JPH0323221A - Production of titanium dioxide pigment - Google Patents
Production of titanium dioxide pigmentInfo
- Publication number
- JPH0323221A JPH0323221A JP15384889A JP15384889A JPH0323221A JP H0323221 A JPH0323221 A JP H0323221A JP 15384889 A JP15384889 A JP 15384889A JP 15384889 A JP15384889 A JP 15384889A JP H0323221 A JPH0323221 A JP H0323221A
- Authority
- JP
- Japan
- Prior art keywords
- titanium dioxide
- slurry
- coating
- minutes
- gloss
- 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.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000000049 pigment Substances 0.000 title claims abstract description 34
- 239000004408 titanium dioxide Substances 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000000576 coating method Methods 0.000 claims abstract description 51
- 239000011248 coating agent Substances 0.000 claims abstract description 48
- 239000002002 slurry Substances 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 229910052718 tin Inorganic materials 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 5
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 30
- 238000010298 pulverizing process Methods 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000011282 treatment Methods 0.000 abstract description 17
- 238000001238 wet grinding Methods 0.000 abstract description 15
- 239000002932 luster Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910017053 inorganic salt Inorganic materials 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- 239000004576 sand Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 238000009837 dry grinding Methods 0.000 description 4
- 150000002484 inorganic compounds Chemical class 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000019983 sodium metaphosphate Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 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
- 239000011324 bead Substances 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 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
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000379 antimony sulfate Inorganic materials 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- QIESBVQBFFBEJV-UHFFFAOYSA-N chloro hypochlorite;tin Chemical compound [Sn].ClOCl QIESBVQBFFBEJV-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- -1 titanium halides Chemical class 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、分散性・光沢、耐久性などの顔料特性に優れ
た二酸化チタン顔料の製造方法に関する．本発明方法で
得られる二酸化チタン顔料は、一般の二酸化チタン顔料
と同様に、塗料、プラスチック、インキなどに使用され
得る他に、特にその優れた分散性・光沢、耐久性を利用
して自動車用塗料に代表される高級工業用塗料に有用な
ものである．
〔従来の技術〕
二酸化チタン顔料は、隠蔽力、着色力に優れた白色顔料
として塗料、プラスチック、インキなどの幅広い分野で
使用されているが、要求される顔料特性は年々厳しいも
のになってきている．一般に、二酸化チタン顔料は、二
酸化チタン粗顔料一湿式粉砕一表面被覆一ろ過・洗浄・
乾燥一乾式粉砕の工程で仕上げ処理され、その分散性・
光沢、耐久性などの顔料特性を改善するために前記表面
被覆工程でその表面がアルミニウム、ケイ素、チタニウ
ム、ジルコニウム、スズなどの含水酸化物或は酸化物で
被覆されている．表面被覆物は、要求される顔料特性に
応じて選択され、例えば分散性・光沢を改善するときは
、アルミニウム、チタニウムなどの含水酸化物を、耐久
性を改善するときは、ケイ素、ジルコニウム、スズなど
の含水酸化物を被覆処理するのが普通である。より望ま
しい耐久性を付与するために表面被ｒｆｌ後５００℃以
上の温度で焼成し、その後更に表面被覆する方法（特公
昭４７−１９５１４号）或は表面被ｆｆｉ後乾式粉砕し
、その後更に表面被覆する方法（特公昭４０１２１６６
号）などが提案されている．〔発明が解決しようとする
問題点〕
特公昭４７−１９５１４号に提案されている方法では、
表面被覆後焼成することにより耐久性の著しい向上がも
たらされる半面、焼戒による焼結等の悪影響で分散性・
光沢が著しく低下し、またコスト高となり経済的でない
．特公昭４０−１２１６６号に提案されている方法は、
表面被覆後ろ過、洗浄、乾燥し、その後乾式粉砕を行な
った後更に表面被覆するものであり、工程が複雑となっ
て経済的でないと共に分散性・光沢、耐久性などの改善
が不十分である．
このように、従来技術では近年要求されている高度の耐
久性と分散性・光沢とを同時に満足するものは得られ難
い現状である．
〔問題点を解決するための手段〕
本発明者等は前記従来技術の問題点を解決するべく、表
面被覆工程及びその前後の処理工程の各処理条件と顔料
特性との関係について詳細に検討した．その結果（イ）
二酸化チタン分ｆｉｋスラリー中で、該二酸化チタンの
表面に金属の含水酸化物を沈殿させ、被覆すると二酸化
チタン粒子が凝集し、その後更に被覆を繰り返す場合は
該′ｌｉｌ集粒子の表面を被覆することとなり、これが
分散性・光沢、耐久性低下の原因となっていること、（
ロ〉表面被覆によるＤ集の程度は主に被覆物の種類によ
って異なり、ケイ素、ジルコニウムの含水酸化物を被覆
した場合が凝集が強く、アルミニウム、チタニウム、ス
ズの含水酸化物の場合は比較的弱いこと、（ハ）＠集の
比較的弱い含水酸化物でも被覆量が多い場合に１よ擬集
を招くこと、（二）表面被覆による凝集粒子を粉砕、分
散するために湿式粉砕を行なうと意外にも表面被覆物の
剥離の発生もなく良好な二酸化ヂタン分敗スラリーとな
り、その後繰り返す表面被覆処理も順調に行なえること
、（ホ〉このようにして得られる二酸化チタン顔料は、
単一粒子近くまでよく分敗された粒子の表面に各種の含
水酸化物が被覆されているので分敗性・光沢及び耐久性
の向上が著しいことなどの知見が得られた．本発明はこ
のような知見に基づくものである．
すなわち本発明は、二酸化チタンの水性スラリー中で該
粒子の表面にケイ素、ジルコニウム、チタニウム、アル
ξニウム、アンチモン、スズ及びセリウムから或る群よ
り選択される二種以上の金属の含水酸化物を被覆する方
法において、該被覆工程の途中で１回以上の湿式粉砕を
行なうことを特徴とする二酸化チタン顔料の製造方法で
ある．本発明において、該粒子としての二酸化チタン（
粗顔料）は、チタン塩水溶液を加水分解して得られる含
水酸化チタンを焼或する方法（硫酸法）や、ハロゲン化
チタンを気相酸化する方法（塩素法）によって製造され
た単一粒子径０．１〜０．４μｍのルチル型結晶の焼結
凝集物を、予め水に分敗させて水性スラリーとし、アル
カリを加えてｐｌ１を８、５〜１２に調整した後分散剤
を添加し、次に湿式粉砕、分級処理して出来るだけ単一
粒子に近い粒径に調整して用いる．ルチル型結晶の焼結
凝？物に代えてアナタース型結晶ａ集物或は、ルチル型
とアナタース型の混合物を用いることも出来るが、その
改良された耐久性は、ルチル型のものに比較すると、か
なり低いレベルである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a titanium dioxide pigment having excellent pigment properties such as dispersibility, gloss, and durability. The titanium dioxide pigment obtained by the method of the present invention, like general titanium dioxide pigments, can be used in paints, plastics, inks, etc. In addition, it can be used in automobiles by taking advantage of its excellent dispersibility, gloss, and durability. It is useful for high-grade industrial paints such as paints. [Prior Art] Titanium dioxide pigments are used in a wide range of fields such as paints, plastics, and inks as white pigments with excellent hiding power and coloring power, but the required pigment properties are becoming more severe year by year. There is. In general, titanium dioxide pigments are produced by: - crude titanium dioxide pigment - wet grinding - surface coating - filtration, washing, and
