JP6361205B2 - Light reflecting resin composition - Google Patents
Light reflecting resin composition Download PDFInfo
- Publication number
- JP6361205B2 JP6361205B2 JP2014059752A JP2014059752A JP6361205B2 JP 6361205 B2 JP6361205 B2 JP 6361205B2 JP 2014059752 A JP2014059752 A JP 2014059752A JP 2014059752 A JP2014059752 A JP 2014059752A JP 6361205 B2 JP6361205 B2 JP 6361205B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium dioxide
- coating layer
- weight
- parts
- fluoroalkyl group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011342 resin composition Substances 0.000 title claims description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 205
- 239000004408 titanium dioxide Substances 0.000 claims description 96
- 239000011247 coating layer Substances 0.000 claims description 70
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 50
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 36
- 229920005992 thermoplastic resin Polymers 0.000 claims description 35
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 23
- -1 silane compound Chemical class 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 20
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 15
- 150000004706 metal oxides Chemical class 0.000 claims description 15
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 13
- 238000004898 kneading Methods 0.000 claims description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 229920001225 polyester resin Polymers 0.000 claims description 6
- 239000004645 polyester resin Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 27
- 239000011347 resin Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 10
- 230000006866 deterioration Effects 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000011164 primary particle Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004383 yellowing Methods 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000002345 surface coating layer Substances 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- XOVNCWWRDSAYNE-UHFFFAOYSA-N 2,4,6,8-tetramethyl-2,4,6,8-tetrakis(3,3,3-trifluoropropyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound FC(F)(F)CC[Si]1(C)O[Si](C)(CCC(F)(F)F)O[Si](C)(CCC(F)(F)F)O[Si](C)(CCC(F)(F)F)O1 XOVNCWWRDSAYNE-UHFFFAOYSA-N 0.000 description 2
- URZHQOCYXDNFGN-UHFFFAOYSA-N 2,4,6-trimethyl-2,4,6-tris(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[Si]1(C)O[Si](C)(CCC(F)(F)F)O[Si](C)(CCC(F)(F)F)O1 URZHQOCYXDNFGN-UHFFFAOYSA-N 0.000 description 2
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QOGFQIGEQMWCJB-UHFFFAOYSA-N COC(OC)[Si]CCC(F)(F)F Chemical compound COC(OC)[Si]CCC(F)(F)F QOGFQIGEQMWCJB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SVWGMNVDRHEOQI-UHFFFAOYSA-N trimethyl-[methyl-(3,3,3-trifluoropropyl)-trimethylsilyloxysilyl]oxysilane Chemical compound C[Si](C)(C)O[Si](C)(O[Si](C)(C)C)CCC(F)(F)F SVWGMNVDRHEOQI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 150000000190 1,4-diols Chemical class 0.000 description 1
- OLFNXLXEGXRUOI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C(N2N=C3C=CC=CC3=N2)=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 OLFNXLXEGXRUOI-UHFFFAOYSA-N 0.000 description 1
- YSUHBROHWRSYSF-UHFFFAOYSA-N 2-[3-[carboxy(hydroxy)methyl]phenyl]-2-hydroxyacetic acid Chemical compound OC(=O)C(O)C1=CC=CC(C(O)C(O)=O)=C1 YSUHBROHWRSYSF-UHFFFAOYSA-N 0.000 description 1
- FKLAJCGHOJXZRK-UHFFFAOYSA-N 2-[4-[carboxy(hydroxy)methyl]phenyl]-2-hydroxyacetic acid Chemical compound OC(=O)C(O)C1=CC=C(C(O)C(O)=O)C=C1 FKLAJCGHOJXZRK-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- BKFXSOCDAQACQM-UHFFFAOYSA-N 3-chlorophthalic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1C(O)=O BKFXSOCDAQACQM-UHFFFAOYSA-N 0.000 description 1
- KFIRODWJCYBBHY-UHFFFAOYSA-N 3-nitrophthalic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1C(O)=O KFIRODWJCYBBHY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LFEWXDOYPCWFHR-UHFFFAOYSA-N 4-(4-carboxybenzoyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C=C1 LFEWXDOYPCWFHR-UHFFFAOYSA-N 0.000 description 1
- LABJFIBQJFPXHZ-UHFFFAOYSA-N 4-(carboxymethoxy)benzoic acid Chemical compound OC(=O)COC1=CC=C(C(O)=O)C=C1 LABJFIBQJFPXHZ-UHFFFAOYSA-N 0.000 description 1
- DMEDOWYXHVUPMO-UHFFFAOYSA-N 4-(carboxymethyl)benzoic acid Chemical compound OC(=O)CC1=CC=C(C(O)=O)C=C1 DMEDOWYXHVUPMO-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004358 Butane-1, 3-diol Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004420 Iupilon Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- OHABWQNEJUUFAV-UHFFFAOYSA-N dichloro-methyl-(3,3,3-trifluoropropyl)silane Chemical compound C[Si](Cl)(Cl)CCC(F)(F)F OHABWQNEJUUFAV-UHFFFAOYSA-N 0.000 description 1
- SNVXETNSVRUKHB-UHFFFAOYSA-N dichloro-methyl-(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane Chemical compound C[Si](Cl)(Cl)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNVXETNSVRUKHB-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 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
- 150000007522 mineralic acids Chemical class 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- WEUBQNJHVBMUMD-UHFFFAOYSA-N trichloro(3,3,3-trifluoropropyl)silane Chemical compound FC(F)(F)CC[Si](Cl)(Cl)Cl WEUBQNJHVBMUMD-UHFFFAOYSA-N 0.000 description 1
- BVQYIDJXNYHKRK-UHFFFAOYSA-N trimethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BVQYIDJXNYHKRK-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- VIYXXANHGYSBLY-UHFFFAOYSA-N trimethylsilyl 2,2,2-trifluoroacetate Chemical compound C[Si](C)(C)OC(=O)C(F)(F)F VIYXXANHGYSBLY-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Optical Elements Other Than Lenses (AREA)
Description
本発明は光線反射樹脂組成物に関する。 The present invention relates to a light reflecting resin composition.
現在、ディスプレイ、照明の光源には、蛍光灯、白熱灯、冷陰極管、ＬＥＤが使用されており、これらの光源光を面全体に拡散させ、視認性や電力を削減するため、光源の背面に光線反射板等が設けられている。一般的に光線反射板には、金属系反射板や熱可塑性樹脂反射シートが使用されている。 Currently, fluorescent lamps, incandescent lamps, cold-cathode tubes, and LEDs are used as light sources for displays and lighting. These light sources are diffused over the entire surface to reduce visibility and power. Is provided with a light reflector or the like. In general, a metal reflector or a thermoplastic resin reflector is used as the light reflector.
上記金属系反射板には、一般的に白色に塗装された鋼板や、アルミニウム板などが使用されているが、金属系の反射板は光源からの光が特定方向への反射となり面全体での均一な反射効果が得られにくい。一方、樹脂系の反射シートは、反射特性は優れるものの、光源の高寿命化や、高出力化に伴いシートの耐熱、耐光劣化が促進され、経時で黄変するため反射率の低下が問題となっている。そのため、反射板に二酸化チタンと紫外線吸収剤を配合して樹脂劣化を抑制し、反射性能を維持できるとした技術や、硫酸バリウムと二酸化チタンを併用した特許が開示されている（特許文献１、２）。 The metal reflector is generally made of white coated steel plate or aluminum plate, but the metal reflector reflects the light from the light source in a specific direction and is reflected over the entire surface. It is difficult to obtain a uniform reflection effect. On the other hand, although the resin-based reflection sheet has excellent reflection characteristics, the heat resistance and light resistance deterioration of the sheet are promoted with the extension of the life of the light source and the increase in output, and the deterioration of the reflectance is caused by yellowing with time. It has become. For this reason, a technique is disclosed in which titanium dioxide and an ultraviolet absorber are blended in the reflector plate to suppress resin deterioration and the reflection performance can be maintained, and a patent that uses barium sulfate and titanium dioxide in combination is disclosed (Patent Document 1, 2).
しかし、反射率を上げるために樹脂中に二酸化チタンを多量に含む反射板用途において、樹脂組成物を作製する際に紫外線吸収剤を単に配合する方法では、紫外線吸収剤が二酸化チタンに物理的に遮蔽され、効率的な紫外線遮蔽ができない。また、効率的に紫外線を遮蔽するために紫外線吸収剤を多量に配合すると、ブリードアウト現象が生じ、経時で遮蔽効果の低下や、他の物性に悪影響を及ぼすことがある。また、ブリードアウトは、温度が高いほど生じやすく、高出力の光源ほど起こりやすいため、近年多用されている光源ではより顕著となる。そのため、紫外線吸収剤を用いず、二酸化チタンの無機表面処理により耐熱、耐光性を付与する試みがなされている。しかし、樹脂に混合する場合、無機処理のみでは二酸化チタンが凝集し、樹脂中に均一に分散しないため反射率の低下を招く。そのため、有機処理を施す必要があるが、一般的に有機処理は耐熱、耐光性に乏しく、成形品の黄色を促進する問題がある。 However, in a reflector application containing a large amount of titanium dioxide in the resin in order to increase the reflectivity, in the method of simply adding an ultraviolet absorber when preparing a resin composition, the ultraviolet absorber is physically added to the titanium dioxide. It is shielded and efficient UV shielding is not possible. In addition, when a large amount of an ultraviolet absorber is blended in order to efficiently shield ultraviolet rays, a bleed-out phenomenon occurs, which may deteriorate the shielding effect over time and adversely affect other physical properties. In addition, bleedout is more likely to occur at higher temperatures, and more likely to occur at higher output light sources. Therefore, an attempt has been made to impart heat resistance and light resistance by using an inorganic surface treatment of titanium dioxide without using an ultraviolet absorber. However, when mixed with a resin, titanium dioxide aggregates only with inorganic treatment and does not uniformly disperse in the resin, leading to a decrease in reflectance. Therefore, it is necessary to perform organic treatment, but generally organic treatment is poor in heat resistance and light resistance and has a problem of promoting yellowness of a molded product.
本発明は、長期間光源にさらされても低分子化合物のブリード現象や成形品の黄変がなく、反射率の低下を抑制できる光線反射用樹脂組成物、及びマスターバッチとその成形品の提供を目的とする。 The present invention provides a resin composition for light reflection that can suppress a decrease in reflectivity without causing bleeding of a low molecular compound or yellowing of a molded product even when exposed to a light source for a long period of time, and a masterbatch and a molded product thereof With the goal.
本発明は、酸化アルミニウムを含む金属酸化物で形成してなる第一被覆層と、フルオロアルキル基含有有機ケイ素化合物で形成してなる第二の被覆層を有する二酸化チタンと、熱可塑性樹脂を含む光線反射樹脂組成物である。 The present invention includes a first coating layer formed of a metal oxide containing aluminum oxide, titanium dioxide having a second coating layer formed of a fluoroalkyl group-containing organosilicon compound, and a thermoplastic resin. It is a light reflecting resin composition.
