the silicon- and titanium-based polymer dispersion (P-2) prepared in 1 was used.
- the average particle size of the oligomer-modified fine particles was 27 nm as measured by a dynamic light scattering method. Further, this oligomer-modified fine particle dispersion had a pH of 4.5 and a viscosity of 3.3 mPa ⁇ s. Further, the solid content concentration of the oligomer-modified fine particles was 30.5%, and the unit viscosity value was 0.11 mPa ⁇ s /%.
- CP-2 propylene glycol monomethyl ether
- tris (2,4-pentanedionato) aluminum III Tokyo Chemical Industry Co., Ltd.
- a silicone surfactant manufactured by Toray Dow Corning Co., Ltd., L-7604
- Example 3 Preparation of oligomer- modified inorganic oxide fine particles (3)
- Process (1) Preparation of mixed solution containing oligomer (3)
- a mixed solution of methyl polysilicate, denatured alcohol, and aqueous hydrochloric acid solution was stirred at room temperature for 15 minutes, and then at 100 ° C. in an autoclave.
- a mixture containing an oligomer of a metal alkoxide containing silicon in the same manner as in “Preparation of mixed solution containing oligomer (1)” in Example 1, except that heating was carried out at a temperature of 100 ° C. for 240 minutes instead of heating for 60 minutes.
- a solution (P-3) was obtained.
- Step (2) “Preparation of oligomer-modified inorganic oxide fine particles (described in Example 1)” except that 0.5 kg of this oligomer mixed solution (P-3) was used instead of the mixed solution (P-1) of Example 1.
- a methanol dispersion (CP-3) of oligomer-modified inorganic oxide fine particles was obtained by the same method as in step (2) of “1)”.
- the average particle size of the oligomer-modified inorganic oxide fine particles by dynamic light scattering was 23 nm
- the pH of the methanol dispersion of the oligomer-modified inorganic oxide fine particles was 4.5
- the viscosity was 3.5 mPa ⁇ s.
- the solid content concentration of the methanol dispersion of the oligomer-modified inorganic oxide fine particles was 30.5% by weight
- the unit viscosity value was 0.11 mPa ⁇ s / (% by weight).
- coating composition (H3) for forming a hard coat layer film 177.3 g of ⁇ -glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol) (Concentration: 99.9% by weight)
- methanol produced by Hayashi Junyaku Co., Ltd., methyl alcohol
- oligomer-modified inorganic oxide fine particles in methanol (CP-3) 402.1 g, propylene glycol monomethyl ether (manufactured by Dow Chemical) 40.6 g, tris (2,4-pentanedionato) aluminum III (Tokyo Kasei) Kogyo Co., Ltd.) (7.1 g) and 1.1 g of a silicone surfactant (Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added, and the mixture was stirred at room temperature all day and night to form a hard coat layer film-forming coating material A composition (H3) was prepared.
- Example 4 Preparation of inorganic oxide fine particles (2) (Preparation of core particles) Zirconium oxychloride 8-hydrate in pure water 18.57Kg (Taiyo ore Engineering Co., ZrOCl 2 ⁇ 8H 2 O) was dissolved 0.50 kg, was added thereto 10 wt% KOH aqueous solution 17.56kg A zirconium hydroxide hydrogel (ZrO 2 concentration 1% by weight) was prepared. Next, the obtained zirconium hydroxide hydrogel was washed by an ultrafiltration membrane method until the conductivity reached 0.5 mS / cm or less.
- the solid content of the aqueous dispersion was 10% by weight on a ZrO 2 conversion basis.
- 10.10 kg of the aqueous dispersion of the core particles was spray-dried using a spray dryer (NIRO ATOMIZER manufactured by NIRO).
- NIRO ATOMIZER manufactured by NIRO
- 0.90 kg of a dry powder of composite oxide fine particles (core particles) mainly composed of zirconium was obtained.
- the average particle diameter of the core particles contained in the obtained dry powder was about 2 ⁇ m.
- 0.90 kg of the dry powder obtained above was calcined in an air atmosphere at a temperature of 500 ° C. for 2 hours to obtain a calcined powder of composite oxide fine particles (core particles) mainly composed of zirconium. 0.84 kg was obtained.
- 0.84 kg of the calcined powder obtained above was dispersed in 0.74 kg of pure water, and 0.55 kg of a 28.6% strength tartaric acid aqueous solution and 0.23 kg of a 50% strength by weight KOH aqueous solution were sufficiently added thereto.
- alumina beads having a particle diameter of 0.1 mm are added, and this is subjected to a wet pulverizer (batch type tabletop sand mill manufactured by Campehapio Co., Ltd.) for 180 minutes. Were pulverized and dispersed.
- alumina beads are separated and removed using a stainless steel filter having an aperture of 44 ⁇ m, and 6.65 kg of pure water is further added and stirred, so that water of complex oxide fine particles (core particles) mainly composed of zirconium is added. 8.84 kg of dispersion was obtained. The solid content of this aqueous dispersion was 11% by weight.
- the content of the metal component contained in the core particles was 98.5% by weight of ZrO 2 and 1.5% by weight of K 2 O on the basis of oxide conversion of each metal component.
- Preparation of core-shell type inorganic oxide fine particles After diluting commercially available water glass (manufactured by AGC S-Itech Co., Ltd., JIS No. 3 water glass, SiO 2 concentration 24 mass%) with pure water, it was removed using a cation exchange resin (manufactured by Mitsubishi Chemical Corporation). Alkaline and a pH containing 4.5% by weight of silicic acid solution in terms of SiO 2 gave a 2.3 aqueous silicic acid solution.
- aqueous dispersion (C-2) of composite oxide fine particles (core particles) mainly composed of zirconium obtained in the above step was added to 0.3 kg of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation). After removing the alkali using the resin, the resin was separated to obtain an aqueous dispersion sol.
- aqueous dispersion sol 100.0 g of the aqueous silicic acid solution was gradually added with stirring, and after the addition was completed, the aqueous dispersion was obtained by aging under stirring for 1 hour while maintaining the temperature at 35 ° C.
- a 10.0 wt% aqueous sodium hydroxide solution is added to the aqueous dispersion to adjust the pH to 10.0, and the mixture is aged for 1 hour with stirring while maintaining the temperature at 85 ° C.
- An aqueous dispersion (CW-2) of core-shell type inorganic oxide fine particles in which the surface of the oxide fine particles (core particles) was coated with silica was obtained.
- 204 g of cation exchange resin was added while stirring 2000 g of the core-shell type inorganic oxide fine particle aqueous dispersion (CW-2) obtained in the above step and stirred at room temperature for 1 hour, and then the resin was separated. .
- the dispersion solvent of the obtained aqueous dispersion was changed from water to methanol (manufactured by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9) using an ultrafiltration membrane device (filtration membrane manufactured by Asahi Kasei Corporation, SIP-1013). % By weight).
- CM-2 The resulting core-shell inorganic oxide fine particle methanol dispersion (hereinafter referred to as “CM-2”) had a water content of about 0.5 wt% and a solid content concentration of 10 wt%.
- CM-1 methanol dispersion liquid
- CM-2 methanol dispersion liquid
- CP-4 methanol dispersion of oligomer-modified inorganic oxide fine particles was obtained in the same manner as in steps (1) and (2) of “1)”.
- the average particle diameter of the oligomer-modified inorganic oxide fine particles measured by the dynamic light scattering method is 30 nm
- the pH of the methanol dispersion of the oligomer-modified inorganic oxide fine particles is 4.5
- the viscosity is 3.3 mPa ⁇ s. Met.
- the oligomer-modified inorganic oxide fine particles had a solid content concentration of 30.5% by weight and a unit viscosity value of 0.11 mPa ⁇ s / (% by weight).