It is finished in the process of drying and dry grinding, and its dispersibility and
In order to improve pigment properties such as gloss and durability, the surface is coated with a hydrous oxide or oxide of aluminum, silicon, titanium, zirconium, tin, etc. in the surface coating step. The surface coating is selected depending on the required pigment properties. For example, to improve dispersibility and gloss, use hydrous oxides such as aluminum or titanium, and to improve durability, use silicon, zirconium, or tin. It is common to coat with a hydrous oxide such as. In order to impart more desirable durability, the surface is coated with rfl, then fired at a temperature of 500°C or higher, and then the surface is further coated (Japanese Patent Publication No. 47-19514), or after the surface is coated with ffi, it is dry-pulverized, and then the surface is further coated. How to
) have been proposed. [Problems to be solved by the invention] In the method proposed in Japanese Patent Publication No. 47-19514,
Although firing after surface coating significantly improves durability, it also reduces dispersibility and
The gloss is significantly reduced and the cost is high, making it uneconomical. The method proposed in Special Publication No. 40-12166 is
After surface coating, the product is filtered, washed, dried, and then dry-pulverized before further surface coating.The process is complicated and uneconomical, and improvements in dispersibility, gloss, durability, etc. are insufficient. ．． As described above, it is currently difficult to obtain a product that simultaneously satisfies the high degree of durability, dispersibility, and gloss required in recent years using conventional techniques. [Means for Solving the Problems] In order to solve the problems of the prior art, the present inventors conducted a detailed study on the relationship between the pigment properties and each treatment condition of the surface coating step and the treatment steps before and after the surface coating step. ．． The result (a)
In the titanium dioxide component fik slurry, a hydrous oxide of the metal is precipitated on the surface of the titanium dioxide, and when the titanium dioxide particles are coated, the titanium dioxide particles agglomerate, and if coating is repeated thereafter, the surface of the 'lil aggregate particles is coated. This is the cause of the decrease in dispersibility, gloss, and durability (
B> The degree of D collection due to surface coating mainly depends on the type of coating, with strong aggregation when coated with hydrous oxides of silicon and zirconium, and relatively weak when coated with hydrous oxides of aluminum, titanium, and tin. (3) Even a relatively weak hydrous oxide with a concentration of 1 will cause agglomeration if the amount of coating is large, and (2) unexpected problems will occur if wet pulverization is used to crush and disperse agglomerated particles due to surface coating. (E) The titanium dioxide pigment obtained in this way has the following characteristics: a good titane dioxide decomposition slurry is obtained without any peeling of the surface coating, and subsequent surface coating treatments can be carried out smoothly;
It was found that the surface of the particles, which were well separated to almost a single particle, was coated with various hydrous oxides, which resulted in remarkable improvements in breakage resistance, gloss, and durability. The present invention is based on such knowledge. That is, the present invention provides hydrous oxides of two or more metals selected from a group consisting of silicon, zirconium, titanium, aluminum, antimony, tin, and cerium on the surface of the particles in an aqueous slurry of titanium dioxide. This is a method for producing a titanium dioxide pigment, characterized in that, in the coating method, wet pulverization is performed one or more times during the coating step. In the present invention, titanium dioxide (
Coarse pigments) are single particle particles produced by sintering hydrous titanium oxide obtained by hydrolyzing an aqueous titanium salt solution (sulfuric acid method) or gas phase oxidation of titanium halides (chlorine method). Sintered aggregates of rutile type crystals of 0.1 to 0.4 μm are predissolved in water to form an aqueous slurry, and after adjusting the pl1 to 8, 5 to 12 by adding alkali, a dispersant is added, Next, use wet grinding and classification to adjust the particle size to as close to a single particle as possible. Sintering of rutile type crystal? Although anatase-type crystal collections or a mixture of rutile and anatase types can be used instead of the rutile-type crystals, the improved durability thereof is at a considerably lower level than that of the rutile-type crystals.