即ち、本発明は、二酸化チタン（Ａ）と、熱可塑性樹脂（Ｂ）とを含み、前記二酸化チタン（Ａ）が、酸化アルミニウムを含む金属酸化物で形成してなる第一の被覆層と、フルオロアルキル基含有有機ケイ素化合物で形成してなる第二の被覆層を有する光線反射樹脂組成物に関する。 That is, the present invention comprises a first coating layer comprising titanium dioxide (A) and a thermoplastic resin (B), wherein the titanium dioxide (A) is formed of a metal oxide containing aluminum oxide; The present invention relates to a light reflecting resin composition having a second coating layer formed of a fluoroalkyl group-containing organosilicon compound.
また、本発明は、前記フルオロアルキル基含有有機ケイ素化合物が、フルオロアルキル基含有シラン、フルオロアルキル基含有シロキサンの少なくともいずれかであることを特徴とする前記光線反射樹脂組成物に関する。 In addition, the present invention relates to the light reflecting resin composition, wherein the fluoroalkyl group-containing organosilicon compound is at least one of a fluoroalkyl group-containing silane and a fluoroalkyl group-containing siloxane.
また、本発明は、前記フルオロアルキル基含有シランが、下記一般式（１）で表されるシラン化合物およびその加水分解縮合反応物の少なくともいずれかであることを特徴とする前記光線反射樹脂組成物に関する。
一般式（１） （ＣxＨ2x+1-yＦy）zＳｉ（ＯＲ）4-z
（式中、ｘは１〜１２の整数であり、ｙは３〜２５の整数であり、zは１〜３の整数であり、Ｒは、アルキル基、アリール基、アシル基を表す。ここで、zが１または２の場合、Ｒは同一でも相違していても良い）
Further, in the present invention, the light reflecting resin composition is characterized in that the fluoroalkyl group-containing silane is at least one of a silane compound represented by the following general formula (1) and a hydrolysis condensation reaction product thereof: About.
Formula (1) (C x H 2x + 1-y F y) z Si (OR) 4-z
(In the formula, x is an integer of 1 to 12, y is an integer of 3 to 25, z is an integer of 1 to 3, and R represents an alkyl group, an aryl group, or an acyl group. , When z is 1 or 2, R may be the same or different)
また、本発明は、前記金属酸化物が、さらにケイ素酸化物およびジルコニウム酸化物の少なくともいずれかを含むことを特徴とする前記光線反射樹脂組成物に関する。 The present invention also relates to the light reflecting resin composition, wherein the metal oxide further contains at least one of silicon oxide and zirconium oxide.
また、本発明は、前記第二の被覆層が、表面被覆する前の二酸化チタン１００重量部に対して０．３〜３重量部被覆してなることを特徴とする前記光線反射樹脂組成物に関する。 Further, the present invention relates to the light reflecting resin composition, wherein the second coating layer is formed by coating 0.3 to 3 parts by weight with respect to 100 parts by weight of titanium dioxide before surface coating. .
また、本発明は、二酸化チタンと酸化アルミニウムとを撹拌して第一の被覆層を形成する工程、
次いで二酸化チタンとフルオロアルキル基含有有機ケイ素化合物とを撹拌して第二の被覆層を形成し二酸化チタン（Ａ）を得る工程、
前記二酸化チタン（Ａ）と熱可塑性樹脂（Ｂ）を混練造粒する工程を含む光線反射樹脂組成物の製造方法に関する。
The present invention also includes a step of stirring the titanium dioxide and aluminum oxide to form the first coating layer,
Next, the titanium dioxide and the fluoroalkyl group-containing organosilicon compound are stirred to form a second coating layer to obtain titanium dioxide (A),
The present invention relates to a method for producing a light reflecting resin composition comprising a step of kneading and granulating the titanium dioxide (A) and a thermoplastic resin (B).
また、本発明は、熱可塑性樹脂（Ｂ）１００重量部と、二酸化チタン（Ａ）５０〜１６０重量部とを含み、
前記二酸化チタン（Ａ）は、表面被覆する前の二酸化チタン１００重量部に対して、酸化アルミニウム１．０〜５重量部で形成してなる第一の被覆層、およびフルオロアルキル基含有有機ケイ素化合物０．３〜３重量部で形成してなる第二の被覆層を備えたことを特徴とする光線反射用マスターバッチに関する。
The present invention also includes 100 parts by weight of the thermoplastic resin (B) and 50 to 160 parts by weight of titanium dioxide (A),
The titanium dioxide (A) is a first coating layer formed of 1.0 to 5 parts by weight of aluminum oxide with respect to 100 parts by weight of titanium dioxide before surface coating, and a fluoroalkyl group-containing organosilicon compound The present invention relates to a light reflecting masterbatch comprising a second coating layer formed by 0.3 to 3 parts by weight.
また、本発明は、前記光線反射樹脂組成物、前記製造方法で得た光線反射樹脂組成物、または熱可塑性樹脂と前記光線反射用マスターバッチとの混合物のいずれかを成形してなる反射板に関する。 The present invention also relates to a reflector formed by molding any one of the light reflecting resin composition, the light reflecting resin composition obtained by the manufacturing method, or a mixture of a thermoplastic resin and the light reflecting master batch. .
上記構成の本発明によれば、二酸化チタンを使用したことで可視領域の波長を反射させることができるため、ディスプレイ等の視認性向上、消費電力の削減に寄与する。また、赤外領域の光を反射することで成形品内の蓄熱を防止し、耐久性の向上も期待される。また、酸化アルミニウムで形成した第一の被覆層に加えて、フルオロアルキル基含有有機ケイ素化合物で形成した第二の被覆層を有する二酸化チタンを含むことで光源の熱、光による劣化を抑制することができる。また、耐光性を付与するために紫外線吸収剤を配合する場合と比較してブリードアウトが無く、経時での汚染、黄変による反射率低下や、物性低下を生じにくくし、持続して高い反射率が得られる。 According to the present invention having the above-described configuration, the use of titanium dioxide can reflect the wavelength in the visible region, which contributes to improving the visibility of displays and the like and reducing power consumption. In addition, reflecting the light in the infrared region prevents heat storage in the molded product, and is expected to improve durability. Moreover, in addition to the first coating layer formed of aluminum oxide, titanium dioxide having a second coating layer formed of a fluoroalkyl group-containing organosilicon compound is included to suppress deterioration of the light source due to heat and light. Can do. In addition, there is no bleed-out compared to the case where a UV absorber is added to provide light resistance, and it is difficult to cause a decrease in reflectance and physical properties due to contamination over time, yellowing, and high reflection continuously. Rate is obtained.
本発明により、二酸化チタンの反射効果によるディスプレイ等の視認性向上、消費電力の削減が可能で、長期間使用した場合でも、光源の熱、光によって起こるブリードアウト現象、成形品の黄色が起こりにくい光線反射シートを形成できる光線反射樹脂組成物を提供できる。 According to the present invention, it is possible to improve the visibility of a display or the like due to the reflection effect of titanium dioxide and reduce power consumption. Even when used for a long period of time, the bleed-out phenomenon caused by the heat of the light source and light, and the yellow color of the molded product hardly occur. A light reflecting resin composition capable of forming a light reflecting sheet can be provided.
まず、本発明を詳細に説明する。なお、本明細書において、「任意の数Ａ以上、任意の数Ｂ以下」及び「任意の数Ａ〜任意の数Ｂ」の記載は、数Ａ及び数Ａより大きい範囲であって、数Ｂ及び数Ｂより小さい範囲を意味する。 First, the present invention will be described in detail. In the present specification, the description of “any number A or more and any number B or less” and “any number A to any number B” is a range larger than the number A and the number A, and the number B And a range smaller than the number B.
本発明の光線反射樹脂組成物は、二酸化チタン（Ａ）と、熱可塑性樹脂（Ｂ）とを含み、前記二酸化チタン（Ａ）は、酸化アルミニウムを含む金属酸化物で形成してなる第一の被覆層と、フルオロアルキル基含有有機ケイ素化合物で形成してなる第二の被覆層を有する。この光線反射樹脂組成物は、樹脂層に成形して使用し、ディスプレイ用反射板、照明用反射板等に使用することができる。 The light reflecting resin composition of the present invention contains titanium dioxide (A) and a thermoplastic resin (B), and the titanium dioxide (A) is a first oxide formed of a metal oxide containing aluminum oxide. A coating layer and a second coating layer formed of a fluoroalkyl group-containing organosilicon compound are included. This light reflecting resin composition is molded into a resin layer and used, and can be used for a reflection plate for display, a reflection plate for illumination, and the like.
本発明において二酸化チタン（Ａ）は、可視光、赤外光を反射する性質を有する。また、前記二酸化チタン（Ａ）は、酸化アルミニウムを含む金属酸化物で形成した第一の被覆層およびフルオロアルキル基含有有機ケイ素化合物で形成した第二の被覆層を有するため、二酸化チタンが樹脂中に均一に分散し、光源による熱劣化、光劣化による樹脂の黄変や分解を抑制し、高い反射率を持続することができる。これは、第二の被覆層フルオロアルキル基による耐熱、耐光性向上によるものと考えられる。フルオロアルキル基は、他の官能基と比較し臨界表面張力が低い。そのため、樹脂に配合された場合、樹脂−空気界面において表面自由エネルギーを小さくしようとする力が働く。そのため、界面にフルオロアルキル基が偏析しやすくなり、結合エネルギーの大きい炭素−フッ素結合による優れた耐熱、耐光性と、界面付近のチタン存在量の増加により樹脂劣化の抑制を可能にしていると推察される。 In the present invention, titanium dioxide (A) has a property of reflecting visible light and infrared light. In addition, since the titanium dioxide (A) has a first coating layer formed of a metal oxide containing aluminum oxide and a second coating layer formed of a fluoroalkyl group-containing organosilicon compound, the titanium dioxide is contained in the resin. It is possible to maintain a high reflectivity by uniformly dispersing the resin, suppressing the heat deterioration due to the light source and the yellowing and decomposition of the resin due to the light deterioration. This is considered to be due to the improvement of heat resistance and light resistance by the second coating layer fluoroalkyl group. A fluoroalkyl group has a lower critical surface tension than other functional groups. Therefore, when it is blended with a resin, a force that reduces the surface free energy acts at the resin-air interface. As a result, fluoroalkyl groups are easily segregated at the interface, and it is assumed that the resin-deterioration can be suppressed by the excellent heat resistance and light resistance due to the carbon-fluorine bond having a large binding energy and the increase in the amount of titanium present near the interface. Is done.
本発明において、二酸化チタン（Ａ）は、平均一次粒子径０．１５〜１．０μｍが好ましい。平均一次粒子径が、０．１５〜１．０μｍの範囲にあることで可視領域から赤外領域の幅広い波長領域で反射効果が得られる。特に、光源の可視領域の高い反射効果を得たい場合、平均一次粒子径０．１５〜０．３５μｍの二酸化チタンを用いることが好ましく、赤外領域の反射効果を得たい場合、０．３５〜１．０μｍの二酸化チタンを用いることが好ましい。また、広波長領域にわたって反射効果を高めるため、平均一次粒子径が異なる２種以上の二酸化チタンを用いることもできる。
二酸化チタン（Ａ）の結晶形態は、ルチル型、アナターゼ型、およびブルカイト型が使用できるが、ルチル型が好ましい。ルチル型は、他のタイプと比較して、屈折率が高く、反射効率が高い。
なお、平均一次粒子径は、走査電子顕微鏡の拡大画像（例えば千倍〜一万倍）から観察できる粒子径（例えば５０個程度）を平均したものである。二酸化チタン（Ａ）の粒子形状は、球状、楕円体状等公知の粒子形状を使用できる。
In the present invention, the titanium dioxide (A) preferably has an average primary particle size of 0.15 to 1.0 μm. When the average primary particle diameter is in the range of 0.15 to 1.0 μm, a reflection effect can be obtained in a wide wavelength region from the visible region to the infrared region. In particular, when it is desired to obtain a high reflection effect in the visible region of the light source, it is preferable to use titanium dioxide having an average primary particle diameter of 0.15 to 0.35 μm. It is preferable to use 1.0 μm titanium dioxide. Further, in order to enhance the reflection effect over a wide wavelength region, two or more types of titanium dioxide having different average primary particle diameters can be used.