- coating composition (H4) for forming a hard coat layer film 162.7 g of ⁇ -glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol) (Concentration: 99.9% by weight) 55.5 g of a 0.01N aqueous hydrochloric acid solution was added dropwise to 28.8 g of the mixed solution with stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.
- ⁇ -glycidoxypropyltrimethoxysilane Z-6040 manufactured by Toray Dow Corning Co., Ltd.
- methanol produced by Hayashi Junyaku Co., Ltd., methyl alcohol
- Example 5 Preparation of inorganic oxide fine particles (3) (Preparation of core particles) 12.1 kg of titanium tetrachloride aqueous solution containing 7.75% by weight of titanium tetrachloride (Osaka Titanium Technologies Co., Ltd.) in terms of TiO 2 and ammonia water containing 15% by weight of ammonia (manufactured by Ube Industries, Ltd.) 4 7 kg was mixed to prepare a white slurry liquid having a pH of 9.5. The slurry was then filtered and washed with pure water to obtain 9.9 kg of a hydrous titanate cake having a solid content of 10% by weight.
- the solids contained in the mixed aqueous solution thus obtained were measured by the above method. As a result, they were composite oxide fine particles (titanium-based fine particles) containing titanium and tin having a rutile crystal structure. Furthermore, when the content of the metal component contained in the titanium-based fine particles was measured, TiO 2 : 87.2% by weight, SnO 2 : 11.0% by weight, and K based on the oxide conversion standard of each metal component. 2 O: 1.8% by weight. The pH of the mixed aqueous solution was 10.0.
- aqueous dispersion sol having a solid content of 11 wt% was added. Obtained.
- the aqueous dispersion sol containing titanium-based fine particles obtained by pulverization in this manner was milky white.
- the average particle diameter of the titanium-based fine particles contained in the water-dispersed sol was 106 nm, and the distribution frequency of coarse particles having a particle diameter of 100 nm or more was 59.1%.
- the cation exchange resin was separated and removed using a stainless steel filter having an opening of 44 ⁇ m, and this water-dispersed sol was subjected to a centrifuge (CR-21G manufactured by Hitachi Koki Co., Ltd.) at 12,000 rpm. The treatment was carried out at a speed for 1 hour to classify and remove coarse particles having a particle diameter of 100 nm or more. As a result, 1.13 kg of an aqueous dispersion sol having a solid content of 6.4% by weight was obtained.
- the average particle diameter of the core-shell type inorganic oxide fine particles measured by a dynamic light scattering method was 25 nm, and the BET specific surface area was 82 m 2 / g.
- step (2) of “Preparation of oligomer-modified inorganic oxide fine particles (1)” described in Example 1 methanol dispersion liquid (CM-1) 1 of core-shell type inorganic oxide fine particles prepared in Example 1
- CM-3 methanol-dispersed core-shell type inorganic oxide fine particles
- a methanol dispersion (CP-5) of oligomer-modified inorganic oxide fine particles was obtained in the same manner as in steps (1) and (2) of “1)”.
- the average particle diameter of the oligomer-modified inorganic oxide fine particles measured by the dynamic light scattering method is 23 nm
- the pH of the methanol dispersion of the oligomer-modified inorganic oxide fine particles is 4.5
- the viscosity is 3.3 mPa.s. ⁇ It was s.
- the solid content concentration of the methanol dispersion of the oligomer-modified inorganic oxide fine particles was 30.5% by weight
- the unit viscosity value was 0.11 mPa ⁇ s / (% by weight).
- coating composition (H5) for forming a hard coat layer film 165.3 g of ⁇ -glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol) (Concentration: 99.9% by weight) 56.3 g of a 0.01N aqueous hydrochloric acid solution was added dropwise to 29.3 g of the mixed solution with stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.
- primer layer film-forming coating composition 161.0 g of polyurethane emulsion “Superflex 150” (Daiichi Kogyo Seiyaku Co., Ltd., water-dispersed urethane elastomer solid content 30%), which is a commercially available thermoplastic resin, A container was prepared, and 205.9 g of a methanol dispersion (CP-5) of oligomer-modified inorganic oxide fine particles prepared in this example and 97.1 g of ion-exchanged water were added thereto, followed by stirring for 1 hour.
- CP-5 methanol dispersion
- the ion exchange resin was separated, and the obtained aqueous dispersion and 2.0 kg of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) were mixed. Furthermore, after adding 38.5 g of normal ethyl silicate (manufactured by Tama Chemical Co., Ltd.) containing 28% by weight of a silicon component in terms of SiO 2 in the mixed solution, the mixed solution was heated to a temperature of 50 ° C. And stirred for 18 hours. The molecular weight of the component derived from the silane coupling agent contained in the mixed solution when 38.5 g of ethyl orthosilicate was mixed with 1800 g of water and 2 kg of methanol and heated at 50 ° C.
- the surface-treated core-shell type inorganic oxide fine particles had an average particle diameter of 21 nm by dynamic light scattering, the pH of this methanol dispersion was 4.4, and the viscosity was 1.4 mPa ⁇ s.
- the methanol dispersion had a solid content concentration of 30.5% by weight and a unit viscosity value of 0.05 mPa ⁇ s / (% by weight).
- a forming coating composition (Y2) was prepared.
- Preparation of primer layer film forming coating composition (Z1 ) 217.8 g of polyurethane emulsion “Superflex 150” (Daiichi Kogyo Seiyaku Co., Ltd., water-dispersed urethane elastomer solid content 30%), which is a commercially available thermoplastic resin.
- a container was prepared, and 150.0 g of the surface-treated core-shell inorganic oxide fine particle methanol dispersion (CL-1) prepared in this example and 97.1 g of ion-exchanged water were added thereto for 1 hour. Stir.
- primer layer film-forming coating composition (Z2 ) 161.0 g of polyurethane emulsion “Superflex 150” (Daiichi Kogyo Seiyaku Co., Ltd., water-dispersed urethane elastomer solid content 30%), which is a commercially available thermoplastic resin.
- a container was prepared, and 205.9 g of a methanol-dispersed core-shell type inorganic oxide fine particle (CL-1) prepared in this example and 97.1 g of ion-exchanged water were added for 1 hour. Stir.
- Step (2) In this step (2) of “Preparation of oligomer-modified inorganic oxide fine particles (1)” described in Example 1, instead of using 0.5 kg of the mixed solution (P-1) prepared in Example 1, this comparative example The oligomer-modified inorganic oxide was prepared in the same manner as in step (2) of “Preparation of oligomer-modified inorganic oxide fine particles (1)” in Example 1, except that 0.5 kg of the mixed solution (L-1) prepared in step 1 was used. A fine particle methanol dispersion (CL-2) was obtained. The core-shell type inorganic oxide fine particles prepared in Example 1 were used as the inorganic oxide fine particles of the oligomer-modified inorganic oxide fine particles.
- the average particle size of the oligomer-modified fine particles was 46 nm as measured by a dynamic light scattering method. Furthermore, this oligomer-modified fine particle dispersion had a pH of 4.6 and a viscosity of 40.8 mPa ⁇ s. Further, the solid content concentration of the oligomer-modified fine particles was 30.5%, and the unit viscosity value was 1.34 mPa ⁇ s / (wt%).
- CL-2 propylene glycol monomethyl ether
- tris (2,4-pentanedionato) aluminum III Tokyo Chemical Industry Co., Ltd.
- a silicone surfactant manufactured by Toray Dow Corning Co., Ltd., L-7604
- primer layer film-forming coating composition (Z3 ) 161.0 g of polyurethane emulsion “Superflex 150” (Daiichi Kogyo Seiyaku, water-dispersed urethane elastomer solid content 30%), which is a commercially available thermoplastic resin, A container was prepared, and 205.9 g of a methanol dispersion (CL-2) of oligomer-modified fine particles prepared in this comparative example and 97.1 g of ion-exchanged water were added and stirred for 1 hour.