上記の粗頗料スラリーのＴｉＯ■濃度は１００〜６ ０
０ ｇ７Ｅ、望ましくは１００〜５ ０ ０ ｇ／１
とする．
本発明における表面被覆処理は次のようにして行なう。The TiO concentration of the above crude feed slurry is 100 to 60
0 g7E, preferably 100-500 g/1
Suppose that The surface coating treatment in the present invention is carried out as follows.
すなわち、まず湿式粉砕、分級により得られる上記粗顔
料スラリーを、温度５０℃以上に維持しながら、水溶性
無機塩溶液を加え、引続き酸またはアルカリを加えて該
無機塩を中和し、無機化合物を沈殿させることにより行
なう。沈殿生戒完了後、普通１０分以上熟戒するのが良
い．水溶性無機塩としては、一般に表面被覆剤として使
用されているものでよく、例えば硫酸アルミニウム、塩
化アルミニウム、アル烏ン酸ナトリウム、ケイ酸ナトリ
ウム、ケイ酸カリウム、硫酸チタン、四塩化チタン、塩
化アンチモン、硫酸アンチモン、酸塩化ジルコニウム、
塩化ジルコニウム、硫酸ジルコニウム、硝酸ジルコニウ
ム、塩化スズ、硫酸スズ、酢酸スズ、オキシ塩化スズ、
塩化セリウム、硫酸セリウム、硝酸セリウム、酢酸セリ
ウムなどを挙げることができる．中和剤として使用する
酸としては例えば硫酸、塩酸などが、アルカリとしては
例えばアルカリ及びアルカリ土類金属の水酸化物または
炭酸塩、アンモニア、アミン類などが挙げられる．
本発明においては、表面被覆処理工程の途中で、すなわ
ち二酸化チタン粗顔料のスラリーに水溶性無機塩の少な
くとも一種を加え酸またはアルカリによる中和反応によ
り、その含水酸化物を沈殿、被覆した後であって、次の
被覆を行なう前に湿式粉砕を行ない、表面被覆で生じた
二酸化チタン粒子の凝集をほぐすことに特徴がある．従
って、二種以上の金属の含水酸化物で被覆する本発明に
おいては、被覆工程の途中で１回以上の湿式粉砕を行な
うこととなるが、ケイ素或はジルコニウムの含水酸化物
を被覆した後に湿式粉砕した場合、特にその効果は大き
い．特に耐久性を向上させるためには、前記ケイ素の含
水酸化物は特公昭４７−４５１７３号公報に記載されて
いるような方法で処理してち密な無定形シリカとするの
が良い．無機化合物の表面被覆総量は、粗頗料のＴｉＯ
ｚ重量基準で各酸化物として０． ５〜１５％、好まし
くはｌ〜ｌＯ％である．
前記湿式粉砕に際し、第１の表面被覆後のスラリーを予
めアルカリを加えてｐｌ１を８．５〜ｌ２に調整し、必
要に応じ更に分敗剤を加えておくのが望ましい ｉ式粉
砕は、一般に使用されているわ）砕機、例えばサンドミ
ル、振動２ル、ボールミル、ベブルミル、ビーズミルな
どを用いて行なうことができる．使用する籾砕機の種類
によって粉砕条件は異なるが、普通、凝集粒子が殆んど
分敗するまで粉砕すればよく、例えばサンド藁ルを用い
て粉砕する場合は、粉砕メディアとして直径約１關のジ
ルコニアビーズを用い、サンドミル中でのスラリーの滞
留時間が３分〜５分になるようにスラリーを供給し、し
かも該スラリーを１〜４回通過するように条件設定する
のが望ましい．必要に応じ、湿式粉砕後分級、整粒した
り、スラリー中のＴｉ（ｈ濃度を調整したりする．
このように、本発明においては、Ｔｉ（ｈ粗顔料調製の
際の湿式粉砕処理を含めると、湿式粉砕処理を２回以上
行なうものであるが、全体の湿式粉砕時間を一定とした
場合には、粗顔料スラリーの調製時の湿式粉砕処理に比
較して、表面処理工程の途中で行なう湿式粉砕の強度を
高める方が分散性・光沢の改善効果の点から望ましい．
粉砕強度を高めるには、例えばサンドミルの場合被処理
スラリーのサンドミル内での滞留時間を長くしたり、サ
ンドミルへの供給回数を多くしたり、粉砕メディアの材
質、直径、充填量或はスラリー粘度、顔料濃度を適宜選
定することによって行なうことができる．
本発明においては、湿式粉砕処理後ろ過、洗浄すること
なく引続き水性スラリーに水溶性無機塩溶液を加え、中
和して第２以降の表面被覆処理を行なう．この処理は第
１の表面被覆処理と同様に、前記無機化合物のうち少な
くとも一種を適宜選択して被覆することができる。なお
、複数の無機化合物を被覆する場合は、各化合物の被覆
毎に被覆後湿式粉砕を行なうのが好ましい。また、複数
の無機化合物を被覆する場合は、各化合物を順番に沈殿
させたり、または同時に共沈させたりしても良い．
本発明における被覆処理は、水性スラリー中に水溶性無
機塩溶液を加え、これを酸またはアルカリで中和して含
水酸化物を沈殿させる。この場合、無機塩溶液を加えた
後、酸またはアルカリを加えて中和する方法、予め、酸
またはアルカリを加えた後無機塩溶液を加えて中和する
方法、無機堪溶液と酸またはアルカリとを同時に加えな
がら中和する方法などが知られているが、これらの方法
を適宜選択することができる。That is, first, a water-soluble inorganic salt solution is added to the crude pigment slurry obtained by wet grinding and classification while maintaining the temperature at 50° C. or higher, and then an acid or alkali is added to neutralize the inorganic salt. This is done by precipitating. After completing the precepts, it is usually best to meditate for at least 10 minutes. The water-soluble inorganic salts may be those commonly used as surface coating agents, such as aluminum sulfate, aluminum chloride, sodium alkuronate, sodium silicate, potassium silicate, titanium sulfate, titanium tetrachloride, and antimony chloride. , antimony sulfate, zirconium acid chloride,
Zirconium chloride, zirconium sulfate, zirconium nitrate, tin chloride, tin sulfate, tin acetate, tin oxychloride,
Examples include cerium chloride, cerium sulfate, cerium nitrate, and cerium acetate. Examples of acids used as neutralizing agents include sulfuric acid and hydrochloric acid, and examples of alkalis include hydroxides or carbonates of alkali and alkaline earth metals, ammonia, and amines. In the present invention, in the middle of the surface coating treatment process, that is, after adding at least one water-soluble inorganic salt to the slurry of the titanium dioxide crude pigment and precipitating the hydrous oxide by a neutralization reaction with an acid or alkali, the coating is performed. One of its characteristics is that it performs wet grinding before applying