As the crystal form of titanium dioxide (A), rutile type, anatase type and brookite type can be used, but rutile type is preferred. The rutile type has a higher refractive index and higher reflection efficiency than other types.
In addition, an average primary particle diameter averages the particle diameter (for example, about 50 particles) which can be observed from the enlarged image (for example, 1000 times-10,000 times) of a scanning electron microscope. The particle shape of titanium dioxide (A) can be a known particle shape such as a spherical shape or an ellipsoidal shape.
また、二酸化チタン（Ａ）は、酸化アルミニウムを含む金属酸化物で形成した第一の被覆層と、フルオロアルキル基含有有機ケイ素化合物で形成した第二の被覆層を有することが重要である。これらの被覆層が存在することで、反射シート、板等の成形品の黄色を抑制できる。 In addition, it is important that titanium dioxide (A) has a first coating layer formed of a metal oxide containing aluminum oxide and a second coating layer formed of a fluoroalkyl group-containing organosilicon compound. The presence of these coating layers can suppress yellowing of molded articles such as reflective sheets and plates.
前記第一の被覆層は、金属酸化物で形成し酸化アルミニウムを含むことが必要である。酸化アルミニウムは、アルミニウムの含水酸化物であっても良く、含水アルミナ（Ａｌ2Ｏ3・ｎＨ2Ｏ）が好ましい。その他の金属酸化物としてはアルミニウム、ケイ素、ジルコニウム、亜鉛、チタン、マグネシウム、アンチモン、スズの酸化物や含水酸化物が挙げられる。
前記金属酸化物は、さらにケイ素酸化物およびジルコニウム酸化物を少なくともいずれか含むことが好ましい。ケイ素またはジルコニウム酸化物を含むことで二酸化チタンの光触媒活性をより低減できるため、熱可塑性樹脂の劣化をより抑制することができる。前記ケイ素酸化物は、ケイ素の含水酸化物であっても良く、シリカや含水シリカ（ＳｉＯ2・ｎＨ2Ｏ）が好ましい。また前記ジルコニウム酸化物は、ジルコニウムの含水酸化物（ＺｒＯ2・ｎＨ2Ｏ）で表面被覆されていても良い。なお本発明では、酸化アルミニウムの他に、ケイ素酸化物、ジルコニウム酸化物で形成した被覆層であっても、第一の被覆層とする。
The first coating layer needs to be formed of a metal oxide and include aluminum oxide. The aluminum oxide may be a hydrated oxide of aluminum, and preferably hydrated alumina (Al 2 O 3 .nH 2 O). Examples of other metal oxides include aluminum, silicon, zirconium, zinc, titanium, magnesium, antimony, tin oxide, and hydrous oxide.
The metal oxide preferably further contains at least one of silicon oxide and zirconium oxide. Since the photocatalytic activity of titanium dioxide can be further reduced by including silicon or zirconium oxide, deterioration of the thermoplastic resin can be further suppressed. The silicon oxide may be a hydrous oxide of silicon, and is preferably silica or hydrous silica (SiO 2 .nH 2 O). The zirconium oxide may be surface-coated with a hydrous oxide of zirconium (ZrO 2 · nH 2 O). In the present invention, a coating layer formed of silicon oxide or zirconium oxide in addition to aluminum oxide is used as the first coating layer.
二酸化チタン（Ａ）の第一の被覆層は、表面被覆する前の二酸化チタン１００重量部に対して、酸化アルミニウム１〜５重量部で被覆することが好ましく、より好ましくは１〜４重量部、さらに好ましくは、１．５〜４重量部である。また、ケイ素酸化物またはジルコニウム酸化物は、表面被覆する前の二酸化チタン１００重量部に対して、それぞれ０．１〜３重量部で被覆することが好ましく、より好ましくは、０．１〜２．０重量部である。 The first coating layer of titanium dioxide (A) is preferably coated with 1 to 5 parts by weight of aluminum oxide, more preferably 1 to 4 parts by weight with respect to 100 parts by weight of titanium dioxide before surface coating. More preferably, it is 1.5 to 4 parts by weight. Moreover, it is preferable to coat | cover silicon oxide or zirconium oxide with 0.1-3 weight part respectively with respect to 100 weight part of titanium dioxide before surface-coating, More preferably, 0.1-2. 0 parts by weight.
第二の被覆層は、フルオロアルキル基含有有機ケイ素化合物を使用する。フルオロアルキル基含有有機ケイ素化合物は、フルオロアルキル基含有シラン、フルオロアルキル基含有シロキサンが好ましい。より好ましくは、下記一般式（１）で表されるシラン化合物およびその加水分解縮合反応物の少なくともいずれかである。これらの化合物を用いることで、二酸化チタンへの均一な表面被覆が可能となり、より、耐熱性、耐光性が得られやすくなる。
一般式（１） （ＣxＨ2x+1-yＦy）zＳｉ（ＯＲ）4-z
（式中、ｘは１〜１２の整数であり、ｙは３〜２５の整数であり、zは１〜３の整数であり、Ｒは、アルキル基、アリール基、アシル基を表す。ここで、zが１または２の場合、Ｒは同一でも相違していても良い）
なお、Ｒはメチル、エチル等のアルキル基や、フェニル等のアリール基、アセチル、プロピオニル、ベンゾイル等のアシル基が挙げられるが、加水分解、縮合反応速度の観点からメチル、エチル等のアルキル基が好ましい。ｘはフルオロ基含有アルキルの炭素数を示し、１〜１２の整数が好ましく、炭素数が少ない方が、耐熱、耐光性の観点から好ましい。また、ｙはフルオロ基の数を示し、３〜２５の整数が好ましいが、コスト面から３〜１３の整数がより好ましい。ｚはフルオロアルキル基数を示し、１〜３の整数であるが、二酸化チタン表面への均一な被覆、加水分解速度の観点からｚ＝１が好ましい。
The second coating layer uses a fluoroalkyl group-containing organosilicon compound. The fluoroalkyl group-containing organosilicon compound is preferably a fluoroalkyl group-containing silane or a fluoroalkyl group-containing siloxane. More preferably, it is at least one of a silane compound represented by the following general formula (1) and a hydrolysis condensation reaction product thereof. By using these compounds, it is possible to uniformly coat titanium dioxide, and it becomes easier to obtain heat resistance and light resistance.
Formula (1) (C x H 2x + 1-y F y) z Si (OR) 4-z
(In the formula, x is an integer of 1 to 12, y is an integer of 3 to 25, z is an integer of 1 to 3, and R represents an alkyl group, an aryl group, or an acyl group. , When z is 1 or 2, R may be the same or different)
R includes alkyl groups such as methyl and ethyl, aryl groups such as phenyl, and acyl groups such as acetyl, propionyl, and benzoyl. From the viewpoint of hydrolysis and condensation reaction rate, alkyl groups such as methyl and ethyl are preferred. preferable. x represents the carbon number of the fluoro group-containing alkyl, preferably an integer of 1 to 12, and a smaller number of carbon atoms is preferred from the viewpoints of heat resistance and light resistance. Moreover, y shows the number of fluoro groups, and the integer of 3-25 is preferable, but the integer of 3-13 is more preferable from a cost surface. z represents the number of fluoroalkyl groups and is an integer of 1 to 3, but z = 1 is preferable from the viewpoint of uniform coating on the titanium dioxide surface and hydrolysis rate.
第二の被覆層が、表面被覆する前の二酸化チタン１００重量部に対して０．３〜３重量部被覆することが好ましく、より好ましくは０．３〜２．０重量部、さらに好ましくは０．３〜１．５重量部である。０．３重量部未満の場合、耐熱、耐光性の効果が不足する恐れがあり、３重量部を超える場合、フルオロアルキル基含有有機ケイ素化合物同士での縮合反応が進みすぎて、ゲル状物質が生成する恐れがある。 The second coating layer preferably coats 0.3 to 3 parts by weight, more preferably 0.3 to 2.0 parts by weight, and still more preferably 0 to 100 parts by weight of titanium dioxide before surface coating. .3 to 1.5 parts by weight. If the amount is less than 0.3 parts by weight, the effect of heat resistance and light resistance may be insufficient. If the amount exceeds 3 parts by weight, the condensation reaction between the fluoroalkyl group-containing organosilicon compounds proceeds excessively, and the gel substance is There is a risk of generating.
フルオロアルキル基含有有機ケイ素化合物としては、フルオロアルキル基含有シラン化合物、およびその加水分解物、およびその縮合反応物、ならびにフルオロアルキル基含有シロキサン等が挙げられる。 Examples of the fluoroalkyl group-containing organosilicon compound include a fluoroalkyl group-containing silane compound, a hydrolyzate thereof, a condensation reaction product thereof, and a fluoroalkyl group-containing siloxane.
フルオロアルキル基含有シランとしては、例えば３，３，３−トリフルオロプロピルトリクロロシラン、メチル−３，３，３−トリフルオロプロピルジクロロシラン、トリフルオロアセトキシトリメチルシラン、３，３，４，４，５，５，６，６，６−ノナフルオロヘキシルトリクロロシラン、ジメトキシメチル−３，３，３−トリフロオロプロピルシラン、３,３，３−トリフルオロプロピルトリメトキシシラン、３，３，４，４，５，５，６，６，６−ノナフルオロヘキシルメチルジクロロシラン、３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクチルトリメトキシシラン等が挙げられる。好ましくは、アルキルオキシ基含有のジメトキシメチル−３，３，３−トリフロオロプロピルシラン、３,３，３−トリフルオロプロピルトリメトキシシラン、３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクチルトリエトキシシランであり、さらに好ましくは、アルキル炭素数が少なく、フルオロ基の多い、３,３，３−トリフルオロプロピルトリメトキシシラン、３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクチルトリエトキシシラン等である。 Examples of the fluoroalkyl group-containing silane include 3,3,3-trifluoropropyltrichlorosilane, methyl-3,3,3-trifluoropropyldichlorosilane, trifluoroacetoxytrimethylsilane, 3,3,4,4,5. , 5,6,6,6-nonafluorohexyltrichlorosilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,4,4 , 5,5,6,6,6-nonafluorohexylmethyldichlorosilane, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyltrimethoxy Silane etc. are mentioned. Preferably, alkyloxy group-containing dimethoxymethyl-3,3,3-trifluoropropylsilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,4,4,5,5,6, 6,7,7,8,8,8-tridecafluorooctyltriethoxysilane, more preferably 3,3,3-trifluoropropyltrimethoxysilane having a small number of alkyl carbon atoms and a large number of fluoro groups, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyltriethoxysilane.