- CL-2 methanol dispersion
- Table 1 shows the properties of the particles prepared in Examples 1 to 5 and Comparative Examples 1 and 2.
- Preparation of plastic lens substrate (test piece) for test (1) Pretreatment of plastic lens substrate Commercially available plastic lens substrate “monomer name: MR-8” (Mitsui Chemicals, Inc., refractive index of substrate 1.60) ) And “monomer name: MR-7” (manufactured by Mitsui Chemicals, Inc., base material refractive index 1.67) are immersed in a 10 wt% KOH aqueous solution kept at 40 ° C. for 2 minutes for etching treatment It was. Further, these were taken out, washed with water, and then sufficiently dried. (2) Formation of primer layer film A primer layer film-forming coating composition was applied to each pre-treated plastic lens substrate to form a coating film. In addition, application
- the coating film was heat-treated at 100 ° C. for 10 minutes, and the coating film (primer layer) was preliminarily dried.
- the film thickness of the primer layer thus formed after preliminary curing was approximately 0.5 to 0.7 ⁇ m.
- a coating composition for forming a hard coat layer film is applied to the surface of the plastic lens substrate that has been subjected to the pretreatment or the plastic lens substrate on which the primer layer film has been formed. A film was formed. In addition, application
- the coating film (hard coat layer) was cured by heat treatment at 110 ° C. for 2 hours. At this time, the main curing of the primer layer was also performed at the same time.
- the thickness of the hard coat layer film thus formed after curing was approximately 3.0 to 3.5 ⁇ m.
- An inorganic oxide component having the following constitution was deposited on the surface of the hard coat layer film by a vacuum deposition method.
- Each of the layers of the antireflection layer film laminated in (1) was formed.
- the design wavelength ⁇ was 520 nm.
- coated the coating composition P1 for primer layer film formation and the coating composition H1 for hard coat layer film formation and formed the antireflection layer film was created.
- the test piece 8 which applied the coating composition P2 for forming the primer layer film and the coating composition H5 for forming the hard coat layer film to form the antireflection layer film, and the coating composition Y2 for forming the primer layer film and the hard coat As a base material of the test piece 9 in which the coating composition Z2 for forming a layer film was applied to form an antireflection layer film, “monomer name: MR-7” (manufactured by Mitsui Chemicals, Inc., refractive index of base material 1.67) “Monomer name: MR-7” (manufactured by Mitsui Chemicals, Inc., refractive index of base material: 1.67) was used for the other test piece base materials.
- test pieces obtained by applying the coating compositions prepared in the examples had relatively high scratch resistance and film hardness, and were not cloudy and had high transparency. It was also found that the adhesion was excellent and the weather resistance and light resistance were high.
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Abstract
Description
[1]無機酸化物微粒子の表面に下記式(1)
RnM1(OR’)z-n (1)
M1:Si、Ti、Zr、Alから選ばれた1種以上の元素
R、R’:炭素数1~8のアルキル基、あるいはアリール基またはビニル基から選ばれた一種以上の基
n:0~(z-2)の整数
z:M1の価数
で表される金属アルコキシド(M1、R、R’およびnが異なる金属アルコキシドの混合物を含む)に由来するオリゴマーで修飾されたオリゴマー修飾微粒子であって、該オリゴマーの重合度が3以上であり、かつ該オリゴマーの重量平均分子量が1000~10000の範囲にあることを特徴とするオリゴマー修飾無機酸化物微粒子。
[2]前記オリゴマーは、前記金属アルコキシドの加水分解物および/または部分加水分解物の重縮合物、あるいは該重合物の混合物であることを特徴とする[1]に記載のオリゴマー修飾無機酸化物微粒子。