the next coating to loosen the agglomeration of titanium dioxide particles that occur during the surface coating. Therefore, in the present invention, in which hydrous oxides of two or more metals are coated, wet pulverization is performed at least once during the coating process. The effect is especially great when crushed. In particular, in order to improve durability, it is preferable to treat the hydrous oxide of silicon to form a compact amorphous silica by the method described in Japanese Patent Publication No. 47-45173. The total amount of surface coating of inorganic compounds is
z0.0 for each oxide on a weight basis. 5 to 15%, preferably 1 to 10%. During the wet grinding, it is desirable to add an alkali to the slurry after the first surface coating in advance to adjust the PL1 to 8.5 to 12, and further add a disintegrating agent if necessary. This can be done using a crusher such as a sand mill, vibrating mill, ball mill, bevel mill, or bead mill. Although the crushing conditions differ depending on the type of rice crusher used, it is usually sufficient to crush until most of the aggregated particles are broken down. Using zirconia beads, it is desirable to supply slurry so that the residence time of the slurry in the sand mill is 3 to 5 minutes, and to set conditions such that the slurry is passed 1 to 4 times. If necessary, after wet pulverization, the Ti(h) concentration in the slurry may be adjusted by classifying, sizing, or adjusting the Ti(h) concentration in the slurry. The wet pulverization process is performed two or more times, but when the overall wet pulverization time is constant, compared to the wet pulverization process during the preparation of the coarse pigment slurry, the wet pulverization process is performed in the middle of the surface treatment process. It is desirable to increase the strength of wet grinding from the viewpoint of improving dispersibility and gloss.
In order to increase the grinding strength, for example, in the case of a sand mill, the residence time of the slurry to be processed in the sand mill may be increased, the number of times the slurry is fed to the sand mill may be increased, the material, diameter, filling amount of the grinding media, slurry viscosity, etc. This can be done by selecting the pigment concentration appropriately. In the present invention, after the wet grinding treatment, a water-soluble inorganic salt solution is added to the aqueous slurry without filtration or washing to neutralize it and perform the second and subsequent surface coating treatments. In this treatment, as in the first surface coating treatment, at least one of the above-mentioned inorganic compounds can be appropriately selected and coated. In addition, when coating with a plurality of inorganic compounds, it is preferable to perform wet pulverization after coating each compound. Moreover, when coating with a plurality of inorganic compounds, each compound may be precipitated in order or may be co-precipitated simultaneously. In the coating treatment in the present invention, a water-soluble inorganic salt solution is added to an aqueous slurry, and this is neutralized with an acid or an alkali to precipitate a hydrous oxide. In this case, a method is to add an inorganic salt solution and then add an acid or alkali for neutralization, a method to add an acid or alkali in advance and then add an inorganic salt solution for neutralization, or a method to neutralize by adding an inorganic salt solution and an acid or alkali. There are known methods of neutralizing while simultaneously adding , and these methods can be selected as appropriate.