フルオロアルキル基含有シロキサンとしては、例えば３−（３，３，３−トリフルオロプロピル）−１，１，１，３，５，５，５−ヘプタメチルトリシロキサン、１，３，５−トリス（３，３，３−トリフルオロプロピル）−１，３，５−トリメチルシクロトリシロキサン、１，３，５，７−テトラキス（３，３，３−トリフルオロプロピル）−1，３，５，７−テトラメチルシクロテトラシロキサン、側鎖フルオロアルキル変性ポリシロキサンまたはそれらの共重合体等が挙げられる。好ましくは、フルオロアルキル基数の多い、１，３，５−トリス（３，３，３−トリフルオロプロピル）−１，３，５−トリメチルシクロトリシロキサン、１，３，５，７−テトラキス（３，３，３−トリフルオロプロピル）−1，３，５，７−テトラメチルシクロテトラシロキサン等である。 Examples of the fluoroalkyl group-containing siloxane include 3- (3,3,3-trifluoropropyl) -1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,3,5-tris ( 3,3,3-trifluoropropyl) -1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetrakis (3,3,3-trifluoropropyl) -1,3,5,7 -Tetramethylcyclotetrasiloxane, side chain fluoroalkyl-modified polysiloxane or copolymers thereof. Preferably, 1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5-trimethylcyclotrisiloxane having a large number of fluoroalkyl groups, 1,3,5,7-tetrakis (3 , 3,3-trifluoropropyl) -1,3,5,7-tetramethylcyclotetrasiloxane.
これらのフルオロアルキル基含有有機ケイ素化合物は、１種または２種以上を使用できる。 One or more of these fluoroalkyl group-containing organosilicon compounds can be used.
二酸化チタンと酸化アルミニウムとを撹拌して第一の被覆層を形成する工程、
次いで二酸化チタンとフルオロアルキル基含有有機ケイ素化合物とを撹拌して第二の被覆層を形成し二酸化チタン（Ａ）を得る工程、
前記二酸化チタン（Ａ）と熱可塑性樹脂（Ｂ）を混練造粒する工程を含むことが好ましい。この工程により、経済的かつ簡易的に二酸化チタン表面に被覆することが可能となる。ここで言う表面への被覆は、共有結合、水素結合等の化学結合や、分子間力等による物理吸着が含まれるが、より好ましくは、化学結合の形成である。また、被覆するための撹拌時間は、１分〜２時間が効率、取り扱いの観点から好ましい。より好ましくは、３分〜１時間である。
A step of stirring titanium dioxide and aluminum oxide to form a first coating layer;
Next, the titanium dioxide and the fluoroalkyl group-containing organosilicon compound are stirred to form a second coating layer to obtain titanium dioxide (A),
It is preferable to include a step of kneading and granulating the titanium dioxide (A) and the thermoplastic resin (B). This step makes it possible to coat the titanium dioxide surface economically and simply. The coating on the surface mentioned here includes chemical bonds such as covalent bonds and hydrogen bonds, and physical adsorption by intermolecular forces, and more preferably, the formation of chemical bonds. The stirring time for coating is preferably 1 minute to 2 hours from the viewpoint of efficiency and handling. More preferably, it is 3 minutes to 1 hour.
二酸化チタンに対する被覆層の形成方法を説明する。 A method for forming a coating layer on titanium dioxide will be described.
第一の被覆層を形成する方法は、公知の方法を使用できる。例えば、酸化アルミニウムで被覆する場合、二酸化チタン粒子を分散させた水性スラリーにアルミニウム化合物の水溶液を添加し、酸性化合物または塩基性化合物の水溶液を用いてｐＨ４〜９に調整することで酸化アルミニウムの被覆層を形成できる。その後、必要に応じて濾過、洗浄、乾燥を行っても良い。ｐＨの調整に用いる酸性酸化物としては、硫酸、塩酸等の無機酸、または酢酸、ギ酸等の有機酸を用いることができる。また、塩基性化合物としては、水酸化ナトリウム、水酸化カリウム、アンモニア等の公知の化合物を用いることができる。水性スラリー中の二酸化チタン粒子の不揮発分濃度は、５０〜８００ｇ／ｌが好ましく、１００〜６００ｇ／ｌがより好ましい。所定の不揮発分濃度にすることで均一な厚みの被覆層が得やすくなる。 A known method can be used as a method of forming the first coating layer. For example, when coating with aluminum oxide, an aqueous solution of an aluminum compound is added to an aqueous slurry in which titanium dioxide particles are dispersed, and the pH is adjusted to 4 to 9 using an aqueous solution of an acidic compound or a basic compound, thereby coating the aluminum oxide. Layers can be formed. Then, you may perform filtration, washing | cleaning, and drying as needed. As the acidic oxide used for adjusting the pH, inorganic acids such as sulfuric acid and hydrochloric acid, or organic acids such as acetic acid and formic acid can be used. Moreover, as a basic compound, well-known compounds, such as sodium hydroxide, potassium hydroxide, and ammonia, can be used. The non-volatile content of titanium dioxide particles in the aqueous slurry is preferably 50 to 800 g / l, more preferably 100 to 600 g / l. A coating layer having a uniform thickness can be easily obtained by setting the concentration to a predetermined nonvolatile content.
前記アルミニウム化合物は、例えばアルミン酸ナトリウム、硫酸アルミニウム、および硝酸アルミニウム、塩化アルミニウム、アルミナ、含水アルミナ等が挙げられる。 Examples of the aluminum compound include sodium aluminate, aluminum sulfate, and aluminum nitrate, aluminum chloride, alumina, hydrous alumina, and the like.
ケイ素酸化物またはジルコニウム酸化物で被覆する場合は、ケイ素化合物またはジルコニウム化合物を使用して、酸化アルミニウムと同様の方法でケイ素酸化物または酸化アルミニウムの被覆層を形成できる。また、複数の金属酸化物で被覆層を形成する場合、アルミニウム化合物を含む混合物で被覆層を形成できる。また、各化合物を順次使用して被覆層を形成しても良く被覆層を形成する順序は、制限を受けない。これらの被覆方法の中でも、ケイ素酸化物またはジルコニウム酸化物の被覆層の形成後に酸化アルミニウムが最外層になるように被覆層を形成することが熱可塑性樹脂との分散性の観点からより好ましい。さらに、二酸化チタン（Ａ）の被覆層を形成する際に脱水、乾燥、粉砕などの工程が容易になり歩留まりがより向上する。なお本発明では、金属酸化物で形成した第一の被覆層が、例えば、酸化アルミニウムの被覆層、ケイ素酸化物の被覆層、ジルコニウム酸化物の被覆層と３層を有する場合であっても、第一の被覆層とする。 In the case of coating with silicon oxide or zirconium oxide, a silicon oxide or zirconium oxide can be used to form a silicon oxide or aluminum oxide coating layer in the same manner as aluminum oxide. Moreover, when forming a coating layer with a some metal oxide, a coating layer can be formed with the mixture containing an aluminum compound. In addition, the coating layer may be formed by using each compound sequentially, and the order of forming the coating layer is not limited. Among these coating methods, it is more preferable from the viewpoint of dispersibility with the thermoplastic resin that the coating layer is formed so that the aluminum oxide becomes the outermost layer after the formation of the coating layer of silicon oxide or zirconium oxide. Furthermore, when forming the coating layer of titanium dioxide (A), processes such as dehydration, drying, and pulverization are facilitated, and the yield is further improved. In the present invention, even if the first coating layer formed of the metal oxide has, for example, an aluminum oxide coating layer, a silicon oxide coating layer, a zirconium oxide coating layer and three layers, The first coating layer is used.
前記ケイ素化合物は、例えばケイ酸ナトリウムなどの水溶性ケイ酸アルカリ金属塩が挙げられる。またジルコニウム化合物としては、例えば硫酸ジルコニウム、硝酸ジルコニウム、塩化ジルコニウム等が挙げられる。
前記ジルコニウム化合物は、例えば硫酸ジルコニウム、硝酸ジルコニウム、塩化ジルコニウム等が挙げられる。
Examples of the silicon compound include water-soluble alkali metal silicate salts such as sodium silicate. Examples of the zirconium compound include zirconium sulfate, zirconium nitrate, and zirconium chloride.
Examples of the zirconium compound include zirconium sulfate, zirconium nitrate, and zirconium chloride.
第二の被覆層を形成する方法は、（１）第一の被覆層を有する二酸化チタンを水性スラリーから固液分離し、乾燥した後、前記フルオロアルキル基含有有機ケイ素化合物と気相中で接触させることにより、被覆層を形成する方法（以下、気相法という）、または、（２）第一の被覆層を有する二酸化チタンと前記フルオロアルキル基含有有機ケイ素化合物をスラリー中で接触させることで形成する方法（以下、液相法という）があるが、ハンドリングの観点から気相法の方が好ましい。 The method for forming the second coating layer is as follows. (1) Titanium dioxide having the first coating layer is solid-liquid separated from the aqueous slurry, dried, and then contacted with the fluoroalkyl group-containing organosilicon compound in the gas phase. A method of forming a coating layer (hereinafter referred to as a vapor phase method), or (2) contacting titanium dioxide having a first coating layer with the fluoroalkyl group-containing organosilicon compound in a slurry. Although there is a method of forming (hereinafter referred to as a liquid phase method), the gas phase method is preferred from the viewpoint of handling.
前記気相法は、例えば流体エネルギー粉砕機、衝撃粉砕機等の乾式粉砕機や、ヘンシェルミキサー、スーパーミキサー等の高速攪拌機等を用い、二酸化チタンと前記フルオロアルキル基含有有機ケイ素化合物を攪拌、混合することで実施できる。フルオロアルキル基含有有機ケイ素化合物が室温において固体または、粘度の高い液体である時、アルコール等の有機溶媒で希釈して使用することもできる。この場合、使用する有機溶媒は撹拌機内で揮発させることが好ましい。 The gas phase method uses, for example, a dry pulverizer such as a fluid energy pulverizer or an impact pulverizer, a high-speed agitator such as a Henschel mixer or a super mixer, and the like, and agitation and mixing of titanium dioxide and the fluoroalkyl group-containing organosilicon compound This can be done. When the fluoroalkyl group-containing organosilicon compound is a solid or a highly viscous liquid at room temperature, it can be diluted with an organic solvent such as alcohol. In this case, the organic solvent to be used is preferably volatilized in a stirrer.
前記液相法は、第一の被覆層を形成した後、続けて、当該スラリーに前記フルオロアルキル基含有有機ケイ素化合物を添加し、攪拌、混合することで実施できる。 The liquid phase method can be carried out by adding the fluoroalkyl group-containing organosilicon compound to the slurry, and stirring and mixing after forming the first coating layer.