[3]M1がSiであることを特徴とする[1]または[2]に記載のオリゴマー修飾無機酸化物微粒子。
[4]前記無機酸化物微粒子がチタニウム、ジルコニウム、スズ、ニオブ、タングステン、アンチモン、インジウム、アルミニウムから選ばれた1種以上の金属元素を含む酸化物微粒子または複合酸化物微粒子であることを特徴とする[1]~[3]のいずれかに記載のオリゴマー修飾無機酸化物微粒子。
[5]前記オリゴマー修飾無機酸化物微粒子をメタノールに分散させたメタノール分散液の粘度を該水分散液の固形分濃度で除して求めた単位粘度値が、0.07~0.6565mPa・s/(重量%)の範囲にあることを特徴とする[1]~[4]のいずれかに記載のオリゴマー修飾無機酸化物微粒子。
[6]前記オリゴマーの修飾重量(A)が、前記無機酸化物微粒子の重量(B)に対して(A)/(B)=0.05~5.0の範囲にあることを特徴とする[1]~[5]のいずれかに記載のオリゴマー修飾無機酸化物微粒子。
[7]前記オリゴマー修飾無機酸化物微粒子の平均粒子径が9~65nmの範囲にある[1]~[6]のいずれかに記載のオリゴマー修飾無機酸化物微粒子。
[8]上記[1]~[7]のいずれかに記載のオリゴマー修飾無機酸化物微粒子を含む分散液。
[9]上記[1]~[7]のいずれかに記載のオリゴマー修飾無機酸化物微粒子または[8]に記載の分散液とマトリックス形成成分とを含む塗料。
[10]表面にオリゴマーが修飾されたオリゴマー修飾無機酸化物微粒子の製造方法であって、
下記工程(1)~(2);
工程(1)下記式(1);
RnM1(OR’)z-n (1)
M1:Si、Ti、Zr、Alから選ばれた1種以上の元素
R、R’:炭素数1~8のアルキル基、あるいはアリール基またはビニル基から選ばれた一種以上の基
n:0~(z-2)の整数
z:M1の価数
で表される金属アルコキシド(M1、R、R’およびnが異なる金属アルコキシドの混合物を含む)および/またはその加水分解物に、酸触媒と、水とを添加して、得られた混合溶液を60~120℃、かつ20分~24時間で加水分解および重縮合させることによって、直鎖状の金属アルコキシドのオリゴマーを含む混合溶液を製造する工程、
工程(2)
前記工程(1)で製造した直鎖状の金属アルコキシドのオリゴマーを含む混合溶液から前記酸触媒を除去した混合溶液にチタニウム、ジルコニウム、スズ、ニオブ、タングステン、アンチモン、インジウム、アルミニウムから選ばれた1種以上の金属元素を含む無機酸化物微粒子を添加したのち、5~30℃、0.5~24時間で処理することにより、前記無機酸化物微粒子の表面に、金属アルコキシドのオリゴマーを反応させる工程
を含むオリゴマー修飾無機酸化物微粒子の製造方法。
[11]前記工程(1)において金属アルコキシドを加水分解させるときの混合溶液のpHが2~4の範囲にあることを特徴とする[10]に記載のオリゴマー修飾無機酸化物微粒子の製造方法。
本発明に係わるオリゴマー修飾無機酸化物微粒子は、無機酸化物微粒子の表面に下記式(1)
RnM1(OR’)z-n (1)
M1:Si、Ti、Zr、Alから選ばれた1種以上の元素
R、R’:炭素数1~8のアルキル基、あるいはアリール基またはビニル基から選ばれた一種以上の基
n:0~(z-2)の整数
z:M1の価数
で表される金属アルコキシド(M1、R、R’およびnが異なる金属アルコキシドの混合物を含む)に由来するオリゴマーが修飾されたオリゴマー修飾微粒子であって、該オリゴマーの重合度が3以上であり、かつ該オリゴマーの重量平均分子量が1000~10000の範囲にあることを特徴としている。
分散液
本発明に係わる分散液は、本発明に係わるオリゴマー修飾無機酸化物微粒子を含むことを特徴としている。
塗料
本発明に係わる塗料は、本発明に係わるオリゴマー修飾無機酸化物微粒子または本発明に係わる分散液と、マトリックス成分とを含むことを特徴としている。
オリゴマー修飾無機酸化物微粒子の製造方法
本発明に係わるオリゴマー修飾無機酸化物微粒子の製造方法は下記工程(1)~(2);
工程(1)
下記式(1);
RnM1(OR’)z-n (1)
M1:Si、Ti、Zr、Alから選ばれた1種以上の元素
R、R’:炭素数1~8のアルキル基、あるいはアリール基またはビニル基から選ばれた一種以上の基
n:0~(z-2)の整数
z:M1の価数
で表される金属アルコキシド(M1、R、R’およびnが異なる金属アルコキシドの混合物を含む)および/またはその加水分解物に、酸触媒と、水とを添加して、得られた混合溶液を60~120℃、かつ20分~24時間で加水分解および重縮合させることによって、金属アルコキシドのオリゴマーを含む混合溶液を製造する工程、
工程(2)
前記工程(1)で製造した直鎖状の金属アルコキシドのオリゴマーを含む混合溶液から前記酸触媒を除去した混合溶液にチタニウム、ジルコニウム、スズ、ニオブ、タングステン、アンチモン、インジウム、アルミニウムから選ばれた1種以上の金属元素を含む無機酸化物微粒子を添加したのち5~30℃、0.5~24時間で処理することにより、前記無機酸化物微粒子の表面に、金属アルコキシドのオリゴマーを反応させる工程
を含むことを特徴としている。
工程(1)
この工程では、前記式(1)で表される金属アルコキシドのオリゴマーを含む混合溶液を製造する工程である。
工程(2)
この工程では、前記工程(1)で製造した混合溶液から前記酸触媒を除去し、ついでチタニウム、ジルコニウム、スズ、ニオブ、タングステン、アンチモン、インジウム、アルミニウムから選ばれた1種以上の金属元素を含む無機酸化物微粒子を添加したのち、5~30℃、0.5~24時間で処理することにより、前記無機酸化物微粒子の表面に、金属アルコキシドのオリゴマーを反応させ、オリゴマー修飾無機酸化物微粒子を含む分散液を得る工程である。
塗料の製造方法
本発明に係わる塗料は、上記工程で得られたオリゴマー修飾無機酸化物微粒子の分散液と、マトリックス成分とを混合して製造することができる。
[測定方法および評価試験方法]
次に、本発明の実施例その他で使用された測定方法および評価試験方法を具体的に述べれば、以下の通りである。
(1)平均粒子径の測定方法
無機酸化物微粒子の水分散液(固形分含有量0.15重量%)またはオリゴマー修飾無機酸化物微粒子のメタノール分散液(固形分含有量0.15重量%)20gを、長さ1cm、幅1cm、高さ5cmの石英セルに入れて、超微粒子粒度分析装置(大塚電子株式会社製、型式ELS-Z2)を用いて、動的光散乱法により粒子群の粒子径分布を測定した。なお、本発明でいう平均粒子径は、この測定結果をキュムラント解析して算出された値を示す。
(2)比表面積の測定方法
無機酸化物微粒子を含む分散液を乾燥させて得られた粉体を磁性ルツボ(B-2型)に約30ml採取し、300℃の温度で2時間乾燥後、デシケータに入れて室温まで冷却する。次に、サンプルを1g取り、全自動表面積測定装置(湯浅アイオニクス社製、マルチソーブ12型)を用いて、粒子の比表面積(m2/g)をBET法にて測定した。
(3)無機酸化物微粒子の組成分析方法
ICP装置(島津製作所株式会社製、ICPS-8100、解析ソフトウェアICPS-8000)を用いて、無機酸化物微粒子に含まれる金属元素の重量を酸化物換算基準で求めた。
(4)pHの測定方法
pHメータ(堀場製作所製、F22)にて測定した。
(5)粘度測定
オリゴマー修飾無機酸化物微粒子のメタノール分散液(固形分濃度30.5重量%)20mlを試料とし、粘度計(東機産業株式会社製、TV-10M)を用いて室温にて粘度測定を行った。粘度計のローターは回転数60rpmでは1.0~10.0mPa・sの粘度範囲、回転数30rpmでは10.0~20.0mPa・sの粘度範囲、回転数12rpmでは20.0~50.0mPa・sの粘度範囲、回転数6rpmでは50.0~100.0mPa・sの粘度範囲について測定した。
(6)[オリゴマーの平均分子量の測定方法]
オリゴマーを含む混合溶液(固形分濃度10.0重量%)15.0gとテトラヒドロフラン(関東化学(株)製)35.0gを混合して、固形分濃度3.0%の試料を調製した。このうち0.1mlをマイクロシリンジを用いて採取して試料とした。この試料を、ゲル浸透クロマトグラフィー(東ソー(株)製、HLC-8120GPC)を用いて、カラム(東ソー製TSK-GEL G3000HLLおよびTSK-GEL G2500HXL)に供してオリゴマーのポリスチレン換算での重量平均分子量を測定した。