最終の湿式粉砕の後の表面被覆は凝集力の弱いアルミニ
ウム、チタニウム、スズ、セリウム、アンチモンなどの
含水酸化物が望ましいと考えられるが、一ａによく知ら
れているように、樹脂との親和性の点からアルミニウム
の水酸化物が好まし？。最終の表面被覆量はＴｉＯ■重
遣基準で各酸化物換算で３％以下、好ましくは０． １
〜２％である。For the surface coating after the final wet grinding, it is considered desirable to use hydrous oxides such as aluminum, titanium, tin, cerium, and antimony, which have weak cohesion, but as is well known in 1a, Is aluminum hydroxide preferable in terms of properties? . The final surface coating amount is 3% or less in terms of each oxide based on the weight of TiO, preferably 0. 1
~2%.
ケイ素、ジルコニウムの含水酸化物を最柊に被覆する場
合は１％以下好ましくは０． ５％以下である。When coating the hydrated oxides of silicon and zirconium on the top layer, the amount is 1% or less, preferably 0. It is less than 5%.
以上のようにして表面被覆処理された二酸化チタン顔料
スラリーは、一定時間、普通１０〜６０分間、４０〜９
０℃の温度で熟戒後公知の方法に従ってろ過、洗浄し、
乾燥、乾式粉砕などの工程を経て二酸化チタン顔料製品
とする。この乾燥後の乾式粉砕は通常、ジェットξル、
マイクロミルなどの気流粉砕機で行なうが、本発明方法
では、この乾式粉砕の低エネルギー化も可能である．〔
実施例〕
実施例１
（ＴｉＯｚ粗顔料スラリーの調製〉
四塩化チタンを気相で酸化して得られた二酸化チタンを
含有する水性スラリー（Ｔｉ０２濃度５００ｇ／ｌ）に
水酸化ナトリウム溶液を添加してスラリーのｐｌ１を１
１．０に調整した後、メタリン酸ナトリウムを添加して
二酸化チタンをよく分敗させた．？に、得られたスラリ
ーをサンドミルで、滞留時間５分、１回通しの条件下で
湿式粉砕し、分級整粒してＴｉ（ｂ基準３ ８ ０ ｇ
／Ｉ！の水性スラリーとした．
（被覆処理）
このスラリ−３１！を６０℃に加熱し、この温度に保ち
ながら、ＳｉＯｚとして１００ｇ／１の濃度のケイ酸ナ
トリウム水溶液５ ７ ０ｍｊ！を十分な攪拌下で、３
０分間で添加した。このスラリーを８０℃に昇温し、１
０分間攪拌後、濃度１０重四％の希硫酸を６０分間で添
加し、ｐｌｌ４．０まで中和してち密なシリ力水和物を
被覆した．
（湿式粉砕処理）
次に、水酸化ナトリウム溶液を添加してスラリーのｐｌ
＋を１０．５に調整した後、メタリン酸ナトリウムを添
加し、サンドミルで、滞留時間５分、２回通しの条件下
で湿式粉砕した．
（被覆処理）
このスラリーを６０℃の温度に保ちなからＴｉＯ■とし
て１００ｇ／ｌの濃度の四塩化チタン水溶液２ ２ ８
ｍ７！を攬拌下に２０分間で添加した後濃度１０重量％
の水酸化ナトリウム溶液を添加してスラリーのｐｌ＋を
７．０とし、３０分間攪拌してチタニウムの含水酸化物
を被覆した．
（湿式粉砕処理）
次に、水酸化ナトリウム溶液を添加してスラリ一〇ｐｌ
１を１０．５に調整した後、メタリン酸ナトリウムを添
加し、サンドミルで滞留時間５分、１回通しの条件下で
湿式粉砕した．
（被覆処理）
このスラリーを６０℃に保ちなから＾ｌ８０，として１
００ｇ／１の濃度のアル旦ン酸ナトリウム水溶液１ ７
１＋ｍｌを撹拌下で、２０分間で添加した後、濃度１
０重量％の希硫酸を添加してスラリーのｐｌ＋を７．２
とし、６０分間Ｐ威してアルミニウムの含水酸化物を被
覆した．
この後、ろ過、洗浄し、１２０℃で５時問乾燥し気流粉
砕機（ジェットミル、冨士産業製、２００ＡＦ型）で粉
砕して本発明方法による二酸化ヂタン顛料（Ａ）を得た
。The titanium dioxide pigment slurry surface-coated as described above is coated for a certain period of time, usually 10 to 60 minutes, for 40 to 90 minutes.
After careful study at a temperature of 0°C, filter and wash according to known methods,
It is made into titanium dioxide pigment products through processes such as drying and dry grinding. This dry pulverization after drying is usually carried out by jet
This is carried out using an air flow mill such as a micro mill, but the method of the present invention also allows for low-energy dry milling. [
Examples] Example 1 (Preparation of TiOz crude pigment slurry) A sodium hydroxide solution was added to an aqueous slurry containing titanium dioxide (TiO2 concentration 500 g/l) obtained by oxidizing titanium tetrachloride in the gas phase. slurry pl1 to 1
After adjusting the titanium dioxide to 1.0, sodium metaphosphate was added to thoroughly decompose the titanium dioxide. ? Next, the obtained slurry was wet-pulverized in a sand mill under conditions of a residence time of 5 minutes and one pass, and was classified and sized to obtain Ti (b standard 380 g).