本発明において熱可塑性樹脂（Ｂ）は、従来既知の熱可塑性樹脂が使用でき、ポリエチレン樹脂、ポリプロピレン樹脂、塩化ビニル樹脂、エチレン酢酸ビニル共重合体樹脂、酢酸ビニル樹脂、ポリスチレン樹脂、ポリアクリレート樹脂、ポリアセタール樹脂、ＡＢＳ樹脂、ポリアミド樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリエチレンナフタレート樹脂、ポリエーテルイミド樹脂、ポリエーテルスルホン樹脂、ポリエーテルエーテルケトン樹脂、ポリフェニレンスルフィド樹脂、ポリスルホン樹脂、ポリメチルペンテン樹脂、含フッ素樹脂等があげられるが、耐熱性、機械物性の観点からポリエステル樹脂が好ましい。 In the present invention, as the thermoplastic resin (B), conventionally known thermoplastic resins can be used, polyethylene resin, polypropylene resin, vinyl chloride resin, ethylene vinyl acetate copolymer resin, vinyl acetate resin, polystyrene resin, polyacrylate resin, Polyacetal resin, ABS resin, polyamide resin, polycarbonate resin, polyester resin, polyethylene naphthalate resin, polyetherimide resin, polyethersulfone resin, polyetheretherketone resin, polyphenylene sulfide resin, polysulfone resin, polymethylpentene resin, fluorine-containing Examples thereof include resins, and polyester resins are preferred from the viewpoints of heat resistance and mechanical properties.
本発明で使用するポリエステル樹脂とは、分子の主鎖にエステル結合を持っている高分子量の熱可塑性樹脂であり、ジカルボン酸またはその誘導体と２価アルコールまたは２価フェノール化合物とから得られる重縮合化合物、ジカルボン酸またはその誘導体と環状エーテル化合
物とから得られる重縮合化合物、環状エーテル化合物の開環重合物などが挙げられる。ここで、ジカルボン酸の誘導体とは酸無水物、エステル化物である。ジカルボン酸は脂肪族であっても芳香族であってもよいが、耐熱性の観点から芳香族がより好ましい。また、芳香族ジカルボン酸または脂環族ジカルボン酸等の酸成分とジオール成分による重合体であり、ホモポリマーであってもコポリマーであってもよい。また、これらの混合などによるポリマーブレンドでもよい。芳香族ジカルボン酸としては、例えば、テレフタル酸、イソフタル酸、フタル酸、クロルフタル酸、ニトロフタル酸、ｐ−カルボキシルフェニル酢酸、ｍ−フェニレンジグリゴール酸、ｐ−フェニレンジグリコール酸、ジフェニルジ酢酸、ジフェニル−ｐ，ｐ′−ジカルボン酸、ジフェニル−４，４′−ジ酢酸、ジフェニルメタン−ｐ，ｐ′−ジカルボン酸、ジフェニルエタン− ｍ，ｍ′−ジカルボン酸、スチルベンジルカルボン酸、ジフェニルブタン−ｐ，ｐ′−ジカルボン酸、ベンゾフェノン− ４，４′−ジカルボン酸、ナフタリン− １，４−ジカルボン酸、ナフタリン−１，５−ジカルボン酸、ナフタリン−２，６−ジカルボン酸、ナフタリン−２，７−ジカルボン酸、ｐ−カルボキシフェノキシ酢酸、ｐ−カルボキシフェノキシブチル酸、１，２−ジフェノキシプロパン−ｐ，ｐ′−ジカルボン酸、１，５−ジフェノキシペンタン−ｐ，ｐ′−ジカルボン酸、１，６−ジフェノキシヘキサン−ｐ，ｐ′−ジカルボン酸、ｐ−（ｐ−カルボキシフェノキシ）安息香酸、１，２−ビス（２−メトキシフェノキシ）−エタン−ｐ，ｐ′−ジカルボン酸、１，３−ビス（２−メトキシフェノキシ）プロパン−ｐ，ｐ′−ジカルボン酸、１，４−ビス（２−メトキシフェノキシ）ブタン−ｐ，ｐ′−ジカルボン酸、１，５−ビス（２−メトキシフェノキシ）−３−オキシペンタン−ｐ，ｐ′−ジカルボン酸などを挙げることができ、また脂肪酸ジカルボン酸としては、例えば、シュウ酸、コハク酸、アジピン酸、コルク酸、マゼライン酸、セバシン酸、ドデカンジカルボン酸、ウンデカンジカルボン酸、マレイン酸、フマル酸などが挙げられる。好ましいジカルボン酸の例は、芳香族ジカルボン酸類である。２価アルコールとしては、例えば、エチレングリコール、トリメチレングリコール、ブタン−１，３−ジオール、ブタン−１，４−ジオール、２，２−ジメチルプロパン−１，４−ジオール、ｃｉｓ−２−ブテン−１，４−ジオール、テトラメチレングリコール、ペンタメチレングリコール、ヘキサメチレングリコール、オクタメチレングリコール、デカメチレングリコール、シクロヘキサンジメタノールなどが挙げられる。好ましい２価アルコールの例は、エチレングリコール、ブタン−１，４−ジオール、あるいはシクロヘキサンジメタノールである。２価フェノール化合物の例としては、例えば、ヒドロキノン、レゾルシノール、ビスフェノールＡなどを挙げることができる。前記環状エーテル化合物としては、エチレンオキサイド、プロピレンオキサイドを挙げることができる。これらジオール成分は、一種のみを用いてもよく、二種以上を併用してもよい。
The polyester resin used in the present invention is a high molecular weight thermoplastic resin having an ester bond in the main chain of the molecule, and polycondensation obtained from dicarboxylic acid or a derivative thereof and a dihydric alcohol or a dihydric phenol compound. Examples thereof include polycondensation compounds obtained from compounds, dicarboxylic acids or derivatives thereof and cyclic ether compounds, and ring-opening polymers of cyclic ether compounds. Here, the derivatives of dicarboxylic acid are acid anhydrides and esterified products. The dicarboxylic acid may be aliphatic or aromatic, but aromatic is more preferable from the viewpoint of heat resistance. Moreover, it is a polymer by acid components, such as aromatic dicarboxylic acid or alicyclic dicarboxylic acid, and a diol component, and may be a homopolymer or a copolymer. Further, a polymer blend by mixing them may be used. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxylphenylacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, diphenyldiacetic acid, diphenyl- p, p'-dicarboxylic acid, diphenyl-4,4'-diacetic acid, diphenylmethane-p, p'-dicarboxylic acid, diphenylethane-m, m'-dicarboxylic acid, stilbenzylcarboxylic acid, diphenylbutane-p, p '-Dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid , P-carboxyphenoxyacetic acid, p-carboxyphenoxyb Phosphoric acid, 1,2-diphenoxypropane-p, p'-dicarboxylic acid, 1,5-diphenoxypentane-p, p'-dicarboxylic acid, 1,6-diphenoxyhexane-p, p'-dicarboxylic acid P- (p-carboxyphenoxy) benzoic acid, 1,2-bis (2-methoxyphenoxy) -ethane-p, p'-dicarboxylic acid, 1,3-bis (2-methoxyphenoxy) propane-p, p '-Dicarboxylic acid, 1,4-bis (2-methoxyphenoxy) butane-p, p'-dicarboxylic acid, 1,5-bis (2-methoxyphenoxy) -3-oxypentane-p, p'-dicarboxylic acid Examples of the fatty acid dicarboxylic acid include oxalic acid, succinic acid, adipic acid, corkic acid, mazeline acid, sebacic acid, dodecanedicarboxylic acid, Dicarboxylic acid, maleic acid, fumaric acid, and the like. Examples of preferred dicarboxylic acids are aromatic dicarboxylic acids. Examples of the dihydric alcohol include ethylene glycol, trimethylene glycol, butane-1,3-diol, butane-1,4-diol, 2,2-dimethylpropane-1,4-diol, cis-2-butene- Examples include 1,4-diol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, and cyclohexanedimethanol. Examples of preferred dihydric alcohols are ethylene glycol, butane-1,4-diol, or cyclohexanedimethanol. Examples of the dihydric phenol compound include hydroquinone, resorcinol, bisphenol A, and the like. Examples of the cyclic ether compound include ethylene oxide and propylene oxide. These diol components may be used alone or in combination of two or more.
本発明の光線反射樹脂組成物は、二酸化チタンを高濃度で配合したペレット状のマスターバッチとして製造することが好ましい。前記マスターバッチは、熱可塑性樹脂（Ｂ）を含む原料を溶融混練し、さらにペレット状に成形することで製造できる。二酸化チタンは、一旦、マスターバッチとして樹脂中に予備分散した後で、希釈樹脂の熱可塑性樹脂と配合（溶融混錬）して所望の成形品を製造すると、二酸化チタン（Ａ）を熱可塑性樹脂中により均一に分散しやすくなる。また、樹脂への熱履歴が少なくなるため、樹脂劣化が抑制される。具体的には、マスターバッチは、熱可塑性樹脂（Ｂ）１００重量部に対して、二酸化チタン（Ａ）を５０〜１６０重量部配合することが好ましい。ここで、原料の溶融混練は、予め原料を一般的な高速せん断型混合機であるヘンシェルミキサー、スーパーミキサー等を用いて混合した後に行っても、混合せずに、溶融混練する際に、別々に混練機に投入してもよい。
前記溶融混練は、例えば単軸混練押出機、二軸混練押出機、またはタンデム式二軸混練押出機等を用いるのが好ましい。
The light reflecting resin composition of the present invention is preferably produced as a pellet master batch in which titanium dioxide is blended at a high concentration. The masterbatch can be produced by melting and kneading the raw material containing the thermoplastic resin (B) and further forming into a pellet. Once titanium dioxide is pre-dispersed in the resin as a masterbatch, it is blended (melt-kneaded) with the thermoplastic resin of the diluted resin to produce the desired molded product. The titanium dioxide (A) is then converted into the thermoplastic resin. It becomes easier to disperse evenly inside. Moreover, since the heat history to resin decreases, resin deterioration is suppressed. Specifically, the master batch preferably contains 50 to 160 parts by weight of titanium dioxide (A) with respect to 100 parts by weight of the thermoplastic resin (B). Here, the melt kneading of the raw materials is performed separately after mixing the raw materials in advance using a general high-speed shearing type mixer such as a Henschel mixer, a super mixer, etc. It may be put into a kneader.
For the melt-kneading, it is preferable to use, for example, a single-screw kneading extruder, a twin-screw kneading extruder, or a tandem twin-screw kneading extruder.
本発明の光線反射樹脂組成物は、例えば、車のヘッドライト、屋外水銀灯、液晶ディスプレイ用バックライト、電飾看板、照明、植物工場、太陽電池裏面保護シートなどの反射板またはシートが好ましい。 The light reflecting resin composition of the present invention is preferably a reflector or a sheet such as a car headlight, an outdoor mercury lamp, a backlight for a liquid crystal display, an electric signboard, illumination, a plant factory, a solar cell back surface protection sheet, and the like.
次に、本発明を具体的に実施例に基づき説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下、部は重量部、％は重量％を意味する。 Next, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. Hereinafter, “part” means “part by weight” and “%” means “% by weight”.
実施例および比較例に用いる原料を以下に示す。 The raw material used for an Example and a comparative example is shown below.
二酸化チタンの金属酸化物による表面被覆方法の例を以下に示す。なお表面被覆方法は、下記方法に限定されないことは言うまでも無い。 The example of the surface coating method by the metal oxide of titanium dioxide is shown below. Needless to say, the surface coating method is not limited to the following method.