(7)[オリゴマーの重合度の測定方法]
上記の方法で測定したオリゴマーの平均分子量を、金属アルコキシドが加水分解基を介して直鎖状に重合したとしたときのモノマー単位での繰返し単位の分子量で除した値を重合度とした。
硬化性塗膜について
(8)膜硬度(Bayer値)の測定方法
磨耗試験機BTM(米コルツ社製)およびヘーズ値測定装置(NIPPON DENSHOKU製NDH2000)を使用し、実施例の調製例にて作成した被試験レンズと、基準レンズとのヘーズ値の変化によりBayer値を測定する。基準レンズは市販のプラスチックレンズ基材CR-39基材(ジエチレングリコールビスアリルカーボネート、PPG社製モノマー使用、基材の屈折率1.60)を使用し、まずそれぞれのヘーズ値を測定する。基準レンズの初期ヘーズ値をD(std0)、被試験レンズの初期ヘーズ値をD(test0)とする。それぞれのレンズを耐摩耗性試験機パンに設置し、その上に研磨材(専用砂)500gを充填し、600回左右に振動させ試験を行う。試験後の基準レンズのヘーズ値をD(stdf)、被試験レンズのヘーズ値をD(testf)とする。Bayer試験値(R)は以下の数式から算出する。
(9)塗膜の外観(干渉縞)の評価方法
内壁が黒色である箱の中に蛍光灯「商品名:メロウ5N」(東芝ライテック株式会社製、三波長型昼白色蛍光灯)を取り付け、蛍光灯の光を試料基板のハードコート層膜(前記オリゴマー修飾無機酸化物微粒子を含む)上に形成された反射防止膜表面で反射させ、光の干渉による虹模様(干渉縞)の発生を目視にて確認し、以下の基準で評価する。
A:干渉縞が目立たない
B:干渉縞が認められるが、許容範囲にある
C:干渉縞が目立つ
D:ぎらつきのある干渉縞がある。
(10)塗膜の外観(曇り)の評価方法
内壁が黒色である箱の中に蛍光灯「商品名:メロウ5N」(東芝ライテック株式会社製、三波長型昼白色蛍光灯)を取り付け、前記オリゴマー修飾無機酸化物微粒子を含むハードコート層膜を有する試料基板を蛍光灯の直下に垂直に置き、これらの透明度(曇りの程度)を目視にて確認し、以下の基準で評価する。
B:僅かに曇りがある
C:明らかな曇りがある
D:著しい曇りがある。
(11)塗膜の耐擦傷性の評価方法
実施例の調製例にて作成した試験片の表面を、ボンスタースチールウール♯0000(日本スチールウール株式会社製)に1kgの荷重をかけ、3cmの距離を50往復/100秒の条件で擦った後、傷の入り具合を目視にて判定し、以下の基準で評価した。
B:若干の傷が入る
C:かなりの傷が入る
D:擦った面積のほぼ全面に傷が入る。
(12)塗膜の密着性の評価方法
ハードコート層膜を形成した試料基板のレンズ表面に、ナイフにより1mm間隔で切れ目を入れ、1平方mmのマス目を100個形成し、セロハン製粘着テープを強く押し付けた後、プラスチックレンズ基板の面内方向に対して90度方向へ急激に引っ張り、この操作を合計5回行い、剥離しないマス目の数を数え、以下の基準で評価する。
不良:剥離していないマス目の数が95個未満。
(13)塗膜の耐候的な密着性の評価方法
ハードコート層膜を形成した試料基板をキセノンウエザーメーター(スガ試験機株式会社製X-75型)で曝露試験をした後、外観の確認および前記の密着性の評価と同様の評価を行い、以下の基準で評価する。なお、曝露時間は、反射防止膜を有している基板は250時間、反射防止膜を有していない基板は50時間とする。
不良:剥離していないマス目の数が95個未満。
(14)塗膜の耐光性の評価方法
退色試験用水銀ランプ(東芝株式会社製H400-E)により紫外線を50時間照射し、試験前後のレンズ色の目視確認を行い、以下の基準で評価する。なお、ランプと試験片との照射距離は、70mmとし、ランプの出力は、試験片の表面温度が45±5℃となるように調整する。また、この試験は、反射防止膜をハードコート層の表面に施したプラスチックレンズを対象として行ったものである。
△:若干の変色が認められる
×:明らかな変色が認められる。
[実施例1]基準例
無機酸化物微粒子の調製(1)
(コア粒子の調製)
四塩化チタン(大阪チタニウムテクノロジ-ズ(株)製)をTiO2換算基準で7.75重量%含む四塩化チタン水溶液93.7kgと、アンモニアを15重量%含むアンモニア水(宇部興産(株)製)36.3kgとを混合し、pH9.5の白色スラリー液を調製した。次いで、このスラリーを濾過した後、純水で洗浄して、固形分含有量が10重量%の含水チタン酸ケーキ72.6kgを得た。
(コアシェル型無機酸化物微粒子の調製)
オキシ塩化ジルコニウム(太陽鉱工(株)製)をZrO2換算基準で2重量%含むオキシ塩化ジルコニウム水溶液26.3kgに、アンモニアを15重量%含むアンモニア水を撹拌下で徐々に添加して、pH8.5のスラリー液を得た。次いで、このスラリーを濾過した後、純水で洗浄して、ジルコニウム成分をZrO2に換算基準で10重量%含むケーキ5.26kgを得た。
上記の工程で得られたコアシェル型無機酸化物微粒子の水分散液(CW-1)2000gを撹拌しながら陽イオン交換樹脂204gを添加し、室温にて1時間撹拌した後、樹脂を分離した。次いで、得られた水分散液の分散溶媒を限外濾過膜装置(旭化成株式会社製濾過膜、SIP-1013)を用いて水からメタノール(林純薬株式会社製、メチルアルコール濃度:99.9重量%)に置換した。
オリゴマー修飾無機酸化物微粒子の調製(1)
工程(1)
オリゴマーを含む混合溶液の調製(1)
メチルポリシリケート(多摩化学工業株式会社製、Mシリケート51;重合度3~5、平均分子量470)17.6kgおよび変性アルコール(日本アルコール販売(株)製、エキネンF-1)61.5kgの混合液中に攪拌しながら0.15%の塩酸水溶液10.9kgを添加した。更に、この混合液を室温で15分間攪拌した後、オートクレーブ(耐圧硝子工業(株)製、120L)中で100℃の温度で60分間加熱することにより、ケイ素を含む金属アルコキシドのオリゴマーを含む混合溶液(P-1)88.9kgを得た。
工程(2)
前記で得られた混合溶液(P-1)0.5kgに両性イオン交換樹脂150gを混合し、室温で3時間撹拌した後に樹脂を分離し、酸触媒である塩酸が除去された混合溶液を得た。
ついで、前記工程で調製されたコアシェル型無機酸化物微粒子のメタノール分散液(CM-1)1.5kgを撹拌しながら、前記工程で調製した、酸触媒が除去されたオリゴマーの混合溶液0.5kgを滴下した。
更に、この混合溶液を10℃で18時間撹拌した後、限外濾過膜装置(旭化成(株)製、SIP-1013)を用いて固形分含有量30.5重量%に濃縮することにより、オリゴマーで修飾されたコアシェル型無機酸化物微粒子のメタノール分散液(CP-1)650.0gが得られた。
ハードコート層膜形成用塗料組成物(H1)の調製
γ―グリシドキシプロピルトリメトキシシラン(東レ・ダウコーニング株式会社製Z-6040)177.3gおよびメタノール(林純薬株式会社製、メチルアルコール濃度:99.9重量%)31.4gの混合液混合液中に攪拌しながら0.01Nの塩酸水溶液60.43gを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行った。
プライマー層膜形成用塗料組成物(P1)の調製
市販の熱可塑性樹脂であるポリウレタンエマルジョン「スーパーフレックス150」(第一工業製薬製、水分散型ウレタンエラストマー固形分含有量30%)161.0gを入れた容器を用意し、これに、本実施例で調製したオリゴマー修飾微粒子のメタノール分散液(CP-1)205.9gおよびイオン交換水97.1gを加えて、1時間攪拌した。
[実施例2]
オリゴマー修飾無機酸化物微粒子の調製(2)
工程(1)
オリゴマーを含む混合溶液の調製(2)
メチルポリシリケート(多摩化学工業(株)製、Mシリケート51;SinO(n-1)(OCH3)2(n+1)を主成分とする。重合度3~5、平均分子量470、繰返し単位{-SiO(OCH3)2-}(分子量106))15.8kg、ジルコニウムトリブトキシモノアセチルアセトネート(マツモトファインケミカル(株)製、オルガチックス ZC-540、Zr(O-n-C4H9)3(C5H7O2)を成分とする。分子量409、繰返し単位は[―ZrO(OC4H9)(C5H7O2)―]で分子量279とした)の2-プロパノール溶液(成分濃度10%)18.0kgおよび変性アルコール(日本アルコール販売(株)製、エキネンF-1)45.3kgの混合液中に攪拌しながら0.15%の塩酸水溶液10.9kgを添加した。更に、この混合液を室温で15分間攪拌した後、オートクレーブ(耐圧硝子工業(株)製、120L)中で100℃の温度で30分間加熱することにより、ケイ素およびジルコニウムを含む金属アルコキシドのオリゴマーを含む混合溶液(P-2)89.0kgを得た。
工程(2)
実施例1に記載された「オリゴマー修飾無機酸化物微粒子のメタノール分散液調製」の工程において、実施例1で調製したケイ素系ポリマー分散液(P-1)0.5kgを用いる代わりに本実施例で調製したケイ素及びチタニウム系ポリマー分散液(P-2)0.5kgを用いた以外は実施例1の「オリゴマー修飾微粒子のメタノール分散液調製」と同様な方法によりチタニウムを主成分とする無機酸化物微粒子をケイ素系オリゴマー修飾した微粒子のメタノール分散液(CP-2)を得た。
ハードコート層膜形成用塗料組成物(H2)の調製
γ―グリシドキシプロピルトリメトキシシラン(東レ・ダウコーニング株式会社製Z-6040)177.3gおよびメタノール(林純薬株式会社製、メチルアルコール濃度:99.9重量%)31.4gの混合液混合液中に攪拌しながら0.01Nの塩酸水溶液60.43gを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行った。
[実施例3]
オリゴマー修飾無機酸化物微粒子の調製(3)
工程(1)
オリゴマーを含む混合溶液の調製(3)
実施例1の「オリゴマーを含む混合溶液の調製(1)」の工程において、メチルポリシリケートと、変性アルコールと、塩酸水溶液との混合液を室温で15分間攪拌した後、オートクレーブ中で100℃で60分間加熱する代わりに、100℃の温度で240分間加熱した以外は、実施例1の「オリゴマーを含む混合溶液の調製(1)」と同様の方法でケイ素を含む金属アルコキシドのオリゴマーを含む混合溶液(P-3)を得た。
得られた混合溶液は、固形分10.0重量%、pH3.3であって、含まれるオリゴマーの分子量は9000で、繰返し単位の質量は106とした場合の重合度は84.9であった。
工程(2)
このオリゴマーの混合溶液(P-3)0.5kgを、実施例1の混合溶液(P-1)のかわりに使用した以外は、実施例1に記載の「オリゴマー修飾無機酸化物微粒子の調製(1)」の工程(2)と同様の方法により、オリゴマー修飾無機酸化物微粒子のメタノール分散液(CP-3)を得た。
ハードコート層膜形成用塗料組成物(H3)の調製
γ―グリシドキシプロピルトリメトキシシラン(東レ・ダウコーニング株式会社製Z-6040)177.3gおよびメタノール(林純薬株式会社製、メチルアルコール濃度:99.9重量%)31.4gの混合液混合液中に攪拌しながら0.01Nの塩酸水溶液60.43gを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行った。
[実施例4]
無機酸化物微粒子の調製(2)
(コア粒子の調製)
純水18.57kgにオキシ塩化ジルコニウム8水和物(太陽鉱工株式会社製、ZrOCl2・8H2O)0.50kgを溶解し、これに濃度10重量%のKOH水溶液17.56kgを添加してジルコニウム水酸化物ヒドロゲル(ZrO2濃度1重量%)を調製した。ついで、得られたジルコニウム水酸化物ヒドロゲルを、限外濾過膜法により電導度が0.5mS/cm以下になるまで洗浄した。
この前駆体スラリーを3等分してオートクレーブ(耐圧硝子工業株式会社製、100L)に充填し、150℃で11時間水熱処理を行った後、遠心沈降法によりジルコニア系複合酸化物微粒子を分離し、これを充分に洗浄したのちイオン交換水に分散させて、ジルコニウムを主成分とする複合酸化物微粒子(コア粒子)の水分散液10.10kgを得た。この水分散液の固形分含有量はZrO2換算基準で10重量%であった。
次いで、前記コア粒子の水分散液10.10kgをスプレードライヤー(NIRO社製NIRO ATOMIZER)に供して噴霧乾燥した。これにより、ジルコニウムを主成分とする複合酸化物微粒子(コア粒子)の乾燥粉体0.90kgを得た。得られた乾燥粉体に含まれるコア粒子の平均粒子径は約2μmであった。
次に、上記で得られた乾燥粉体0.90kgを、空気雰囲気下、500℃の温度にて2時間焼成して、ジルコニウムを主成分とする複合酸化物微粒子(コア粒子)の焼成粉体0.84kgを得た。
上記で得られた焼成粉体0.84kgを純水0.74kgに分散させ、これに、濃度28.6%の酒石酸水溶液0.55kg、濃度50重量%のKOH水溶液0.23kgを加えて充分攪拌した。ついで、粒子径0.1mmのアルミナビーズ(大明化学工業株式会社製 高純度アルミナビーズ)を加え、これを湿式粉砕機(カンペハピオ株式会社製バッチ式卓上サンドミル)に供して180分間、前記焼成粉体の粉砕及び分散処理を行った。その後、アルミナビーズを目開き44μmのステンレス製フィルターを用いて分離・除去したのち、さらに純水6.65kgを添加して撹拌し、ジルコニウムを主成分とする複合酸化物微粒子(コア粒子)の水分散液8.84kgを得た。この水分散液の固形分含有量は11重量%であった。
ついで、限外濾過膜を用いてイオン交換水で洗浄した後、陰イオン交換樹脂(三菱化学株式会社製:SANUPC)0.43kgを加えて脱イオン処理をした後、遠心分離機(日立工機株式会社製CR-21G)に供して12,000rpmの速度で1時間処理して、ZrO2換算基準の固形分濃度が10重量%のジルコニウムを主成分とする複合酸化物微粒子(コア粒子)の水分散液9.50(C-2)kgを得た。前記水分散液に含まれるコア粒子の平均粒子径は28nmであった。
さらに、このコア粒子に含まれる金属成分の含有量は、各金属成分の酸化物換算基準で、ZrO298.5重量%およびK2O1.5重量%であった。
(コアシェル型無機酸化物微粒子の調製)
市販の水ガラス(AGCエスアイテック(株)製、JIS3号水硝子、SiO2濃度24質量%)を純水にて希釈した後、陽イオン交換樹脂(三菱化学(株)製)を用いて脱アルカリして、珪酸液をSiO2換算基準で4.5重量%含むpHは、2.3の珪酸水溶液を得た。
上記の工程で得られたコアシェル型の無機酸化物微粒子の水分散液(CW-2)2000gを撹拌しながら陽イオン交換樹脂204gを添加し、室温にて1時間撹拌した後、樹脂を分離した。次いで、得られた水分散液の分散溶媒を限外濾過膜装置(旭化成株式会社製濾過膜、SIP-1013)を用いて水からメタノール(林純薬株式会社製、メチルアルコール濃度:99.9重量%)に置換した。
オリゴマー修飾無機酸化物微粒子の調製(4)
実施例1に記載された「オリゴマー修飾無機酸化物微粒子の調製(1)」の工程(2)において、実施例1で調製したコアシェル型の無機酸化物微粒子のメタノール分散液(CM-1)1.5kgを用いる代わりに本実施例で調製したコアシェル型の無機酸化物微粒子のメタノール分散液(CM-2)1.5kgを用いた以外は実施例1の「オリゴマー修飾無機酸化物微粒子の調製(1)」の工程(1)、および工程(2)と同様な方法によりオリゴマー修飾無機酸化物微粒子のメタノール分散液(CP-4)を得た。
ハードコート層膜形成用塗料組成物(H4)の調製
γ―グリシドキシプロピルトリメトキシシラン(東レ・ダウコーニング株式会社製Z-6040)162.7gおよびメタノール(林純薬株式会社製、メチルアルコール濃度:99.9重量%)28.8gの混合液混合液中に攪拌しながら0.01Nの塩酸水溶液55.5gを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行った。
[実施例5]
無機酸化物微粒子の調製(3)
(コア粒子の調製)