/I! It was made into an aqueous slurry. (Coating treatment) This slurry-31! was heated to 60°C, and while keeping it at this temperature, 570 mj of an aqueous sodium silicate solution with a concentration of 100 g/1 as SiOz! under thorough stirring, 3
Added in 0 minutes. This slurry was heated to 80°C and
After stirring for 0 minutes, dilute sulfuric acid with a concentration of 10:4% was added over 60 minutes to neutralize to a pll of 4.0 and coat the compact silicate hydrate. (Wet grinding process) Next, add sodium hydroxide solution to pl of the slurry.
After adjusting the + to 10.5, sodium metaphosphate was added, and the mixture was wet-milled in a sand mill under conditions of a residence time of 5 minutes and two passes. (Coating treatment) While maintaining this slurry at a temperature of 60°C, titanium tetrachloride aqueous solution with a concentration of 100 g/l as TiO 2 2 8
m7! was added under stirring for 20 minutes to a concentration of 10% by weight.
of sodium hydroxide solution was added to bring the pl+ of the slurry to 7.0 and stirred for 30 minutes to coat the hydrous titanium oxide. (Wet grinding process) Next, add sodium hydroxide solution to make 10 pl of slurry.
1 was adjusted to 10.5, sodium metaphosphate was added, and wet milling was carried out in a sand mill under conditions of a residence time of 5 minutes and one pass. (Coating treatment) This slurry must be kept at 60℃.
Sodium altanate aqueous solution with a concentration of 00g/1 7
After adding 1+ml under stirring in 20 minutes, a concentration of 1
0 wt% dilute sulfuric acid was added to bring the pl+ of the slurry to 7.2.
The hydrated oxide of aluminum was coated by applying P for 60 minutes. Thereafter, it was filtered, washed, dried at 120° C. for 5 hours, and pulverized with an air flow pulverizer (Jet Mill, manufactured by Fuji Sangyo, Model 200AF) to obtain a ditane dioxide material (A) according to the method of the present invention.
実施例２〜１２
実施例ｌにおいて、表面被覆剤、被覆扉及び湿式わ｝砕
の処理時間を表１のように変更にすること以外は同様に
処理して本発明方法による二酸化チタン顔料（Ｂ）〜（
Ｌ）を得た。なお、ジルコニウム、スズの含水酸化物を
被覆するために二酸化チタンのスラリーには、それぞれ
硫酸ジルコニウム及び塩化スズを添加した．
比較例１〜６
前記各実施例において、表１に示すように表面被覆後の
湿式粉砕を行なわないこと以外は同様に処理して二酸化
チタン顔料（Ｍ）〜（Ｒ）を得た．比較例７
実施例ｌ２においてち密なシリ力水和物を被覆した後、
湿式粉砕を行なうことなく、これに代えてろ過、洗浄し
、１２０℃で５時間乾燥し、その後ジェットミル（富士
産業製、２００八Ｆ゛型）で、Ｉ Ｋｇ／５分の処理量
で乾式粉砕し、引続き水中に投入したこと以外は同様に
処理して二酸化チタン顔料（Ｓ）を得た。Examples 2 to 12 Titanium dioxide pigments (B )～(
L) was obtained. Note that zirconium sulfate and tin chloride were added to the titanium dioxide slurry to coat the hydrous oxides of zirconium and tin, respectively. Comparative Examples 1 to 6 Titanium dioxide pigments (M) to (R) were obtained in the same manner as in each of the above Examples, except that wet pulverization after surface coating was not performed as shown in Table 1. Comparative Example 7 After coating the dense silicate hydrate in Example 12,
Instead of wet grinding, it was filtered, washed, dried at 120°C for 5 hours, and then dry-milled using a jet mill (Fuji Sangyo, Model 2008F) at a throughput of I kg/5 minutes. A titanium dioxide pigment (S) was obtained by the same treatment except that it was pulverized and then poured into water.
？施例１３
前記実施例１において、シリカの含水酸化物の被覆処理
を次のようにして行ない、チタニウムの含水酸化物の被
覆量をＴｉＯｔｆＥ量基準でＴｉＯ■として１．０％と
すること以外は同様に処理して本発明方法による二酸化
チタン顔料（Ｔ）を得た．（シリカの含水酸化物の被覆
）
実施例ＩのＴｉｌｔ粗頭料スラリー（Ｔｉｅ．基準３８
０ｇ／ｌ＞ ３ｔｔを６０℃に加熱し、この温度に保ち
ながら、Ｓｉｎ．として１ ０ ０ ｇ／ｌの濃度のケ
イ酸ナトリウム水溶液５ １ｍｌを、十分な攪拌下で２
０分間で添加した．引き続き、このスラリーを１０分間
撹拌後、濃度１０ｆＥ量％の希硫酸を添加してスラリー
のｐｌ１を７．０とし、３０分間攪拌してシリカの含水
酸化物を被覆した．
実施例１４及び比較例８
実施例ｌ３において、湿式粉砕の処理の回数、時間を表
３のように変更すること以外は同様に処理して二酸化チ
タン顔料（Ｕ）及び（Ｖ）を得た．試験例
前記実施例及び比較例の二酸化チタン顔料（Ａ）〜（Ｖ
）についてその性能を試験し、表１〜表４の結果を得た
．