[フルオロアルキル基含有有機ケイ素化合物]
（ｃ−１）３，３，３−トリフルオロプロピルトリメトキシシラン：信越化学工業製Ｌ Ｓ−１０９０
（ｃ−２）３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオ クチルトリエトキシシラン：デグサ社製Ｆ８２６１
（ｃ−３）３−（３，３，３−トリフルオロプロピル）−１，１，１，３，５，５，５− ヘプタメチルトリシロキサン：信越化学工業製ＬＳ−８２１０
[Fluoroalkyl group-containing organosilicon compound]
(C-1) 3,3,3-trifluoropropyltrimethoxysilane: Shin-Etsu Chemical L S-1090
(C-2) 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyltriethoxysilane: F8261 manufactured by Degussa
(C-3) 3- (3,3,3-trifluoropropyl) -1,1,1,3,5,5,5-heptamethyltrisiloxane: LS-8210 manufactured by Shin-Etsu Chemical Co., Ltd.
［非フルオロアルキル基含有有機ケイ素化合物］
（ｄ−１）ｎ−プロピルトリメトキシシラン：信越化学工業製ＬＳ−１３８２
（ｄ−２）オクチルトリエトキシシラン：信越化学工業製ＬＳ−５５８０
[Non-fluoroalkyl group-containing organosilicon compound]
(D-1) n-propyltrimethoxysilane: LS-1382 manufactured by Shin-Etsu Chemical Co., Ltd.
(D-2) Octyltriethoxysilane: LS-5580 manufactured by Shin-Etsu Chemical
＜二酸化チタンの表面被覆層形成１＞
ルチル型二酸化チタン粒子を水と混合して、二酸化チタンの重量として３００ｇ／ｌの水性スラリーを調整した。このスラリーを６０℃に保持したまま、撹拌しながら二酸化チタン１００重量部に対して、アルミン酸ナトリウムをＡｌ2Ｏ3換算で２．０重量部添加した後、硫酸でｐＨを５に調整することでアルミニウム酸化物の第一の被覆層を形成した。その後、濾過、洗浄し、さらに１２０℃で１６時間乾燥した。その後、表面被覆する前の二酸化チタン１００重量部に対して３，３，３−トリフルオロプロピルトリメトキシシラン０．５重量部を添加して１１０℃になるまで混合することで第二の被覆層を形成した。これによりアルミニウムの含水酸化物及びフルオロアルキル基含有有機ケイ素化合物を使用した表面被覆層を有する平均一次粒子径０．２１μｍの二酸化チタン（Ａ−１）を得た。なお、二酸化チタンの平均一次粒子径は、走査電子顕微鏡の拡大画像から観察できる粒子径（２０個〜５０個）を平均したものである。
<Titanium dioxide surface coating layer formation 1>
Rutile titanium dioxide particles were mixed with water to prepare an aqueous slurry having a titanium dioxide weight of 300 g / l. While maintaining this slurry at 60 ° C., after adding 2.0 parts by weight of sodium aluminate in terms of Al 2 O 3 to 100 parts by weight of titanium dioxide while stirring, the pH is adjusted to 5 with sulfuric acid. A first coating layer of aluminum oxide was formed. Then, it filtered, wash | cleaned, and also dried at 120 degreeC for 16 hours. Thereafter, 0.5 parts by weight of 3,3,3-trifluoropropyltrimethoxysilane is added to 100 parts by weight of titanium dioxide before surface coating, and mixed until 110 ° C., whereby the second coating layer is formed. Formed. As a result, titanium dioxide (A-1) having an average primary particle diameter of 0.21 μm having a surface coating layer using a hydrous oxide of aluminum and a fluoroalkyl group-containing organosilicon compound was obtained. In addition, the average primary particle diameter of titanium dioxide averages the particle diameter (20-50 particles) which can be observed from the enlarged image of a scanning electron microscope.
＜二酸化チタンの表面被覆層形成２＞
ルチル型二酸化チタン粒子を水と混合して、二酸化チタンの重量として３００ｇ／ｌの水性スラリーを調整した。このスラリーを６０℃に保持したまま、撹拌しながら二酸化チタンの１００重量部に対して、ケイ酸ナトリウムをＳｉＯ2換算で０．５重量部添加した。次いで硫酸でｐＨを約５に調整することでケイ素酸酸化物の被覆層を形成した。引き続き撹拌しながら表面被覆する前の二酸化チタンの１００重量部に対して、アルミン酸ナトリウムをＡｌ2Ｏ3換算で４．０重量部添加した後、硫酸でｐＨを５に調整することでアルミニウム酸化物の被覆層を形成した。その後、濾過、洗浄し、さらに１２０℃で１６時間乾燥した。その後、表面被覆する前の二酸化チタン１００重量部に対して３，３，３−トリフルオロプロピルトリメトキシシラン１．０重量部を添加して１１０℃になるまで混合することで第二の被覆層を形成した。これによりアルミニウムの含水酸化物、ケイ素の含水酸化物及びフルオロアルキル基含有有機ケイ素化合物を使用した表面被覆層を有する平均一次粒子径０．３１μｍの二酸化チタン（Ａ−２）を得た。
<Titanium dioxide surface coating layer formation 2>
Rutile titanium dioxide particles were mixed with water to prepare an aqueous slurry having a titanium dioxide weight of 300 g / l. While maintaining this slurry at 60 ° C., 0.5 part by weight of sodium silicate in terms of SiO 2 was added to 100 parts by weight of titanium dioxide while stirring. Next, the coating layer of silicon oxide was formed by adjusting the pH to about 5 with sulfuric acid. Subsequently, after adding 4.0 parts by weight of sodium aluminate in terms of Al 2 O 3 to 100 parts by weight of titanium dioxide before surface coating with stirring, aluminum oxidation is performed by adjusting the pH to 5 with sulfuric acid. A coating layer of the product was formed. Then, it filtered, wash | cleaned, and also dried at 120 degreeC for 16 hours. Thereafter, the second coating layer is prepared by adding 1.0 part by weight of 3,3,3-trifluoropropyltrimethoxysilane to 100 parts by weight of titanium dioxide before surface coating and mixing until 110 ° C. Formed. As a result, titanium dioxide (A-2) having an average primary particle size of 0.31 μm having a surface coating layer using a hydrous oxide of aluminum, a hydrous oxide of silicon, and a fluoroalkyl group-containing organosilicon compound was obtained.
上記（Ａ−１）と同様の方法により（Ａ−４）、（Ａ−５）、（Ａ−７）、（Ａ−１１）について表１に記載した比率で、二酸化チタンに被覆層を形成した。また、上記（Ａ−２）と同様の方法により（Ａ−３）、（Ａ−６）、（Ａ−８）、（Ａ−９）、（Ａ−１０）についても表１に記載した比率で、二酸化チタンに被覆層を形成した。 A coating layer is formed on titanium dioxide at the ratio described in Table 1 for (A-4), (A-5), (A-7), and (A-11) by the same method as (A-1) above. did. The ratios described in Table 1 for (A-3), (A-6), (A-8), (A-9), and (A-10) by the same method as in (A-2) above. Then, a coating layer was formed on titanium dioxide.
さらに、上記（Ａ−１）と同様の方法により（Ａ−１３）は、表１の記載に従って第一の被覆層と、フルオロアルキル基含有有機ケイ素化合物以外の第二の被覆層を形成した。また、上記（Ａ−２）と同様の方法により（Ａ−１２）は、表１の記載に従って第一の被覆層と、フルオロアルキル基含有有機ケイ素化合物以外の第二の被覆層を形成した。 Furthermore, (A-13) formed the 2nd coating layer other than the fluoroalkyl group containing organosilicon compound according to description of Table 1 by the method similar to the said (A-1). Moreover, (A-12) formed the 2nd coating layer other than a fluoroalkyl group containing organosilicon compound according to description of Table 1 by the method similar to said (A-2).
二酸化チタンの被覆層および被覆量を表１に示す。 Table 1 shows the titanium dioxide coating layer and the coating amount.
＜二酸化チタン＞
表１に示した被覆層を有する二酸化チタン。
＜熱可塑性樹脂＞
（Ｂ−１）ポリエチレンテレフタレート（三井化学社製ＳＡ１３５）
（Ｂ−２）ポリシクロヘキシレンエチレンテレフタレート（デュポン社製サーミックスＰ ＣＴ）
（Ｂ−３）ポリカーボネート（三菱エンジニアリングプラスチックス社製ユーピロンＳ３ ０００）
<Titanium dioxide>
Titanium dioxide having the coating layer shown in Table 1.
<Thermoplastic resin>
(B-1) Polyethylene terephthalate (SA135 manufactured by Mitsui Chemicals)
(B-2) Polycyclohexyleneethylene terephthalate (Thermix PCT manufactured by DuPont)
(B-3) Polycarbonate (Iupilon S3000 manufactured by Mitsubishi Engineering Plastics)
［実施例１］
熱可塑性樹脂（Ｂ−１）１００重量部と二酸化チタン（Ａ−１）１００重量部とを別々の供給口から二軸押出機（日本製鋼所社製）を用いて２９０℃で溶融混練し、ペレタイザーを使用してペレット状のマスターバッチとしての光線反射樹脂組成物を得た。
[Example 1]
100 parts by weight of the thermoplastic resin (B-1) and 100 parts by weight of titanium dioxide (A-1) are melt-kneaded at 290 ° C. using a twin screw extruder (manufactured by Nippon Steel Works) from separate supply ports, A light reflecting resin composition as a pellet-like masterbatch was obtained using a pelletizer.
得られた光線反射樹脂組成物２０重量部と熱可塑性樹脂（Ｂ−１）８０重量部の混合物に単層Ｔダイフィルム成形機（東洋精機社製）を用いて温度２８０℃にて押出し成形を行い、耐久試験（耐熱、耐光試験）、反射率測定、ブリード試験に使用する光線反射シート（それぞれ厚さ５００μｍ）を得た。 A mixture of 20 parts by weight of the obtained light reflecting resin composition and 80 parts by weight of the thermoplastic resin (B-1) was extruded at a temperature of 280 ° C. using a single layer T-die film molding machine (manufactured by Toyo Seiki Co., Ltd.). The light reflection sheet (each having a thickness of 500 μm) used for the durability test (heat resistance, light resistance test), reflectance measurement, and bleed test was obtained.
［実施例２〜１５］
光線反射樹脂組成物の原料および配合量を調整して、それぞれ表２に示す配合に変更し
た以外は実施例１と同様にして光線反射樹脂組成物を使用した光線反射シートを得た。
ただし、実施例９〜１３は参考例である。
[Examples 2 to 15]
A light reflecting sheet using the light reflecting resin composition was obtained in the same manner as in Example 1 except that the raw material and the blending amount of the light reflecting resin composition were adjusted and changed to the blending shown in Table 2, respectively.
However, Examples 9 to 13 are reference examples.
なお、表２および表３の配合比は、光線反射樹脂組成物を用いたシート成形後の重量比を示している。 In addition, the compounding ratio of Table 2 and Table 3 has shown the weight ratio after sheet | seat shaping | molding using a light reflection resin composition.