四塩化チタン(大阪チタニウムテクノロジ-ズ株式会社製)をTiO2換算基準で7.75重量%含む四塩化チタン水溶液12.1kgと、アンモニアを15重量%含むアンモニア水(宇部興産株式会社製)4.7kgとを混合し、pH9.5の白色スラリー液を調製した。次いで、このスラリーを濾過した後、純水で洗浄して、固形分含有量が10重量%の含水チタン酸ケーキ9.9kgを得た。
次いで、前記チタン系微粒子を含む混合水溶液9.00kgをスプレードライヤー(NIRO社製NIRO ATOMIZER)に供して噴霧乾燥(入口温度:260℃、出口温度:55℃)した。これにより、平均粒子径が約2μmの複合酸化物粒子からなる乾燥粉体0.63kgを得た。
次に、上記で得られたチタン系微粒子の乾燥粉体0.63kgを、空気雰囲気下、700℃の温度にて1時間焼成して、チタン系微粒子の焼成粉体0.59kgを得た。
次に、得られたチタン系微粒子の焼成粉体0.17kgを純水250.4gに分散させ、これに10重量%濃度の水酸化カリウム水溶液24.8gを添加してpH11.0に調整した。
次いで、この混合水溶液に粒子径0.1mmのアルミナビーズ(大明化学工業株式会社製 高純度アルミナビーズ)1.27kgを加えて、これを湿式粉砕機(カンペ株式会社製バッチ式卓上サンドミル)に供して180分間、前記チタン系微粒子の粉砕処理を行った。その後、石英ビーズを目開き44μmのステンレス製フィルターを用いて分離・除去したのち、さらに純水840.0gを添加して撹拌し、固形分含有量が11重量%の水分散ゾル1.17kgを得た。
このように粉砕して得られたチタン系微粒子を含む水分散ゾルは乳白色であった。また、この水分散ゾル中に含まれる前記チタン系微粒子の平均粒子径は106nmであり、さらに100nm以上の粒子径を有する粗大粒子の分布頻度は59.1%であった。
次いで、前記水分散ゾル1.17kgに純水0.12kgを添加して、固形分濃度が10重量%の水分散ゾルとし、さらに陰イオン交換樹脂(三菱化学株式会社製)0.29kgを混合して15分間攪拌した。次に、前記陰イオン交換樹脂を目開き44μmのステンレス製フィルターを用いて分離・除去したのち、陽イオン交換樹脂(三菱化学株式会社製)39.4gを混合して15分間攪拌した。次いで、前記陽イオン交換樹脂を目開き44μmのステンレス製フィルターを用いて分離・除去したのち、この水分散ゾルを遠心分離機(日立工機株式会社製CR-21G)に供して12,000rpmの速度で1時間処理して、100nm以上の粒子径を有する粗大粒子を分級して取り除いた。これにより、固形分含有量が6.4重量%の水分散ゾル1.13kgを得た。
(コアシェル型無機酸化物微粒子の調製)
実施例1に記載された(コアシェル型微粒子の調製)の工程において、実施例1で調製したチタニウムを主成分とする複合酸化物微粒子(コア粒子)の水分散液(C-1)3.0kgを用いる代わりに本実施例で調製したチタン系微粒子(コア粒子)を含む水分散液(C-3)15.0kgを用いた以外は実施例1の(コアシェル型粒子の調製)と同様な方法によりコアシェル型の無機酸化物微粒子の水分散液(CW-3)およびコアシェル型微粒子のメタノール分散液(CM-3)を得た。
このコアシェル型無機酸化物微粒子の、動的光散乱法により測定した平均粒子径は25nmで、BET比表面積は82m2/gであった。
オリゴマー修飾無機酸化物微粒子の調製(5)
実施例1に記載された「オリゴマー修飾無機酸化物微粒子の調製(1)」の工程(2)において、実施例1で調製したコアシェル型の無機酸化物微粒子のメタノール分散液(CM-1)1.5kgを用いる代わりに本実施例で調製したコアシェル型の無機酸化物微粒子のメタノール分散液(CM-3)1.5kgを用いた以外は実施例1の「オリゴマー修飾無機酸化物微粒子の調製(1)」の工程(1)、工程(2)と同様な方法によりオリゴマー修飾無機酸化物微粒子のメタノール分散液(CP-5)を得た。
ハードコート層膜形成用塗料組成物(H5)の調製
γ―グリシドキシプロピルトリメトキシシラン(東レ・ダウコーニング株式会社製Z-6040)165.3gおよびメタノール(林純薬株式会社製、メチルアルコール濃度:99.9重量%)29.3gの混合液混合液中に攪拌しながら0.01Nの塩酸水溶液56.3gを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行った。
プライマー層膜形成用塗料組成物(P2)の調製
市販の熱可塑性樹脂であるポリウレタンエマルジョン「スーパーフレックス150」(第一工業製薬製、水分散型ウレタンエラストマー固形分含有量30%)161.0gを入れた容器を用意し、これに、本実施例で調製したオリゴマー修飾無機酸化物微粒子のメタノール分散液(CP-5)205.9gおよびイオン交換水97.1gを加えて、1時間攪拌した。
[比較例1]
シランカップリング剤で表面処理した微粒子の調製
実施例1で調製したコアシェル型の無機酸化物微粒子の水分散液(CW-1)2000gを撹拌しながら陽イオン交換樹脂53gを混合し、室温で1時間撹拌した。次いで、イオン交換樹脂を分離して、得られた水分散液とメタノール(林純薬株式会社製、メチルアルコール濃度:99.9重量%)2.0kgとを混合した。さらに、この混合液中に、ケイ素成分をSiO2換算基準で28重量%含む正珪酸エチル(多摩化学工業株式会社製)38.5gを滴下した後、この混合溶液を50℃の温度に加熱して18時間、攪拌した。
なお、正珪酸エチル38.5gを水1800gとメタノール2kgに混合して50℃、18時間加熱したときの混合溶液に含まれるシランカップリング剤由来成分の分子量は192、繰り返し単位の分子量134(構造式{-SiO(OC2H5)2-})としたときの重合度は1.4であったことから、粒子表面に修飾されたシランカップリング剤の重合度と分子量についても同様であると推測された。
次に、得られた混合溶液を室温まで冷却してから、限外濾過膜(旭化成株式会社製、SIP-1013)を用いてメタノールを除去して分散媒を水に置換した。さらに、濃縮して固形分含有量が30.5重量%のメタノール分散ゾルを調製した。これにより、前記コアシェル型微粒子の表面を正珪酸エチルの加水分解縮合物で表面処理したコアシェル型無機酸化物微粒子のメタノール分散液(CL-1)650.0gを得た。
ハードコート層膜形成用塗料組成物(Y1)の調製
γ―グリシドキシプロピルトリメトキシシラン(東レ・ダウコーニング株式会社製Z-6040)222.5gおよびメタノール(林純薬株式会社製、メチルアルコール濃度:99.9重量%)39.4gの混合液混合液中に攪拌しながら0.01Nの塩酸水溶液75.8gを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行った。
ハードコート層膜形成用塗料組成物(Y2)の調製
γ―グリシドキシプロピルトリメトキシシラン(東レ・ダウコーニング株式会社製Z-6040)167.4gおよびメタノール(林純薬株式会社製、メチルアルコール濃度:99.9重量%)29.6gの混合液混合液中に攪拌しながら0.01Nの塩酸水溶液57.1gを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行った。
プライマー層膜形成用塗料組成物(Z1)の調製
市販の熱可塑性樹脂であるポリウレタンエマルジョン「スーパーフレックス150」(第一工業製薬製、水分散型ウレタンエラストマー固形分含有量30%)217.8gを入れた容器を用意し、これに、本実施例で調製した表面処理したコアシェル型無機酸化物微粒子のメタノール分散液(CL-1)150.0gおよびイオン交換水97.1gを加えて、1時間攪拌した。
プライマー層膜形成用塗料組成物(Z2)の調製
市販の熱可塑性樹脂であるポリウレタンエマルジョン「スーパーフレックス150」(第一工業製薬製、水分散型ウレタンエラストマー固形分含有量30%)161.0gを入れた容器を用意し、これに、本実施例で調製した表面処理したコアシェル型無機酸化物微粒子のメタノール分散液(CL-1)205.9gおよびイオン交換水97.1gを加えて、1時間攪拌した。
[比較例2]
オリゴマー修飾無機酸化物微粒子の調製
工程(1)
オリゴマーを含む混合溶液の調製(4)
実施例1に記載された「オリゴマーを含む混合溶液の調製(1)」の工程において、メチルポリシリケートと変性アルコールと塩酸水溶液との混合液をオートクレーブ中で100℃で60分間加熱する条件を用いる代わりに、100℃の温度で48時間加熱した以外は実施例1の「オリゴマーを含む混合溶液の調製(1)」の工程(1)と同様の方法によりオリゴマーを含む混合溶液(L-1)を得た。
工程(2)
実施例1に記載された「オリゴマー修飾無機酸化物微粒子の調製(1)」の工程(2)において、実施例1で調製した混合溶液(P-1)0.5kgを用いる代わりに本比較例で調製した混合溶液(L-1)0.5kgを用いた以外は実施例1の「オリゴマー修飾無機酸化物微粒子の調製(1)」の工程(2)と同様な方法でオリゴマー修飾無機酸化物微粒子のメタノール分散液(CL-2)を得た。
なお、このオリゴマー修飾無機酸化物微粒子の無機酸化物微粒子には、実施例1で調製したコアシェル型無機酸化物微粒子を用いた。
ハードコート層膜形成用塗料組成物(Y3)の調製
γ―グリシドキシプロピルトリメトキシシラン(東レ・ダウコーニング株式会社製Z-6040)177.3gおよびメタノール(林純薬株式会社製、メチルアルコール濃度:99.9重量%)31.4gの混合液混合液中に攪拌しながら0.01Nの塩酸水溶液60.43gを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行った。
プライマー層膜形成用塗料組成物(Z3)の調製
市販の熱可塑性樹脂であるポリウレタンエマルジョン「スーパーフレックス150」(第一工業製薬製、水分散型ウレタンエラストマー固形分含有量30%)161.0gを入れた容器を用意し、これに、本比較例で調製したオリゴマー修飾微粒子のメタノール分散液(CL-2)205.9gおよびイオン交換水97.1gを加えて、1時間攪拌した。
試験用プラスチックレンズ基板(試験片)の作成
(1)プラスチックレンズ基材の前処理
市販のプラスチックレンズ基材「モノマー名:MR-8」(三井化学株式会社製、基材の屈折率1.60)および「モノマー名:MR-7」(三井化学株式会社製、基材の屈折率1.67)を、40℃に保った10重量%濃度のKOH水溶液に2分間浸漬してエッチング処理を行った。更に、これらを取り出して水洗したのち、十分に乾燥させた。
(2)プライマー層膜の形成
前処理を行ったプラスチックレンズ基材にプライマー層膜形成用塗料組成物をそれぞれ塗布して塗膜を形成した。なお、この塗料組成物の塗布は、ディッピング法(引き上げ速度120mm/分)を用いて行った。
(3)ハードコート層膜の形成
前記前処理を行ったプラスチックレンズ基材、またはプライマー層膜を形成したプラスチックレンズ基材の表面に、ハードコート層膜形成用の塗料組成物を塗布して塗膜を形成した。なお、この塗料組成物の塗布は、ディッピング法(引き上げ速度250mm/分)を用いて行った。
(4)反射防止膜層の形成
前記ハードコート層膜の表面に、以下に示す構成の無機酸化物成分を真空蒸着法によって蒸着させた。ここでは、ハードコート層側から大気側に向かって、SiO2:0.06λ、ZrO2:0.15λ、SiO2:0.04λ、ZrO2:0.25λ、SiO2:0.25λの順序で積層された反射防止層膜の層をそれぞれ形成した。また、設計波長λは、520nmとした。
外観、耐擦傷性、密着性、耐候性の評価
実施例1~5、比較例1~2で得られたハードコート層膜形成用の塗料組成物H1、H2、H3、H4、H5、Y1、Y2、Y3と、プライマー層膜形成用塗料組成物P1、P2およびZ1、Z2を用いて、表2に示す組み合わせで前処理を行ったプラスチックレンズ基材上にプライマー層膜およびハードコート層膜を形成して試験片1~9を作製した。
さらに、プライマー層膜形成用塗料組成物P2とハードコート層膜形成用塗料組成物H5を塗布し反射防止層膜を形成した試験片8、および、プライマー層膜形成用塗料組成物Y2とハードコート層膜形成用塗料組成物Z2を塗布し反射防止層膜を形成した試験片9の基材としては「モノマー名:MR-7」(三井化学株式会社製、基材の屈折率1.67)を用い、それ以外の試験片の基材には「モノマー名:MR-7」(三井化学株式会社製、基材の屈折率1.67)を用いた。
Claims (11)
- 無機酸化物微粒子の表面に下記式(1)
RnM1(OR’)z-n (1)
M1:Si、Ti、Zr、Alから選ばれた1種以上の元素
R、R’:炭素数1~8のアルキル基、あるいはアリール基またはビニル基から選ばれた一種以上の基
n:0~(z-2)の整数
z:M1の価数
で表される金属アルコキシド(M1、R、R’およびnが異なる金属アルコキシドの混合物を含む)に由来するオリゴマーで修飾されたオリゴマー修飾微粒子であって、該オリゴマーの重合度が3以上であり、かつ該オリゴマーの重量平均分子量が1000~10000の範囲にあることを特徴とするオリゴマー修飾無機酸化物微粒子。 - 前記オリゴマーは、前記金属アルコキシドの加水分解物および/または部分加水分解物の重縮合物、あるいは該重合物の混合物であることを特徴とする請求項1に記載のオリゴマー修飾無機酸化物微粒子。
- M1がSiであることを特徴とする請求項1または2に記載のオリゴマー修飾無機酸化物微粒子。
- 前記無機酸化物微粒子がチタニウム、ジルコニウム、スズ、ニオブ、タングステン、アンチモン、インジウム、アルミニウムから選ばれた1種以上の金属元素を含む酸化物微粒子または複合酸化物微粒子であることを特徴とする請求項1~3のいずれか1項に記載のオリゴマー修飾無機酸化物微粒子。
- 前記オリゴマー修飾無機酸化物微粒子をメタノールに分散させたメタノール分散液の粘度を該水分散液の固形分濃度で除して求めた単位粘度値が、0.07~0.6565mPa・s/(重量%)の範囲にあることを特徴とする請求項1~4のいずれか1項に記載のオリゴマー修飾無機酸化物微粒子。
- 前記オリゴマーの修飾重量(A)が、前記無機酸化物微粒子の重量(B)に対して(A)/(B)=0.05~5.0の範囲にあることを特徴とする請求項1~5のいずれか1項に記載のオリゴマー修飾無機酸化物微粒子。
- 前記オリゴマー修飾無機酸化物微粒子の平均粒子径が9~65nmの範囲にある請求項1~6のいずれか1項に記載のオリゴマー修飾無機酸化物微粒子。
- 請求項1~7のいずれか1項に記載のオリゴマー修飾無機酸化物微粒子を含む分散液。
- 請求項1~7のいずれか1項に記載のオリゴマー修飾無機酸化物微粒子または請求項8に記載の分散液とマトリックス形成成分とを含む塗料。
- 表面にオリゴマーが修飾されたオリゴマー修飾無機酸化物微粒子の製造方法であって、
下記工程(1)~(2);
工程(1)下記式(1);
RnM1(OR’)z-n (1)
M1:Si、Ti、Zr、Alから選ばれた1種以上の元素
R、R’:炭素数1~8のアルキル基、あるいはアリール基またはビニル基から選ばれた一種以上の基
n:0~(z-2)の整数
z:M1の価数
で表される金属アルコキシド(M1、R、R’およびnが異なる金属アルコキシドの混合物を含む)および/またはその加水分解物に、酸触媒と、水とを添加して、得られた混合溶液を60~120℃、かつ20分~24時間で加水分解および重縮合させることによって、直鎖状の金属アルコキシドのオリゴマーを含む混合溶液を製造する工程、
工程(2)前記工程(1)で製造した直鎖状の金属アルコキシドのオリゴマーを含む混合溶液から前記酸触媒を除去した混合溶液にチタニウム、ジルコニウム、スズ、ニオブ、タングステン、アンチモン、インジウム、アルミニウムから選ばれた1種以上の金属元素を含む無機酸化物微粒子を添加したのち、5~30℃、0.5~24時間で処理することにより、前記無機酸化物微粒子の表面に、金属アルコキシドのオリゴマーを反応させる工程
を含むオリゴマー修飾無機酸化物微粒子の製造方法。 - 前記工程(1)において金属アルコキシドを加水分解させるときの混合溶液のpHが2~4の範囲にあることを特徴とする請求項10に記載のオリゴマー修飾無機酸化物微粒子の製造方法。
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