なお、表１及び表３の処理内容で、「湿・粉」とは湿式
粉砕を「乾・粉」とは乾式粉砕を、その後のカツコ内の
数字は粉砕時間（単位、分〉を示す．また、ｒＳｉ（５
％）」のように元素名とカツコ内の数字で表示したのは
、表面被覆物及び被覆！（酸化物換算、二酸化チタン粗
顔料のＴｉ０２重量基準）を示している．
表１〜表４の性能評価は次のようにして行なった．
試験板の作成
Ｔｌ＋ 光沢測定用５，＜験板
実施例及び比較例で得られた二酸化チタン顔料をヤシ油
変性短油アルキド樹脂／プチル化メラごン樹脂（７／３
重量比）ワニス中へ混和し、ペイントシェーカー（レフ
ドデビル社製＃５１１０）で分＋ｉＩｉ．ｔ，て塗料化
した．
このものをガラス板（１ ５ｃＩＩＸ １ ０ａｍ）に
ドクターブレードを用い約４５μ厚（乾燥塗膜として）
で塗布し、１２０℃で３０分間焼付けて試験板を作成し
た．なお、過焼付後の光沢は、この試験板の初期光沢を
測定した後、更に１８０℃で３０分間焼付けて得られた
ものを試験板とした．（２）耐久性測定用試験仮
前記（１）項と同じ塗料をリン酸亜鉛処理鋼仮（７Ｃｌ
ｌ Ｘ ｌ ５ ｃｍ）にワイヤー・アプリケーターを
用い約６０μ厚（乾燥塗膜として）で塗布し、１３０℃
で３０分間焼付けて試験板を作威した．光沢度の測定
試験板の初期光沢及び過焼付後の光沢について２０°−
２０°及び６０°−６０”鏡面光沢をグロスメーター（
村上色彩技術研究所製ＧＭ− ２ ６Ｄ型）で測定した
．また、耐久性測定用試験板については初期光沢（６０
°−６０°鏡面光沢）を同様に測定した．
耐久性評価
光沢保持性は、カーボンアーク型サンシャインウエザー
メーター装置（スカ１式験機ＫＫ製、ＷＥ−ＳＵＮ−Ｄ
Ｃ型）内で試験板を促進曝ｎ（６０分照射中に１２分降
水、ブラックパネル温度６３±３℃）し、一定時間毎に
６０”−６０＠鏡面光沢度を測定して評価した．また、
耐白亜化性は、白亜化開姑時間及び日本塗料検査協会の
塗膜評価基準にしたがって測定した１０００時間或は７
６０時間曝露後の塗面の白亜化発生程度（０〜１０）で
評価した．発生程度１０は白亜化が発生していないこと
を示し、以下数値が小さくなるに従って白亜化発生程度
が大きいことを示す．
〔発明の効果〕
本発明方法では、表面被覆で発生した二酸化チタンの凝
集粒子を湿式粉砕してほぐし、引き続き表面被覆をする
ので、この表面被覆は、単一粒子に近い、非常に分散の
良い状態で均一に行なわれる．従って、表１〜表４の結
果から明らかなように、本発明方法で得られる二酸化チ
タン顔料は、分散性・光沢、耐久性（光沢保持性及び耐
白亜化性）とも優れた性能を示す．? Example 13 In Example 1 above, the coating treatment with the hydrated oxide of silica was carried out as follows, except that the coating amount of the hydrated oxide of titanium was 1.0% as TiO■ based on the amount of TiOtfE. A titanium dioxide pigment (T) obtained by the method of the present invention was obtained by the same treatment. (Coating of hydrous oxide of silica) Tilt coarse head slurry of Example I (Tie. Standard 38
0g/l>3tt was heated to 60°C, and while keeping it at this temperature, Sin. 5 1 ml of an aqueous sodium silicate solution with a concentration of 100 g/l as
Added in 0 minutes. Subsequently, after stirring this slurry for 10 minutes, dilute sulfuric acid with a concentration of 10 fE mass % was added to adjust the PL1 of the slurry to 7.0, and the slurry was stirred for 30 minutes to coat the hydrous oxide of silica. Example 14 and Comparative Example 8 Titanium dioxide pigments (U) and (V) were obtained in the same manner as in Example 13, except that the number and time of wet pulverization were changed as shown in Table 3. Test Examples Titanium dioxide pigments (A) to (V) of the above Examples and Comparative Examples
), and the results shown in Tables 1 to 4 were obtained. In addition, in the processing details in Tables 1 and 3, "wet/powder" refers to wet grinding, "dry/powder" refers to dry grinding, and the numbers in brackets after that indicate grinding time (unit, minutes). Also, rSi(5
%)” The element name and number in brackets indicate surface coatings and coatings! (In terms of oxide, based on the weight of Ti02 of the crude titanium dioxide pigment). Performance evaluations in Tables 1 to 4 were performed as follows. Preparation of test plate Tl+ For gloss measurement 5, <Test plate The titanium dioxide pigment obtained in the example and comparative example was mixed with coconut oil-modified short oil alkyd resin/butylated melagon resin (7/3
Weight ratio) Mix into varnish and shake for +ii. It was made into paint. Apply this material to a glass plate (15cIIX 10am) using a doctor blade to a thickness of approximately 45μ (as a dry coating).
A test plate was prepared by coating the film with the following methods and baking it at 120°C for 30 minutes. The gloss after overbaking was determined by measuring the initial gloss of this test plate and then baking it at 180°C for 30 minutes. (2) Preliminary test for durability measurement The same paint as in item (1) above was applied to zinc phosphate treated steel (7Cl).
1 x 1 5 cm) using a wire applicator to a thickness of approximately 60 μm (as a dry film) and heated at 130°C.
A test plate was prepared by baking it for 30 minutes. Measurement of Glossiness Regarding the initial gloss and gloss after overbaking of the test plate, 20°-
20° and 60°-60” specular gloss using a gloss meter (
Measurements were made using a GM-2 6D model (manufactured by Murakami Color Research Institute). In addition, the initial gloss (60
The specular gloss (°-60°) was measured in the same manner. Durability evaluation Gloss retention was evaluated using a carbon arc type sunshine weather meter device (manufactured by Suka 1 Kenki KK, WE-SUN-D).
The test plate was subjected to accelerated exposure (12 minutes of precipitation during 60 minutes of irradiation, black panel temperature: 63±3°C) in a Type C), and the 60''-60@ specular gloss was measured at regular intervals for evaluation. Also,
Chalking resistance is measured in accordance with the chalking opening time and the paint film evaluation standards of the Japan Paint Inspection Association.
Evaluation was made based on the degree of chalking (0 to 10) on the painted surface after 60 hours of exposure. A degree of occurrence of 10 indicates that no chalking has occurred, and the smaller the value, the greater the degree of chalking. [Effects of the Invention] In the method of the present invention, agglomerated particles of titanium dioxide generated during surface coating are loosened by wet grinding, and then surface coating is applied. It is done uniformly in all conditions. Therefore, as is clear from the results in Tables 1 to 4, the titanium dioxide pigment obtained by the method of the present invention exhibits excellent performance in terms of dispersibility, gloss, and durability (gloss retention and chalking resistance).
Claims (1)
、ジルコニウム、チタニウム、アルミニウム、アンチモ
ン、スズ及びセリウムから成る群より選択される二種以
上の金属の含水酸化物を被覆する方法において、該被覆
工程の途中で１回以上の湿式粉砕を行なうことを特徴と
する二酸化チタン顔料の製造方法。In a method of coating the surface of the particles with a hydrous oxide of two or more metals selected from the group consisting of silicon, zirconium, titanium, aluminum, antimony, tin and cerium in an aqueous slurry of titanium dioxide, the coating step A method for producing a titanium dioxide pigment, which comprises performing wet pulverization one or more times during the process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15384889A JPH0323221A (en) | 1989-06-16 | 1989-06-16 | Production of titanium dioxide pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15384889A JPH0323221A (en) | 1989-06-16 | 1989-06-16 | Production of titanium dioxide pigment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0323221A true JPH0323221A (en) | 1991-01-31 |
Family
ID=15571425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15384889A Pending JPH0323221A (en) | 1989-06-16 | 1989-06-16 | Production of titanium dioxide pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0323221A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0654509A1 (en) * | 1993-11-24 | 1995-05-24 | KERR-McGEE CHEMICAL CORPORATION | Durable pigmentary titanium dioxide and methods of producing the same |
| US6395081B1 (en) * | 2000-04-12 | 2002-05-28 | Millennium Inorganic Chemical, Inc. | Methods for producing titanium dioxide pigments having improved gloss at low temperatures |
| US6695906B2 (en) | 2000-04-12 | 2004-02-24 | Millennium Inorganic Chemicals, Inc. | Continuous processes for producing titanium dioxide pigments |
| JP2007009156A (en) * | 2005-07-04 | 2007-01-18 | Ishihara Sangyo Kaisha Ltd | Method for producing titanium dioxide pigment |
| JP2011523966A (en) * | 2008-06-02 | 2011-08-25 | クローノス インターナショナル インコーポレイテッド | Surface coating method for inorganic solid particles, especially titanium dioxide pigment particles |
| WO2018123928A1 (en) | 2016-12-28 | 2018-07-05 | 中国塗料株式会社 | Anti-fouling paint composition, anti-fouling paint film, base material having anti-fouling paint film attached thereto and method for producing same, and fouling prevention method |
-
1989
- 1989-06-16 JP JP15384889A patent/JPH0323221A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0654509A1 (en) * | 1993-11-24 | 1995-05-24 | KERR-McGEE CHEMICAL CORPORATION | Durable pigmentary titanium dioxide and methods of producing the same |
| US6395081B1 (en) * | 2000-04-12 | 2002-05-28 | Millennium Inorganic Chemical, Inc. | Methods for producing titanium dioxide pigments having improved gloss at low temperatures |
| US6695906B2 (en) | 2000-04-12 | 2004-02-24 | Millennium Inorganic Chemicals, Inc. | Continuous processes for producing titanium dioxide pigments |
| JP2007009156A (en) * | 2005-07-04 | 2007-01-18 | Ishihara Sangyo Kaisha Ltd | Method for producing titanium dioxide pigment |
| JP4668705B2 (en) * | 2005-07-04 | 2011-04-13 | 石原産業株式会社 | Method for producing titanium dioxide pigment |
| JP2011523966A (en) * | 2008-06-02 | 2011-08-25 | クローノス インターナショナル インコーポレイテッド | Surface coating method for inorganic solid particles, especially titanium dioxide pigment particles |
| WO2018123928A1 (en) | 2016-12-28 | 2018-07-05 | 中国塗料株式会社 | Anti-fouling paint composition, anti-fouling paint film, base material having anti-fouling paint film attached thereto and method for producing same, and fouling prevention method |
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