［実施例１６］
熱可塑性樹脂（Ｂ−１）１００重量部と二酸化チタン（Ａ−１）１５０重量部とを別々の供給口から二軸押出機（日本製鋼所製）を用いて２９０℃にて溶融混練することでペレット状のマスターバッチとしての光線反射樹脂組成物を得た。
[Example 16]
Melting and kneading 100 parts by weight of thermoplastic resin (B-1) and 150 parts by weight of titanium dioxide (A-1) at 290 ° C. using a twin screw extruder (manufactured by Nippon Steel) from separate supply ports. Thus, a light reflecting resin composition as a pellet-like masterbatch was obtained.
得られた光線反射樹脂組成物２５重量部と熱可塑性樹脂（Ｂ−１）７５重量部との混合物に単層Ｔダイフィルム成形機（東洋精機社製）を用いて温度２８０℃にて押出し成形を行い、耐久試験、反射率測定、ブリード試験に使用する光線反射シート（それぞれ厚さ５００μｍ）を得た。 A mixture of 25 parts by weight of the obtained light reflecting resin composition and 75 parts by weight of the thermoplastic resin (B-1) was extruded at a temperature of 280 ° C. using a single-layer T-die film molding machine (manufactured by Toyo Seiki Co., Ltd.). Then, a light reflecting sheet (each having a thickness of 500 μm) used for durability test, reflectance measurement, and bleed test was obtained.
[実施例１７］
熱可塑性樹脂（Ｂ−１）１００重量部と二酸化チタン（Ａ−１）６０重量部とを別々の供給口から二軸押出機（日本製鋼所製）を用いて２９０℃にて溶融混練することでペレット状のマスターバッチとしての光線反射樹脂組成物を得た。
[Example 17]
Melting and kneading 100 parts by weight of thermoplastic resin (B-1) and 60 parts by weight of titanium dioxide (A-1) at 290 ° C. using a twin-screw extruder (manufactured by Nippon Steel) from separate supply ports. Thus, a light reflecting resin composition as a pellet-like masterbatch was obtained.
得られた光線反射樹脂組成物４０重量部と熱可塑性樹脂（Ｂ−１）６０重量部との混合
物に単層Ｔダイフィルム成形機（東洋精機社製）を用いて温度２８０℃にて押出し成形を
行い、耐久試験、反射率測定、ブリード試験に使用する光線反射シート（それぞれ厚さ５
００μｍ）を得た。
ただし、実施例５、９〜１３は参考例である。
A mixture of 40 parts by weight of the obtained light reflecting resin composition and 60 parts by weight of the thermoplastic resin (B-1) was extruded at a temperature of 280 ° C. using a single-layer T-die film molding machine (manufactured by Toyo Seiki Co., Ltd.). A light-reflective sheet (thickness 5 each) used for durability test, reflectance measurement, and bleed test
00 μm).
However, Examples 5 and 9 to 13 are reference examples.
[比較例１］
比較例１は、二酸化チタンＡ−１をＡ−１２に変更した以外は実施例２と同様にして、ペレット状のマスターバッチとしての光線反射樹脂組成物を得た後、表３の配合量となるように調整して光線反射シートを得た。
[Comparative Example 1]
Comparative Example 1 was the same as Example 2 except that titanium dioxide A-1 was changed to A-12, and after obtaining a light reflecting resin composition as a pellet-like masterbatch, It adjusted so that it might become, and obtained the light reflection sheet.
[比較例２、３]
比較例２は、熱可塑性樹脂（Ｂ−１）１００重量部とフルオロアルキル基含有有機ケイ素化合物を表面被覆していない二酸化チタン（Ａ−１２）１００重量部とを別々の供給口から二軸押出機（日本製鋼所社製）を用いて２９０℃で溶融混練し、ペレタイザーを使用してペレット状のマスターバッチとしての光線反射樹脂組成物を得た。また、熱可塑性樹脂（Ｂ−１）９５量部と紫外線吸収剤（Ｅ−１）５重量部とを別々の供給口から二軸押出機（日本製綱所社製）を用いて２９０℃で溶融混練し、ペレタイザーを使用してペレット状の紫外線吸収剤マスターバッチを得た。また、比較例３も二酸化チタンＡ−１２をＡ−１３に、紫外線吸収剤Ｅ−１をＥ−２に変更した以外は比較例２と同様にして、光線反射樹脂組成物と紫外線吸収剤マスターバッチを得た。
[Comparative Examples 2 and 3]
In Comparative Example 2, 100 parts by weight of the thermoplastic resin (B-1) and 100 parts by weight of titanium dioxide (A-12) not coated with a fluoroalkyl group-containing organosilicon compound were biaxially extruded from separate feed ports. The mixture was melt kneaded at 290 ° C. using a machine (manufactured by Nippon Steel Co., Ltd.), and a light reflecting resin composition as a pellet master batch was obtained using a pelletizer. In addition, 95 parts by weight of the thermoplastic resin (B-1) and 5 parts by weight of the ultraviolet absorber (E-1) are separately supplied at 290 ° C. using a twin-screw extruder (manufactured by Tsunasho Co., Ltd.). The mixture was melt-kneaded and a pellet-shaped ultraviolet absorber master batch was obtained using a pelletizer. Comparative Example 3 was the same as Comparative Example 2 except that Titanium Dioxide A-12 was changed to A-13, and the UV absorber E-1 was changed to E-2. Got a batch.
得られた光線反射樹脂組成物３０重量部と、紫外線吸収剤マスターバッチ２重量部と熱可塑性樹脂６８重量部を用いて表３の配合量となるようにシート成形時に調整し、それぞれ光線反射シートを得た。 30 parts by weight of the obtained light reflecting resin composition, 2 parts by weight of the UV absorber masterbatch, and 68 parts by weight of the thermoplastic resin were adjusted at the time of forming the sheet so that the blending amounts shown in Table 3 were obtained. Got.
＜紫外線吸収剤＞
（Ｅ−１）２−［２−ヒドロキシ−３，５−ビス（α，α−ジメチルベンジル）フェニル ］−２Ｈ−ベンゾトリアゾール：ＢＡＳＦ社製ＴＩＮＵＶＩＮ２３４
（Ｅ−２）２−（２−ヒドロキシ−５−ｔｅｒｔ−オクチルフェニル）ベンゾトリアゾー ル
：ＢＡＳＦ社製ＴＩＮＵＶＩＮ３２９
<Ultraviolet absorber>
(E-1) 2- [2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole: TINUVIN234 manufactured by BASF
(E-2) 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole: TINUVIN329 made by BASF
実施例１〜１７および比較例１〜３で得られた光線反射シートを以下の基準で評価し、評価結果を表４に示す。 The light reflecting sheets obtained in Examples 1 to 17 and Comparative Examples 1 to 3 were evaluated according to the following criteria, and the evaluation results are shown in Table 4.
＜耐熱性＞
光線反射シートを、オーブンを用いて温度１５０℃の環境下、５０時間静置することにより耐熱性試験を行った。その後、試験前後の黄色度（ＹＩ値）を、分光測色計（倉敷紡績社製）を用いて測定した。なお黄色度は紫外線による劣化度合いを示しており、値が低いほど劣化が少ない。また、光線反射シートの反射率も紫外可視近赤外分光光度計（島津製作所社製）を用いて測定した。反射率は白色標準板に対しての分光反射率を測定したものである。反射率の判定は波長４００〜７００ｎｍの耐熱試験前後の反射率保持率を下記の基準で行った。
◎：反射率保持率が９７％以上であり、実用上優れる。
〇：反射率保持率が９５〜９７％未満であり、実用上問題無し。
△：反射率保持率が９３〜９５％未満であり、実用範囲内。
×：反射率保持率が９３未満であり、実用不可。
<Heat resistance>
A heat resistance test was performed by allowing the light reflecting sheet to stand in an environment of 150 ° C. for 50 hours using an oven. Thereafter, the yellowness (YI value) before and after the test was measured using a spectrocolorimeter (manufactured by Kurashiki Boseki Co., Ltd.). Yellowness indicates the degree of deterioration due to ultraviolet rays, and the lower the value, the less deterioration. Moreover, the reflectance of the light reflection sheet was also measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). The reflectance is obtained by measuring the spectral reflectance with respect to the white standard plate. The reflectance was determined based on the following criteria for the reflectance retention before and after the heat resistance test at a wavelength of 400 to 700 nm.
A: Reflectance retention is 97% or more, which is excellent in practical use.
A: The reflectance retention is 95 to less than 97%, and there is no practical problem.
(Triangle | delta): A reflectance retention is 93 to less than 95%, and is in a practical range.
X: Reflectance retention is less than 93, impractical.
＜耐光性＞
光線反射シートを、アイスーパーＵＶテスター（岩崎電気社製）を用いて温度６３℃、湿度５０％ＲＨ、照射強度１００ｍＷ／ｃｍ2の環境下、１２時間静置することにより耐光性試験を行った。その後、試験前後の黄色度（ＹＩ値）を、分光測色計（倉敷紡績社製）を用いて測定した。また、光線反射シートの反射率を、紫外可視近赤外分光光度計（島津製作所社製）を用いて測定した。反射率は白色標準板に対しての分光反射率を測定したものである。反射率の判定は波長４００〜８００ｎｍの耐光試験前後の反射率保持率を下記の基準で行った。
◎：反射率保持率が９０％以上であり、実用上優れる。
〇：反射率保持率が８５〜９０％未満であり、実用上問題無し。
△：反射率保持率が８０〜８５％未満であり、実用範囲内。
×：反射率保持率が８０未満であり、実用不可。
<Light resistance>
A light resistance test was performed by allowing the light reflecting sheet to stand for 12 hours in an environment of a temperature of 63 ° C., a humidity of 50% RH, and an irradiation intensity of 100 mW / cm 2 using an eye super UV tester (Iwasaki Electric Co., Ltd.). . Thereafter, the yellowness (YI value) before and after the test was measured using a spectrocolorimeter (manufactured by Kurashiki Boseki Co., Ltd.). Moreover, the reflectance of the light reflection sheet was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). The reflectance is obtained by measuring the spectral reflectance with respect to the white standard plate. The reflectance was determined based on the following criteria for the reflectance retention before and after the light resistance test at a wavelength of 400 to 800 nm.
A: The reflectance retention is 90% or more, which is practically excellent.
A: The reflectance retention is less than 85 to 90%, and there is no practical problem.
(Triangle | delta): A reflectance retention is 80 to less than 85%, and is in a practical range.
X: Reflectance retention is less than 80, impractical.
＜耐ブリード性＞
光線反射シートのブリード有無を評価した。なお、試験は光線反射シートをガラスで挟み込み、オーブン内で温度１５０℃の環境下、１２時間静置の条件によりブリード現象を促した。ブリードの判定は下記の基準で行った。
〇：目視によるブリードが確認されない。
×：ガラスへの付着があり、目視でブリードが確認された。
<Bleed resistance>
The presence or absence of bleeding of the light reflecting sheet was evaluated. In the test, a light reflecting sheet was sandwiched between glasses, and the bleeding phenomenon was promoted by leaving it in an oven at a temperature of 150 ° C. for 12 hours. The bleed was determined according to the following criteria.
◯: No visual bleed is confirmed.
X: There was adhesion to glass and bleed was confirmed visually.
表４の結果より、実施例１〜１７は、全ての評価項目において優れた耐熱性、耐光性および耐ブリード性が得られた。一方、比較例１は耐光性、比較例２、３は耐熱性、耐ブリード性が不良となった。本発明では、二酸化チタン表面を、酸化アルミニウムを含む金属酸化物とフルオロアルキル基含有有機ケイ素化合物とで被覆することで、表面被覆を施さない二酸化チタンと比較して耐熱性、耐光性および耐ブリード性のいずれにも優れる結果が得られた。 From the results of Table 4, Examples 1 to 17 obtained excellent heat resistance, light resistance and bleed resistance in all evaluation items. On the other hand, Comparative Example 1 had poor light resistance, and Comparative Examples 2 and 3 had poor heat resistance and bleed resistance. In the present invention, the surface of titanium dioxide is coated with a metal oxide containing aluminum oxide and a fluoroalkyl group-containing organosilicon compound, so that it has heat resistance, light resistance and bleed resistance compared to titanium dioxide without surface coating. Excellent results were obtained in all of the properties.
Claims (7)
前記フルオロアルキル基含有有機ケイ素化合物は、下記一般式（１）で表されるシラン化合物およびその加水分解縮合反応物の少なくともいずれかであり、
前記熱可塑性樹脂（Ｂ）は、ポリエステル樹脂である、光線反射樹脂組成物。
一般式（１） （ＣｘＨ２ｘ＋１−ｙＦｙ）ｚＳｉ（ＯＲ）４−ｚ
（式中、ｘは１〜１２の整数であり、ｙは３〜２５の整数であり、zは１〜３の整数であり、Ｒは、アルキル基、アリール基、アシル基を表す。ここで、zが１または２の場合、Ｒは同一でも相違していても良い） A first coating layer comprising titanium dioxide (A) and a thermoplastic resin (B), wherein the titanium dioxide (A) is formed of a metal oxide containing aluminum oxide; and fluoroalkyl group-containing organosilicon Having a second coating layer formed of a compound;
The fluoroalkyl group-containing organosilicon compound is at least one of a silane compound represented by the following general formula (1) and a hydrolysis condensation reaction product thereof,
The thermoplastic resin (B) is a polyester resins, the light reflective resin composition.
Formula (1) (C x H 2x + 1-y F y) z Si (OR) 4-z
(Wherein, x is an integer of 1 to 12, y is Ri integer der of 3 to 25, z is an integer from 1 to 3, R represents an alkyl group, an aryl group, an acyl group. Here And when z is 1 or 2, R may be the same or different)
次いで二酸化チタンとフルオロアルキル基含有有機ケイ素化合物とを撹拌して第二の被覆層を形成し二酸化チタン（Ａ）を得る工程、
前記二酸化チタン（Ａ）と熱可塑性樹脂（Ｂ）を混練造粒する工程を含み、
前記フルオロアルキル基含有有機ケイ素化合物は、下記一般式（１）で表されるシラン化合物およびその加水分解縮合反応物の少なくともいずれかであり、
前記熱可塑性樹脂（Ｂ）は、ポリエステル樹脂である、
光線反射樹脂組成物の製造方法。
一般式（１） （ＣｘＨ２ｘ＋１−ｙＦｙ）ｚＳｉ（ＯＲ）４−ｚ
（式中、ｘは１〜１２の整数であり、ｙは３〜２５の整数であり、zは１〜３の整数であり、Ｒは、アルキル基、アリール基、アシル基を表す。ここで、zが１または２の場合、Ｒは同一でも相違していても良い） A step of stirring titanium dioxide and aluminum oxide to form a first coating layer;
Next, the titanium dioxide and the fluoroalkyl group-containing organosilicon compound are stirred to form a second coating layer to obtain titanium dioxide (A),
Including kneading and granulating the titanium dioxide (A) and the thermoplastic resin (B),
The fluoroalkyl group-containing organosilicon compound is at least one of a silane compound represented by the following general formula (1) and a hydrolysis condensation reaction product thereof,
The thermoplastic resin (B) is a polyester resins,
The manufacturing method of a light reflection resin composition.
Formula (1) (C x H 2x + 1-y F y) z Si (OR) 4-z
(Wherein, x is an integer of 1 to 12, y is Ri integer der of 3 to 25, z is an integer from 1 to 3, R represents an alkyl group, an aryl group, an acyl group. Here And when z is 1 or 2, R may be the same or different)
（１）第一の被覆層を有する二酸化チタンを水性スラリーから固液分離し、乾燥した後、フルオロアルキル基含有有機ケイ素化合物と気相中で接触させることにより、被覆層を形成する工程、または、
（２）第一の被覆層を有する二酸化チタンと前記フルオロアルキル基含有有機ケイ素化合物
をスラリー中で接触させることで形成する工程
である、請求項４記載の光線反射樹脂組成物の製造方法。 The step of stirring the titanium dioxide and the fluoroalkyl group-containing organosilicon compound to form a second coating layer to obtain titanium dioxide (A),
(1) A step of forming a coating layer by solid-liquid separation of titanium dioxide having a first coating layer from an aqueous slurry and drying, followed by contact with a fluoroalkyl group-containing organosilicon compound in a gas phase, or ,
(2) The method for producing a light-reflecting resin composition according to claim 4, which is a step of forming titanium dioxide having a first coating layer by contacting the fluoroalkyl group-containing organosilicon compound in a slurry.
前記二酸化チタン（Ａ）は、表面被覆する前の二酸化チタン１００重量部に対して、酸化アルミニウム１．０〜５重量部で形成してなる第一の被覆層、およびフルオロアルキル基含有有機ケイ素化合物０．３〜３重量部で形成してなる第二の被覆層を備え、
前記フルオロアルキル基含有有機ケイ素化合物は、下記一般式（１）で表されるシラン化合物およびその加水分解縮合反応物の少なくともいずれかであり、
前記熱可塑性樹脂（Ｂ）は、ポリエステル樹脂である、光線反射用マスターバッチ。
一般式（１） （Ｃ ｘ Ｈ ２ｘ＋１−ｙ Ｆ ｙ ） ｚ Ｓｉ（ＯＲ） ４−ｚ
（式中、ｘは１〜１２の整数であり、ｙは３〜２５の整数であり、zは１〜３の整数であり、Ｒは、アルキル基、アリール基、アシル基を表す。ここで、zが１または２の場合、Ｒは同一でも相違していても良い） Including 100 parts by weight of the thermoplastic resin (B) and 50 to 160 parts by weight of titanium dioxide (A),
The titanium dioxide (A) is a first coating layer formed of 1.0 to 5 parts by weight of aluminum oxide with respect to 100 parts by weight of titanium dioxide before surface coating, and a fluoroalkyl group-containing organosilicon compound A second coating layer formed by 0.3 to 3 parts by weight ,
The fluoroalkyl group-containing organosilicon compound is at least one of a silane compound represented by the following general formula (1) and a hydrolysis condensation reaction product thereof,
The said thermoplastic resin (B) is a masterbatch for light reflection which is a polyester resin .
Formula (1) (C x H 2x + 1-y F y) z Si (OR) 4-z
(In the formula, x is an integer of 1 to 12, y is an integer of 3 to 25, z is an integer of 1 to 3, and R represents an alkyl group, an aryl group, or an acyl group. , When z is 1 or 2, R may be the same or different)
Claims 1-3 light reflective resin composition according to any one, was or reflector obtained by molding a mixture of any of the master batch for light reflection claim 6, wherein the thermoplastic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014059752A JP6361205B2 (en) | 2014-03-24 | 2014-03-24 | Light reflecting resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014059752A JP6361205B2 (en) | 2014-03-24 | 2014-03-24 | Light reflecting resin composition |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2015184414A JP2015184414A (en) | 2015-10-22 |
| JP2015184414A5 JP2015184414A5 (en) | 2016-12-08 |
| JP6361205B2 true JP6361205B2 (en) | 2018-07-25 |
Family
ID=54351028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014059752A Active JP6361205B2 (en) | 2014-03-24 | 2014-03-24 | Light reflecting resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6361205B2 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006123833A1 (en) * | 2005-05-19 | 2006-11-23 | Teijin Chemicals Ltd. | Polycarbonate resin composition |
| US8883878B2 (en) * | 2006-06-29 | 2014-11-11 | Sabic Global Technologies B.V. | Thermoplastic polycarbonate compositions |
| EP2404969B1 (en) * | 2009-03-04 | 2019-08-07 | Mitsubishi Engineering- Plastics Corporation | Aromatic polycarbonate resin composition, process for producing resin composition, and molded article |
| JP5234209B1 (en) * | 2012-07-20 | 2013-07-10 | 東洋インキＳｃホールディングス株式会社 | Resin composition for solar cell encapsulant |
| JP2014036076A (en) * | 2012-08-08 | 2014-02-24 | Toyo Ink Sc Holdings Co Ltd | Resin composition for solar battery sealing material |
-
2014
- 2014-03-24 JP JP2014059752A patent/JP6361205B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015184414A (en) | 2015-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101360892B1 (en) | Polyester Resin Composition Having Good Reflectance, Heat Resistance, Yellowing Resistance and Humidity Resistance | |
| JP5681331B2 (en) | Polyester resin composition and method for producing the same | |
| JP6690530B2 (en) | Infrared light transmitting polyester resin composition | |
| JP6787128B2 (en) | Infrared light transmissive polyester resin composition | |
| KR101566062B1 (en) | Polyester Resin Composition for Reflectors of Light-Emitting Devices and Molded Article Using Same | |
| TWI670322B (en) | Polyester resin composition and parts for light reflector containing the same and light reflector | |
| WO2015072725A1 (en) | Polycyclohexylenedimethylene terephthalate resin composition | |
| JP6492078B2 (en) | RESIN COMPOSITION FOR REFLECTOR AND REFLECTOR CONTAINING THE SAME | |
| JP5957746B1 (en) | Light reflecting resin composition and molded body | |
| KR101717812B1 (en) | Polyester resin composition having improved anti-discoloration and optical properties | |
| JP6361205B2 (en) | Light reflecting resin composition | |
| JP2019127545A (en) | Polyester resin composition for reflection material and reflection material | |
| JP2020019914A (en) | Polyester resin composition for reflector and reflector | |
| WO2016002193A1 (en) | Polyester resin composition for reflective materials and reflection plate containing same | |
| WO2013125454A1 (en) | Polyester resin for surface-mounted led reflective plate | |
| KR101786192B1 (en) | Thermoplastic resin composition and molded article using the same | |
| US9899580B2 (en) | Polyester resin composition having improved mechanical properties and anti-discoloration | |
| KR101539954B1 (en) | Polyester Resin Composition for Reflectors of Light-Emitting Devices and Molded Article Using Same | |
| JP4526756B2 (en) | Thermoplastic resin composition, molded article and lighting fixture comprising the same | |
| JP2016117864A (en) | Resin composition for light reflection and light reflection sheet | |
| CN105462179A (en) | Thermoplastic Resin Composition and Molded Article Using the Same | |
| JP2015175976A (en) | Ray-reflective resin composition | |
| JP2004291492A (en) | Light reflector and lighting equipment equipped with the light reflector | |
| JP6540288B2 (en) | Infrared ray transmitting polyester resin composition | |
| JP6583665B2 (en) | Polyester resin composition for automotive lamp parts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20161019 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20161028 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170615 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170627 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170825 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20170829 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20170829 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20180123 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180328 Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20180328 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20180404 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20180529 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180611 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 6361205 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |