JP2005272298A - Ultrafine mixed-crystal oxide particle, and its use - Google Patents
Ultrafine mixed-crystal oxide particle, and its use Download PDFInfo
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- JP2005272298A JP2005272298A JP2005081575A JP2005081575A JP2005272298A JP 2005272298 A JP2005272298 A JP 2005272298A JP 2005081575 A JP2005081575 A JP 2005081575A JP 2005081575 A JP2005081575 A JP 2005081575A JP 2005272298 A JP2005272298 A JP 2005272298A
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- 239000002245 particle Substances 0.000 title abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 239000011164 primary particle Substances 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
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- 239000010703 silicon Substances 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000004694 iodide salts Chemical class 0.000 claims abstract description 6
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- 239000000203 mixture Substances 0.000 claims description 43
- 239000011882 ultra-fine particle Substances 0.000 claims description 41
- 229920000620 organic polymer Polymers 0.000 claims description 39
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- 150000005309 metal halides Chemical class 0.000 claims description 32
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 14
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- TVCBSVKTTHLKQC-UHFFFAOYSA-M propanoate;zirconium(4+) Chemical compound [Zr+4].CCC([O-])=O TVCBSVKTTHLKQC-UHFFFAOYSA-M 0.000 claims description 3
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- JINJMFAIGCWUDW-UHFFFAOYSA-L zirconium(2+);diacetate Chemical compound [Zr+2].CC([O-])=O.CC([O-])=O JINJMFAIGCWUDW-UHFFFAOYSA-L 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- FMXLGOWFNZLJQK-UHFFFAOYSA-N hypochlorous acid;zirconium Chemical compound [Zr].ClO FMXLGOWFNZLJQK-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 20
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
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- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 5
- 229910002113 barium titanate Inorganic materials 0.000 description 5
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
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- 239000010419 fine particle Substances 0.000 description 3
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- 229910052814 silicon oxide 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
- 239000012808 vapor phase Substances 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
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- MNUKOWCSUUMTRC-UHFFFAOYSA-F zirconium(4+) octachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Zr+4].[Zr+4] MNUKOWCSUUMTRC-UHFFFAOYSA-F 0.000 description 2
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- Cosmetics (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Silicon Compounds (AREA)
- Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Artificial Filaments (AREA)
Abstract
Description
本発明は、気相法により得られる超微粒子混晶酸化物に関し、さらに詳しくはチタン、珪素及びアルミニウムの塩化物、臭化物、沃化物から複数種選ばれた任意の組成比率の混合物を原料とする、混晶状態の一次粒子を含む超微粒子混晶酸化物及びその用途に関する。 The present invention relates to an ultrafine particle mixed crystal oxide obtained by a vapor phase method, and more specifically, a raw material is a mixture of any composition ratio selected from a plurality of chlorides, bromides and iodides of titanium, silicon and aluminum. The present invention relates to an ultrafine mixed crystal oxide containing primary particles in a mixed crystal state and use thereof.
超微粒子酸化物の工業的応用分野は、近年大きく拡大しつつある。例えば、超微粒子状酸化チタンは、紫外線遮蔽材やシリコーンゴムヘの添加剤、光触媒性用途など多岐に亘って検討が進められ、特に紫外線遮蔽効果に注目して化粧料用途が、また光触媒性に注目して防汚、殺菌、消臭用途が注目されている。この背景には、超微粒子状酸化チタンの安全性、加工性、機能性、耐久性が優れている点が挙げられる。超微粒子の定義はこれまで明確ではないが、一般には一次粒子径が約0.1μｍ以下の微粒子に対して呼ばれている。 The industrial application field of ultrafine oxides has been greatly expanding in recent years. For example, ultrafine titanium oxide has been studied extensively, including UV shielding materials, additives to silicone rubber, and photocatalytic applications. Attention has been focused on antifouling, sterilization and deodorization. This is because the safety, workability, functionality, and durability of ultrafine titanium oxide are excellent. Although the definition of ultrafine particles has not been clear so far, it is generally called for fine particles having a primary particle size of about 0.1 μm or less.
酸化チタンが注目される具体的な機能には、紫外線の散乱と吸収があり、特に超微粒子状の酸化チタンはこの２つの機能を好ましく併せ持っている。例えば、一次粒子径が約８０ｎｍの超微粒子状の酸化チタンは、紫外線を効果的に散乱させる働きがあり、また波長が約４００ｎｍ以下の紫外線を効果的に吸収・励起して電子及び／またはホールを該表面近傍に発生させ、前記の防汚、殺菌、消臭を行う光触媒性を発揮する性質が知られている。 Specific functions for which titanium oxide attracts attention include scattering and absorption of ultraviolet rays, and ultrafine titanium oxide particularly preferably has both of these functions. For example, ultrafine titanium oxide having a primary particle diameter of about 80 nm has a function to effectively scatter ultraviolet rays, and also effectively absorbs and excites ultraviolet rays having a wavelength of about 400 nm or less to emit electrons and / or holes. Is known in the vicinity of the surface, and exhibits the photocatalytic property of performing the above-mentioned antifouling, sterilization and deodorization.
しかしながら、現実にこのような機能を有する酸化チタンを化粧料用途に使用する場合、光励起で発生した電子やホールが空気中の酸素や水と反応して様々なラジカル種を発生させ、空気中の有機物を分解する作用があるので、何らかの表面処理（被覆）をしないと不適当とされる場合がある。 However, when titanium oxide having such a function is actually used for cosmetic applications, electrons and holes generated by photoexcitation react with oxygen and water in the air to generate various radical species, and in the air Since it has an action of decomposing organic matter, it may be considered inappropriate unless some surface treatment (coating) is performed.
酸化チタンは、また高性能の誘電体原料としてもよく使用される。例えば、以下の反応式のように、酸化チタンを約1,200℃の温度下で炭酸バリウムと固相反応させて誘電体のチタン酸バリウムが製造される。
この場合、炭酸バリウムが約７００℃で分解してイオン性の高いＢａＯを生成し、これが共有結合性のあるＴｉＯ2粒子中へ拡散固溶してチタン酸バリウムが生成する。チタン酸バリウムの粒径は、反応時のＴｉＯ2の結晶子サイズによって決定されるので、原料としての酸化チタンの結晶性、粒径等が重要となる。また、セラミックコンデンサの高誘電率化や小型化の要求のためには、チタン酸バリウムの超微粒子が求められており、原料の酸化チタンの超微粒子が希求されてきた。 In this case, barium carbonate decomposes at about 700 ° C. to produce highly ionic BaO, which diffuses and dissolves into covalently bonded TiO 2 particles to produce barium titanate. Since the particle size of barium titanate is determined by the crystallite size of TiO 2 at the time of reaction, the crystallinity and particle size of titanium oxide as a raw material are important. Further, in order to increase the dielectric constant and size of ceramic capacitors, ultrafine particles of barium titanate have been demanded, and ultrafine particles of titanium oxide as a raw material have been demanded.
しかしながら、粒径0.1μｍ以下の酸化チタンは、上記反応温度の７００℃近辺では粒成長が著しく、チタン酸バリウムの超微粒子化には余り寄与しないという問題があり、このような課題に適した超微粒子酸化チタンが望まれている。 However, titanium oxide having a particle diameter of 0.1 μm or less has a problem that the grain growth is remarkable near the reaction temperature of 700 ° C. and does not contribute much to the ultrafine particle formation of barium titanate. Fine particle titanium oxide is desired.
一方、酸化チタンを含む複合体微粉の製造法として、ハロゲン化珪素及びハロゲン化チタン混合蒸気を原料として酸素を含有する酸化性ガスと９００℃以上の温度下で反応する、シリカ−チタニア複合体微粉の製造法が知られている（特開昭50-115190号公報：特許文献１）。この方法では、原料の混合蒸気を予熱することなく９００℃以上の高温下で反応させており、その結果製造される該複合体粒子にはその表面に常に結晶性ＴｉＯ2粒子が析出した構造を有している。 On the other hand, as a method for producing a composite fine powder containing titanium oxide, a silica-titania composite fine powder that reacts with an oxidizing gas containing oxygen using silicon halide and titanium halide mixed vapor as a raw material at a temperature of 900 ° C. or higher. Is known (Japanese Patent Laid-Open No. 50-115190: Patent Document 1). In this method, the mixed vapor of the raw material is reacted at a high temperature of 900 ° C. or higher without preheating, and as a result, the composite particles produced have a structure in which crystalline TiO 2 particles are always deposited on the surface. Have.
また、特許第2503370号公報（欧州特許第595078号／特許文献２）には、塩化物を原料とする火炎加水分解法（反応温度は1000℃〜3000℃）により、酸化チタン−酸化アルミニウム−酸化珪素の混合酸化物が製造できることが開示されている。火炎加水分解法であるために、生成するものは、Ａｌ2Ｏ3／ＴｉＯ2混合酸化物またはＳｉＯ2／ＴｉＯ2混合酸化物である。また、特許第2533067号公報（欧州特許第585544号／特許文献３）にも同様に火炎加水分解による酸化アルミニウム−酸化珪素の混合酸化物の製造が開示されている。 Patent No. 2503370 (European Patent No. 595078 / Patent Document 2) discloses titanium oxide-aluminum oxide-oxidation by flame hydrolysis using chloride as a raw material (reaction temperature is 1000 ° C. to 3000 ° C.). It is disclosed that mixed oxides of silicon can be produced. Since it is a flame hydrolysis method, what is produced is an Al 2 O 3 / TiO 2 mixed oxide or an SiO 2 / TiO 2 mixed oxide. Similarly, Japanese Patent No. 2533067 (European Patent No. 585544 / Patent Document 3) discloses the production of a mixed oxide of aluminum oxide and silicon oxide by flame hydrolysis.
このように、金属酸化物の気相製造方法または火炎加水分解法等による金属酸化物または混合金属酸化物の製造方法については既に知られているが、一般に反応温度、ガス流速、冷却速度等により大きく影響を受ける生成物の粒子成長過程は十分解明されていない。 As described above, a method for producing a metal oxide or a mixed metal oxide by a vapor phase production method or a flame hydrolysis method of a metal oxide is already known, but generally depends on a reaction temperature, a gas flow rate, a cooling rate, etc. The particle growth process of products that are greatly affected is not well understood.
本発明は、前記超微粒子金属酸化物の用途に鑑み、表面改質された超微粒子混晶酸化物を提供することを目的とする。 In view of the use of the ultrafine metal oxide, an object of the present invention is to provide a surface-modified ultrafine mixed oxide.
本発明者らは、従来技術を鑑み鋭意検討した結果、チタン、珪素（本発明では金属元素に含める）及びアルミニウムの塩化物、臭化物、沃化物からなる群より選ばれる少なくとも金属元素の異なる２種以上の化合物を含む混合ガス（「混合ハロゲン化金属ガス」と総称する。）と酸化性ガスをそれぞれ５００℃以上に予熱してから反応させることにより、ＢＥＴ比表面積が１０〜２００ｍ2／ｇで混晶状態の一次粒子を含む超微粒子混晶酸化物を製造できることを見出し、前記課題を解決した。 As a result of intensive studies in view of the prior art, the present inventors have found that at least two kinds of metal elements selected from the group consisting of titanium, silicon (included in the metal element in the present invention) and aluminum chloride, bromide, and iodide are different. A BET specific surface area of 10 to 200 m 2 / g is obtained by reacting a mixed gas containing the above compounds (collectively referred to as “mixed metal halide gas”) and an oxidizing gas after preheating them to 500 ° C. or more. The inventors have found that an ultrafine mixed crystal oxide containing primary particles in a mixed crystal state can be produced, and solved the above problems.
すなわち、本発明は
１．チタン、珪素及びアルミニウムの塩化物、臭化物、沃化物からなる群より選ばれる少なくとも金属元素の異なる２種以上の化合物を含む混合ガス（混合ハロゲン化金属ガス）及び酸化性ガスをそれぞれ５００℃以上に予熱した後、それぞれ流速１０ｍ／秒以上で反応管に供給し、高温酸化して製造される、ＢＥＴ比表面積が１０〜２００ｍ2 ／ｇで、混晶状態の一次粒子を含む超微粒子酸化物。
２．８００℃、１時間加熱後のＢＥＴ比表面積減少率が１０％以下である前記１に記載の超微粒子混晶酸化物。
３．９８％グリセリンを溶媒としてサンセットイエローを0.02％溶解し、それに酸化物を0.067％分散させてＢＬＢランプ（紫外線ランプ）にて1.65ｍＷ／ｃｍ2の強度で紫外線照射後、４９０ｎｍにおける吸光度変化（ΔＯＤ）を測定する方法において、その吸光度変化が５（／ｈｒ）以下である前記１乃至２のいずれか１項に記載の超微粒子混晶酸化物。
４．ＢＥＴ比表面積が１０〜２００ｍ2／ｇであり、かつ、一次粒子内にチタン−酸素−珪素結合が存在し、異種金属酸化結晶構造体によってコア（核）／シェル（殻）構造を有する前記１乃至３のいずれか１項に記載の超微粒子混晶酸化物。
５．塩素含有量をＡ（％）、ＢＥＴ比表面積をＢ（ｍ2／ｇ）とした場合、Ａ／Ｂが0.001以下である前記１乃至４のいずれか１項に記載の超微粒子混晶酸化物。
６．前記１乃至５のいずれか１項に記載の超微粒子混晶酸化物を含むことを特徴とする超微粒子混晶酸化物組成物。
７．前記１乃至５のいずれか１項に記載の超微粒子混晶酸化物を含むことを特徴とする顔料、誘電体原料、化粧料、衣料、紫外線遮蔽剤、研磨剤、シリコーンゴム、紙、または光触媒粉体。
８．前記１乃至５のいずれか１項に記載の超微粒子混晶酸化物を含むことを特徴とする水系スラリー。
９．前記１乃至５のいずれか１項に記載の超微粒子混晶酸化物を含むことを特徴とする有機重合体組成物。
１０．有機重合体組成物の有機重合体が、合成熱可塑性樹脂、合成熱硬化性樹脂、及び天然樹脂からなる群より選ばれる少なくとも１種である前記９に記載の有機重合体組成物。
１１．有機重合体が、熱可塑性樹脂、熱硬化性樹脂、合成樹脂、天然樹脂、及び親水性高分子からなる群より選ばれる少なくとも１種である前記９に記載の有機重合体組成物。
１２．有機重合体が、ポリオレフィン、ナイロン６、ナイロン６６、アラミド、ポリアミド、ポリエチレンテレフタレート、ポリエステル、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリエチレンオキサイド、ポリエチレングリコール、シリコン樹脂、ポリビニルアルコール、ビニルアセタール樹脂、ポリアセテート、ＡＢＳ樹脂、エポキシ樹脂、酢酸ビニル樹脂、セルロース、レーヨン、セルロース誘導体、ウレタン樹脂、ポリウレタン、ポリカーボネート、尿素樹脂、フッ素樹脂、ポリフッ化ビニリデン、フェノール樹脂、セルロイド、キチン、澱粉シート、アクリル樹脂、メラミン樹脂、及びアルキド樹脂からなる群より選ばれる１種以上である前記９に記載の有機重合体組成物。
１３．有機重合体組成物が、塗料、コーティング組成物、コンパウンド、及びマスターバッチから選ばれる物品である前記９に記載の有機重合体組成物。
１４．有機重合体組成物中の超微粒子混晶酸化物の濃度が、該組成物全質量中0.01〜８０質量％の範囲である前記９乃至１３のいずれか１項に記載の有機重合体組成物。
１５．前記９乃至１３のいずれか１項に記載の有機重合体組成物を用いた塗料。
１６．有機系バインダーを含有する前記１５記載の塗料。
１７．有機系バインダーが、ポリビニルアルコール、メラミン樹脂、ウレタン樹脂、セルロイド、キチン、澱粉シート、ポリアクリルアミド、及びアクリルアミドからなる群より選ばれる１種以上である前記１５記載の塗料。
１８．無機系バインダーを含有する前記１５記載の塗料。
１９．無機系バインダーが、オキシ塩化ジルコニウム、ヒドロキシ塩化ジルコニウム、硝酸ジルコニウム、硫酸ジルコニウム、二酢酸ジルコニウム、炭酸ジルコニウムアンモニウム、プロピオン酸ジルコニウム、アルコキシドシラン、珪酸塩、アルミニウムアルコキシド、及びチタンアルコキシドからなる群より選ばれる１種以上である前記１８の塗料。
２０．前記９に記載の有機重合体組成物を用いたコンパウンド。
２１．超微粒子混晶酸化物を高濃度に含む前記９に記載の有機重合体組成物を用いた、繊維、フィルム、及びプラスチック成形体からなる群より選ばれる１種以上である成形体用のマスターバッチ。
２２．前記９に記載の超微粒子混晶酸化物を含む有機重合体組成物を成形してなることを特徴とする成形体。
２３．成形体が、繊維、フィルム、及びプラスチック成形体から選ばれるものである前記９に記載の成形体。
２４．前記１乃至５のいずれか１項に記載の超微粒子混晶酸化物を表面に具備することを特徴とする構造体を提供する。
That is, the present invention is 1. A mixed gas (mixed metal halide gas) and an oxidizing gas containing at least two kinds of compounds selected from the group consisting of chlorides, bromides, and iodides of titanium, silicon, and aluminum at least at 500 ° C. or more are used. An ultrafine particle oxide containing primary particles in a mixed crystal state having a BET specific surface area of 10 to 200 m 2 / g, which is produced by preheating and then supplying a reaction tube at a flow rate of 10 m / sec or more and oxidizing at a high temperature.
2. The ultrafine mixed crystal oxide according to 1 above, wherein the BET specific surface area reduction rate after heating at 800 ° C. for 1 hour is 10% or less.
3. Dissolve 0.02% of Sunset Yellow using 98% glycerin as solvent, disperse 0.067% of oxide in it, and change the absorbance at 490nm after UV irradiation with BLB lamp (ultraviolet lamp) at 1.65mW / cm 2 intensity. 3. The ultrafine particle mixed crystal oxide according to any one of 1 to 2 above, wherein in the method for measuring (ΔOD), the change in absorbance is 5 (/ hr) or less.
4). The BET specific surface area is 10 to 200 m 2 / g, the titanium-oxygen-silicon bond is present in the primary particles, and the core (nucleus) / shell (shell) structure is formed by the dissimilar metal oxide crystal structure. 4. The ultrafine particle mixed crystal oxide according to any one of items 1 to 3.
5). 5. The ultrafine particle mixed crystal oxide according to any one of 1 to 4 above, wherein A / B is 0.001 or less when the chlorine content is A (%) and the BET specific surface area is B (m 2 / g). .
6). 6. An ultrafine mixed crystal oxide composition comprising the ultrafine mixed crystal oxide according to any one of 1 to 5 above.
7). A pigment, dielectric material, cosmetic, clothing, ultraviolet shielding agent, abrasive, silicone rubber, paper, or photocatalyst comprising the ultrafine mixed oxide according to any one of 1 to 5 above powder.
8). An aqueous slurry comprising the ultrafine mixed crystal oxide according to any one of 1 to 5 above.
9. 6. An organic polymer composition comprising the ultrafine mixed crystal oxide according to any one of 1 to 5 above.
10. 10. The organic polymer composition according to 9, wherein the organic polymer of the organic polymer composition is at least one selected from the group consisting of a synthetic thermoplastic resin, a synthetic thermosetting resin, and a natural resin.
11. 10. The organic polymer composition according to 9, wherein the organic polymer is at least one selected from the group consisting of a thermoplastic resin, a thermosetting resin, a synthetic resin, a natural resin, and a hydrophilic polymer.
12 Organic polymer is polyolefin, nylon 6, nylon 66, aramid, polyamide, polyethylene terephthalate, polyester, polyvinyl chloride, polyvinylidene chloride, polyethylene oxide, polyethylene glycol, silicone resin, polyvinyl alcohol, vinyl acetal resin, polyacetate, ABS Resin, epoxy resin, vinyl acetate resin, cellulose, rayon, cellulose derivative, urethane resin, polyurethane, polycarbonate, urea resin, fluororesin, polyvinylidene fluoride, phenol resin, celluloid, chitin, starch sheet, acrylic resin, melamine resin, and 10. The organic polymer composition as described in 9 above, which is one or more selected from the group consisting of alkyd resins.
13. 10. The organic polymer composition according to 9, wherein the organic polymer composition is an article selected from a paint, a coating composition, a compound, and a masterbatch.
14 14. The organic polymer composition according to any one of 9 to 13, wherein the concentration of the ultrafine particle mixed crystal oxide in the organic polymer composition is in the range of 0.01 to 80% by mass with respect to the total mass of the composition.
15. 14. A paint using the organic polymer composition according to any one of 9 to 13 above.
16. 16. The coating material according to 15 above containing an organic binder.
17. 16. The paint according to 15, wherein the organic binder is at least one selected from the group consisting of polyvinyl alcohol, melamine resin, urethane resin, celluloid, chitin, starch sheet, polyacrylamide, and acrylamide.
18. 16. The coating material according to 15 above, containing an inorganic binder.
19. 1 wherein the inorganic binder is selected from the group consisting of zirconium oxychloride, zirconium zirconium chloride, zirconium nitrate, zirconium sulfate, zirconium diacetate, ammonium zirconium carbonate, zirconium propionate, alkoxide silane, silicate, aluminum alkoxide, and titanium alkoxide. 18. The paint according to 18 above which is a seed or more.
20. 10. A compound using the organic polymer composition as described in 9 above.
21. 10. A master batch for a molded body, which is one or more selected from the group consisting of fibers, films, and plastic molded bodies, using the organic polymer composition according to the above item 9, which contains ultrafine mixed crystal oxides in a high concentration. .
22. 10. A molded product obtained by molding an organic polymer composition comprising the ultrafine mixed crystal oxide as described in 9 above.
23. 10. The molded product according to 9 above, wherein the molded product is selected from fibers, films, and plastic molded products.
24. 6. A structure comprising the ultrafine particle mixed crystal oxide according to any one of 1 to 5 on a surface thereof.
以下、本発明を詳細に説明する。
本発明は、ハロゲン化金属を酸化性ガスで高温酸化することにより金属酸化物を製造する気相製造法において、ハロゲン化金属がチタン、珪素及びアルミニウムの塩化物、臭化物、沃化物からなる群より選ばれる少なくとも金属元素の異なる２種以上の化合物を含む混合ハロゲン化金属ガスであって、該混合ハロゲン化金属ガス及び酸化性ガスをそれぞれ５００℃以上に予熱してから反応させることにより、ＢＥＴ比表面積が１０〜２００ｍ2／ｇで混晶状態の一次粒子を含む超微粒子酸化物及びその用途に関する。
Hereinafter, the present invention will be described in detail.
The present invention relates to a gas phase production method for producing a metal oxide by oxidizing a metal halide at high temperature with an oxidizing gas, wherein the metal halide is selected from the group consisting of chlorides, bromides and iodides of titanium, silicon and aluminum. A mixed metal halide gas containing at least two kinds of compounds selected from different metal elements, wherein the mixed metal halide gas and the oxidizing gas are each preheated to 500 ° C. or higher and reacted to obtain a BET ratio. The present invention relates to an ultrafine oxide containing primary particles in a mixed crystal state with a surface area of 10 to 200 m 2 / g and use thereof.
前記超微粒子混晶酸化物の製造方法において、混合ハロゲン化金属ガスは、チタン、珪素及びアルミニウムの塩化物、臭化物、沃化物からなる群より選ばれる少なくとも金属元素の異なる２種以上の化合物を含む混合ハロゲン化金属ガスであり、これを反応管へ供給する形態としては、前記ハロゲン化金属１種を単独で気化した後にガス状で混合したものを用いるのが好ましい。酸化性ガスには、酸素もしくは水蒸気またはこれらを含有する混合気体が使用される。 In the method for producing an ultrafine particle mixed crystal oxide, the mixed metal halide gas contains at least two compounds having at least different metal elements selected from the group consisting of chloride, bromide and iodide of titanium, silicon and aluminum. The mixed metal halide gas is preferably supplied to the reaction tube by vaporizing one of the metal halides and then mixing it in a gaseous state. As the oxidizing gas, oxygen or water vapor or a mixed gas containing these is used.
本発明において使用されるチタン、珪素及びアルミニウムの塩化物、臭化物及び沃化物は限定されないが、少なくとも５００℃以上に予熱した時に該ハロゲン化金属ガスを生じることができるハロゲン化金属なら何でもよい。例えばＴｉＣｌ2、ＴｉＣｌ3、ＴｉＣｌ4、ＴｉＢｒ3、ＴｉＢｒ4、ＳｉＣｌ4、Ｓｉ2Ｃｌ6、Ｓｉ3Ｃｌ8、Ｓｉ3Ｃｌ10、Ｓｉ5Ｃｌ12、Ｓｉ10Ｃｌ12、ＳｉＢｒ4、Ｓｉ2Ｂｒ6、Ｓｉ3Ｂｒ8、Ｓｉ4Ｂｒ10、ＳｉＩ4、Ｓｉ2Ｉ6、ＳｉＣｌ2Ｉ2、ＳｉＣｌＩ3、ＳｉＢｒ3Ｉ、ＳｉＨＩ3、ＳｉＣｌ3Ｉ、ＳｉＨ3Ｂｒ、ＳｉＨ2Ｂｒ2、ＳｉＨＢｒ3、ＳｉＣｌ3Ｂｒ、ＳｉＣｌ2Ｂｒ2、ＳｉＣｌＢｒ3、ＡｌＣｌ3、ＡｌＢｒ3及びＡｌＩ3が挙げられる。この中で、ＴｉＣｌ4、ＴｉＢｒ4、ＳｉＣｌ4、ＡｌＣｌ3が特に好ましい。
The titanium, silicon and aluminum chlorides, bromides and iodides used in the present invention are not limited, but any metal halide capable of generating the metal halide gas when preheated to at least 500 ° C. or higher may be used. For example TiCl 2, TiCl 3, TiCl 4 ,
本発明においては、前記混合ハロゲン化金属ガスと酸化性ガスをそれぞれ少なくとも５００℃以上、好ましくは８００℃以上に予熱してから反応させる必要がある。混合ハロゲン化金属ガスと酸化性ガスの予熱温度が５００℃より低いと、均一核の発生が少なく、かつ反応性が低いため超微粒子にはなりにくく、かつ、脱塩素後の残存塩素も多くなる。 In the present invention, the mixed metal halide gas and the oxidizing gas must be preheated to at least 500 ° C. or more, preferably 800 ° C. or more, and then reacted. When the preheating temperature of the mixed metal halide gas and oxidizing gas is lower than 500 ° C., the generation of uniform nuclei is low and the reactivity is low, so that it is difficult to form ultrafine particles, and the residual chlorine after dechlorination increases. .
本発明では、混合ハロゲン化金属ガス及び酸化性ガスのそれぞれを反応管に１０ｍ／秒以上の流速、好ましくは３０ｍ／秒以上の流速で供給することが望ましく、また、反応管内においては６００℃を越える高温度条件下でガスが滞留し反応する時間（以下「高温滞留時間」ということもある。）が１秒以内となるように、これらのガスを反応させることが好ましい。 In the present invention, each of the mixed metal halide gas and the oxidizing gas is desirably supplied to the reaction tube at a flow rate of 10 m / second or more, preferably 30 m / second or more, and 600 ° C. is set in the reaction tube. These gases are preferably reacted so that the time during which the gas stays and reacts under a high temperature condition exceeding the above (hereinafter also referred to as “high temperature residence time”) is within 1 second.
特に、本発明者らは、気相法における粒子の成長機構に関して鋭意検討した結果、粒子の成長に作用する因子としてＣＶＤ（化学的気相成長）機構、粒子衝突による合体・焼結成長機構をいずれの成長時間も短く制御することで、超微粒子状酸化物を好ましく得ることができる。すなわち、前者の成長に関しては、予熱温度を高めておいて化学的反応性（反応速度）を高める結果、酸化物の成長を抑えることができる。後者の成長に関しては、ＣＶＤが完結した後速やかに冷却、希釈等を行い、高温滞留時間を極力小さくすることにより、焼結等による成長を抑えることができる。このように製造条件を設定することにより、ＢＥＴ比表面積が１０ｍ2／ｇ〜２００ｍ2／ｇ、好ましくは１０ｍ2／ｇ〜１００ｍ2／ｇの超微粒子混晶酸化物が得られる。 In particular, as a result of intensive studies on the growth mechanism of particles in the vapor phase method, the present inventors have found that a chemical vapor deposition (CVD) mechanism and a coalescence / sinter growth mechanism due to particle collision are factors that affect particle growth. By controlling any growth time short, an ultrafine oxide can be preferably obtained. That is, with respect to the former growth, as a result of increasing the chemical reactivity (reaction rate) by increasing the preheating temperature, it is possible to suppress oxide growth. With regard to the latter growth, the growth due to sintering or the like can be suppressed by cooling, diluting, etc. promptly after the completion of CVD and minimizing the high temperature residence time. By setting this way manufacturing conditions, BET specific surface area of 10m 2 / g~200m 2 / g, preferably ultrafine mixed crystal oxide 10m 2 / g~100m 2 / g is obtained.
混合ハロゲン化金属ガスと酸化性ガスを反応管に導入する際の流速は、１０ｍ／秒以上であることが好ましい。流速を大きくすることによって、両者のガスの混合が促進されるからである。反応管へのガスの導入温度が５００℃以上であれば、混合と同時に反応は完結するので均一核の発生が増進され、かつ、ＣＶＤ支配による成長した粒子が形成されるゾーンを短くすることができる。 The flow rate when the mixed metal halide gas and oxidizing gas are introduced into the reaction tube is preferably 10 m / second or more. This is because by increasing the flow velocity, mixing of both gases is promoted. If the introduction temperature of the gas into the reaction tube is 500 ° C. or higher, the reaction is completed simultaneously with the mixing, so that the generation of uniform nuclei is promoted, and the zone in which the grown particles are formed under the control of CVD can be shortened. it can.
本発明においては、反応管に導入されたガスが十分に混合されるように、原料ガスを反応管へ導入することが好ましい。ガスが十分に混合されれば、反応管内におけるガスの流体状態については特に制限はないが、好ましくは、例えば、乱流が生じる流体状態である。また、渦巻き流が存在していてもよい。 In the present invention, it is preferable to introduce the raw material gas into the reaction tube so that the gas introduced into the reaction tube is sufficiently mixed. If the gas is sufficiently mixed, there is no particular limitation on the fluid state of the gas in the reaction tube, but preferably, for example, a fluid state in which turbulent flow occurs. Moreover, a swirl flow may exist.
本発明においては、ガスの混合を完全に行うために反応管内に供給されるガスの反応管内における流速は、大きいことが好ましく、特に、平均流速で５ｍ／秒以上であることが好ましい。反応管内のガスの流速が５ｍ／秒以上であれば、反応管内における混合を十分に行うことができる。 In the present invention, the flow rate of the gas supplied into the reaction tube in order to completely mix the gas is preferably large, and in particular, the average flow rate is preferably 5 m / second or more. If the flow rate of the gas in the reaction tube is 5 m / second or more, mixing in the reaction tube can be sufficiently performed.
原料ガスを反応管に導入する導入ノズルとしては、同軸平行流、斜交流、十字流等を与えるノズルが採用されるが、これらに限定されない。一般に同軸平行流ノズルは、斜交流や十字流を与えるノズルに比べて混合の程度は劣るが、構造が簡単なので設計上好ましく用いられる。例えば、同軸平行流ノズルの場合は、内管に塩化物を含有するガスを導入し、外管に酸化性ガスを導入する。ただし、内管径は５０ｍｍ以下、好ましく５０ｍｍ〜１０ｍｍであることが、ガスの混合の観点から好ましい。 As the introduction nozzle for introducing the raw material gas into the reaction tube, a nozzle that gives a coaxial parallel flow, an oblique alternating current, a cross flow or the like is employed, but is not limited thereto. In general, a coaxial parallel flow nozzle is inferior to a nozzle that gives oblique alternating current or cross flow, but is preferably used because of its simple structure. For example, in the case of a coaxial parallel flow nozzle, a gas containing chloride is introduced into the inner tube, and an oxidizing gas is introduced into the outer tube. However, the inner tube diameter is preferably 50 mm or less, and preferably 50 mm to 10 mm from the viewpoint of gas mixing.
反応管内におけるこの反応は発熱反応であり、反応温度は製造された超微粒子酸化チタンの焼結温度より高温である。反応装置からの放熱はあるものの、反応後、急冷しないかぎり製造された微粒子は焼結が進行し、成長した粒子になってしまう。本発明においては、反応管内の６００℃を越える高温滞留時間は１秒以下とし、その後急冷することが好ましい。
反応後の粒子を急冷させる手段としては、反応後の混合物に多量の冷却空気や窒素等のガスを導入したり、水を噴霧したりする手段等が採用される。
This reaction in the reaction tube is an exothermic reaction, and the reaction temperature is higher than the sintering temperature of the produced ultrafine titanium oxide. Although there is heat radiation from the reaction apparatus, the produced fine particles are sintered and become grown particles unless they are rapidly cooled after the reaction. In the present invention, the high temperature residence time exceeding 600 ° C. in the reaction tube is preferably set to 1 second or less and then rapidly cooled.
As a means for rapidly cooling the particles after the reaction, a means for introducing a large amount of cooling air, a gas such as nitrogen, or spraying water into the mixture after the reaction is employed.
図１に本発明の超微粒子混晶酸化物の製造に用いられる、同軸平行流ノズルを備えた反応管の概略模式図を例示する。混合ハロゲン化金属ガスは予熱器２で所定温度まで予熱されて、同軸平行流ノズル部１の内管から反応管３へ導入される。酸化性ガスは予熱器２で所定温度まで予熱されて、同軸平行流ノズル部１の外管から反応管３へ導入される。反応管内に導入されたガスは混合されて反応した後、冷却ガスで急冷され、その後、バグフィルター４に送られて超微粒子混晶酸化物が捕集される。
FIG. 1 illustrates a schematic diagram of a reaction tube equipped with a coaxial parallel flow nozzle used in the production of the ultrafine mixed oxide of the present invention. The mixed metal halide gas is preheated to a predetermined temperature by the preheater 2 and introduced into the
また、原料となる混合ハロゲン化金属ガスは、１００体積％の該混合ハロゲン化金属ガスで用いるか、または好ましくは不活性ガスで希釈して１０体積％以上１００％未満、さらに好ましくは２０体積％以上１００体積％未満で投入することができる。混合ハロゲン化金属ガスの濃度（ハロゲン化金属ガスのトータル濃度）が１０体積％以上のガスを原料として用いると、均一核の発生が多くなり、または反応性が高くなる。前記不活性ガスとしては、混合ハロゲン化金属と反応せずかつ酸化されないものを選択すべきである。具体的には、好ましい希釈ガスとして、窒素、アルゴン等が挙げられる。 Further, the mixed metal halide gas used as a raw material is used in 100% by volume of the mixed metal halide gas, or preferably diluted with an inert gas to be 10% by volume or more and less than 100%, more preferably 20% by volume. More than 100 volume% can be added. When a gas having a mixed metal halide gas concentration (total concentration of metal halide gas) of 10% by volume or more is used as a raw material, the generation of uniform nuclei increases or the reactivity increases. As the inert gas, one that does not react with the mixed metal halide and is not oxidized should be selected. Specifically, nitrogen, argon, etc. are mentioned as preferable dilution gas.
次に、本発明の超微粒子混晶酸化物について以下に説明する。
本発明の超微粒子混晶酸化物は、ＢＥＴ比表面積が１０〜２００ｍ2／ｇであり、原料の混合ハロゲン化金属ガスに、少なくともチタンと珪素の元素を含む２種以上の化合物を使用した場合には、生成一次粒子内にチタン−酸素−珪素結合が存在した混晶状態の超微粒子混晶酸化物が得られる。該超微粒子混晶酸化物の平均一次粒子径は、0.008μm〜0.1μｍ、好ましくは0.015μｍ〜0.1μｍの範囲を有する。
Next, the ultrafine particle mixed crystal oxide of the present invention will be described below.
The ultrafine particle mixed crystal oxide of the present invention has a BET specific surface area of 10 to 200 m 2 / g, and two or more kinds of compounds containing at least titanium and silicon elements are used as a mixed metal halide gas as a raw material. Thus, an ultrafine mixed crystal oxide in a mixed crystal state in which a titanium-oxygen-silicon bond is present in the generated primary particles is obtained. The average primary particle diameter of the ultrafine particle mixed crystal oxide is in the range of 0.008 μm to 0.1 μm, preferably 0.015 μm to 0.1 μm.
超微粒子混晶酸化物の耐焼結性の指標として、加熱後のＢＥＴ比表面積減少率で評価（評価法は後記する。）したところ、チタン−酸素−珪素結合を含む超微粒子混晶酸化物は、８００℃、１時間加熱後のＢＥＴ比表面積減少率が１０％以下である特徴を有する。 As an index of the sintering resistance of the ultrafine particle mixed crystal oxide, the BET specific surface area reduction rate after heating was evaluated (evaluation method will be described later). As a result, the ultrafine particle mixed crystal oxide containing a titanium-oxygen-silicon bond was The BET specific surface area reduction rate after heating at 800 ° C. for 1 hour is 10% or less.
また、本発明の超微粒子混晶酸化物に関し、原料の混合ハロゲン化金属ガスとして少なくともチタンとアルミニウムの元素を含む２種以上の化合物を使用した場合には、一次粒子内にチタン−酸素−アルミニウム結合が存在した混晶状態の超微粒子混晶酸化物が得られる。この場合、チタン−酸素−アルミニウム結合を含む超微粒子混晶酸化物は、８００℃、１時間加熱後のＢＥＴ比表面積減少率が１０％以下である特徴を有する。 Further, in the ultrafine particle mixed crystal oxide of the present invention, when two or more kinds of compounds containing at least titanium and aluminum elements are used as a mixed metal halide gas as a raw material, titanium-oxygen-aluminum is contained in the primary particles. An ultrafine mixed crystal oxide in a mixed crystal state in which bonds are present is obtained. In this case, the ultrafine particle mixed crystal oxide containing a titanium-oxygen-aluminum bond has a feature that the BET specific surface area reduction rate after heating at 800 ° C. for 1 hour is 10% or less.
さらに、本発明の超微粒子混晶酸化物に関し、原料の混合ハロゲン化金属ガスとして、少なくともアルミニウムと珪素の元素を含む２種以上の化合物を使用した場合には、一次粒子内にアルミニウム−酸素−珪素結合が存在した混晶状態の超微粒子混晶酸化物が得られる。この場合、該アルミニウム−酸素−珪素結合を含む超微粒子混晶酸化物は、８００℃、１時間加熱後のＢＥＴ比表面積減少率が１０％以下である特徴を有する。 Further, regarding the ultrafine mixed oxide of the present invention, when two or more kinds of compounds containing at least aluminum and silicon elements are used as the mixed metal halide gas of the raw material, aluminum-oxygen- An ultrafine mixed crystal oxide in a mixed crystal state in which silicon bonds exist can be obtained. In this case, the ultrafine particle mixed crystal oxide containing an aluminum-oxygen-silicon bond has a feature that the BET specific surface area reduction rate after heating at 800 ° C. for 1 hour is 10% or less.
また、本発明の超微粒子混晶酸化物に関する光活性の指標として、紫外線照射時の色素吸光度の減少速度を基に該超微粒子混晶酸化物（例えば、一次粒子内にチタン−酸素−珪素結合、チタン−酸素−アルミニウム結合、または珪素−酸素−アルミニウム結合が存在した混晶状態にあるもの）に特徴づけをしたところ、本発明の超微粒子混晶酸化物は、９８％グリセリンを溶媒としてサンセットイエロー（色素）を0.02％溶解し、それに酸化物を0.067％分散させてＢＬＢランプ（紫外線ランプ）にて1.65ｍＷ／ｃｍ2の強度で紫外線照射後、４９０ｎｍにおける吸光度変化（ΔＯＤ）を測定する方法において、その吸光度変化が５（１時間当たり）以下である特徴を有する。 In addition, as an index of photoactivity related to the ultrafine particle mixed crystal oxide of the present invention, the ultrafine particle mixed crystal oxide (for example, a titanium-oxygen-silicon bond in the primary particle) based on the rate of decrease in dye absorbance upon ultraviolet irradiation. , Titanium-oxygen-aluminum bond, or silicon-oxygen-aluminum bond in a mixed crystal state). As a result, the ultrafine mixed crystal oxide of the present invention is obtained by using 98% glycerin as a solvent. Dissolve 0.02% of set yellow (dye), disperse 0.067% of oxide in it, and measure the change in absorbance (ΔOD) at 490 nm after UV irradiation with a BLB lamp (ultraviolet lamp) at an intensity of 1.65 mW / cm 2. The method is characterized in that the change in absorbance is 5 (per hour) or less.
また、驚くべきことに、酸化珪素が共存する場合においては、脱塩素処理後に得られた酸化物の残存塩素量が酸化珪素が存在しない場合に比べて激減していることが判明した。 Surprisingly, it has been found that when silicon oxide coexists, the amount of residual chlorine in the oxide obtained after dechlorination is drastically reduced as compared to the case where no silicon oxide is present.
本発明においては、本発明の前記各種結合が存在した混晶状態にある超微粒子混晶酸化物に関し、塩素含有量をＡ（％）、ＢＥＴ比表面積をＢ（ｍ2／ｇ）とした場合、Ａ／Ｂが0.001以下であるものが好ましい。 In the present invention, regarding the ultrafine mixed crystal oxide in the mixed crystal state in which the various bonds existed according to the present invention, the chlorine content is A (%) and the BET specific surface area is B (m 2 / g). A / B is preferably 0.001 or less.
本発明の超微粒子混晶酸化物は、好ましくは異種金属酸化結晶構造体によってコア（核）／シェル（殻）構造をとっていてもよい。例えば、一次粒子内にチタン−酸素−珪素結合が存在した混晶状態を含むチタン−珪素系超微粒子混晶酸化物では、コアにＴｉＯ2相が、シェルにＳｉＯ2相が富んだ構造が観測されている。 The ultrafine particle mixed crystal oxide of the present invention may preferably have a core / shell structure by a dissimilar metal oxide crystal structure. For example, in a titanium-silicon ultrafine particle mixed crystal oxide containing a mixed crystal state in which a titanium-oxygen-silicon bond is present in the primary particles, a structure in which the core is rich in TiO 2 phase and the shell is rich in SiO 2 phase is observed. Has been.
また、本発明の超微粒子混晶酸化物は、顔料や誘電体原料、あるいは添加剤として化粧料、衣料、紫外線遮蔽剤、研磨剤またはシリコーンゴム・紙等の各種組成物製品に利用できる。また、チタンを含む珪素混晶系酸化物またはアルミニウム混晶系酸化物は、酸化チタン単独の光触媒活性を低減または増幅できるので、光触媒効果を制御した光触媒粉体として利用できる。 Further, the ultrafine mixed crystal oxide of the present invention can be used in various composition products such as cosmetics, clothing, UV shielding agents, abrasives, silicone rubber and paper as pigments, dielectric raw materials, or additives. Moreover, since the silicon mixed crystal oxide or aluminum mixed crystal oxide containing titanium can reduce or amplify the photocatalytic activity of titanium oxide alone, it can be used as a photocatalyst powder with a controlled photocatalytic effect.
本発明の水系スラリーとは、超微粒子混晶酸化物を含む水分散体をさす。前記スラリー中の超微粒子混晶酸化物の含有割合については特に制限なく、例えば0.01質量％〜５０質量％、さらには１質量％〜４０質量％の範囲が望ましい。超微粒子混晶酸化物の含有量が0.01質量％を下回ると、塗工後に十分な超微粒子混晶酸化物の性能が得られない。一方、５０質量％を超えると増粘等の問題が生じるばかりか経済的に不利となる。 The aqueous slurry of the present invention refers to an aqueous dispersion containing ultrafine mixed crystal oxides. The content ratio of the ultrafine mixed crystal oxide in the slurry is not particularly limited, and is preferably in the range of, for example, 0.01% by mass to 50% by mass, and more preferably 1% by mass to 40% by mass. When the content of the ultrafine mixed crystal oxide is less than 0.01% by mass, sufficient performance of the ultrafine mixed crystal oxide cannot be obtained after coating. On the other hand, if it exceeds 50% by mass, not only problems such as thickening will occur, but it will be economically disadvantageous.
また、この水分散体（スラリー）にバインダーを任意に添加して塗工剤とし、これを後記する各種構造体の表面に塗布することにより、超微粒子混晶酸化物を表面に具備した構造体を製造することができる。本発明においては、バインダー材料について制限されるものではなく有機系バインダーであっても無機系バインダーであっても良い。この様な有機系バインダーの具体例として、ポリビニルアルコール、メラミン樹脂、ウレタン樹脂、セルロイド、キチン、澱粉シート、ポリアクリルアミド、アクリルアミド等が挙げられる。また、無機系バインダーの具体例として、オキシ塩化ジルコニウム、ヒドロキシ塩化ジルコニウム、硝酸ジルコニウム、硫酸ジルコニウム、酢酸ジルコニウム、炭酸ジルコニウムアンモニウム、プロピオン酸ジルコニウム等のジルコニウム化合物、アルコキシドシラン、珪酸塩等の珪素化合物、或いはアルミニウムやチタンの金属アルコキシド等が挙げられる。 In addition, a structure having an ultrafine particle mixed crystal oxide on the surface by arbitrarily adding a binder to the aqueous dispersion (slurry) to form a coating agent and applying it to the surface of various structures described later Can be manufactured. In the present invention, the binder material is not limited and may be an organic binder or an inorganic binder. Specific examples of such an organic binder include polyvinyl alcohol, melamine resin, urethane resin, celluloid, chitin, starch sheet, polyacrylamide, acrylamide and the like. Specific examples of inorganic binders include zirconium compounds such as zirconium oxychloride, zirconium zirconium chloride, zirconium nitrate, zirconium sulfate, zirconium acetate, ammonium zirconium carbonate and zirconium propionate, silicon compounds such as alkoxide silane and silicate, or Examples thereof include metal alkoxides of aluminum and titanium.
また、塗工剤中のバインダーの添加量は、例えば0.01質量％〜２０質量％、さらには１質量％〜１０質量％の範囲が望ましい。もし、バインダーの含有量が0.01質量％未満だと、塗工後に十分な接着性を有さず、また２０質量％を超えると増粘等の問題が生じるばかりか経済的に不利となる。 Moreover, the addition amount of the binder in a coating agent is 0.01 mass%-20 mass%, for example, Furthermore, the range of 1 mass%-10 mass% is desirable. If the binder content is less than 0.01% by mass, it will not have sufficient adhesion after coating, and if it exceeds 20% by mass, problems such as thickening will occur and it will be economically disadvantageous.
本発明の超微粒子混晶酸化物は、有機重合体に添加して組成物として使用できる。ここで、使用できる有機重合体としては、合成熱可塑性樹脂、合成熱硬化性樹脂、天然樹脂などが挙げられる。このような有機重合体の具体例としては、ポリエチレン、ポリプロピレン、ポリスチレンなどのポリオレフィン、ナイロン６、ナイロン６６、アラミドなどのポリアミド、ポリエチレンテレフタレート、不飽和ポリエステルなどのポリエステル、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリエチレンオキサイド、ポリエチレングリコール、シリコン樹脂、ポリビニルアルコール、ビニルアセタール樹脂、ポリアセテート、ＡＢＳ樹脂、エポキシ樹脂、酢酸ビニル樹脂、セルロース及びレーヨンその他のセルロース誘導体、ウレタン樹脂、ポリウレタン、ポリカーボネート、尿素樹脂、フツ素樹脂、ポリフッ化ビニリデン、フェノール樹脂、セルロイド、キチン、澱粉シート、アクリル樹脂、メラミン樹脂、アルキド樹脂などが挙げられる。 The ultrafine mixed oxide of the present invention can be used as a composition by adding to an organic polymer. Here, examples of the organic polymer that can be used include synthetic thermoplastic resins, synthetic thermosetting resins, and natural resins. Specific examples of such an organic polymer include polyolefins such as polyethylene, polypropylene and polystyrene, polyamides such as nylon 6, nylon 66 and aramid, polyesters such as polyethylene terephthalate and unsaturated polyester, polyvinyl chloride, polyvinylidene chloride, Polyethylene oxide, polyethylene glycol, silicone resin, polyvinyl alcohol, vinyl acetal resin, polyacetate, ABS resin, epoxy resin, vinyl acetate resin, cellulose, rayon and other cellulose derivatives, urethane resin, polyurethane, polycarbonate, urea resin, fluorine resin , Polyvinylidene fluoride, phenol resin, celluloid, chitin, starch sheet, acrylic resin, melamine resin, alkyd resin and the like.
本発明の超微粒子混晶酸化物を含むこれら有機重合体組成物は、塗料（コーティング組成物）、コンパウンド、マスターバッチなどの形態で使用できる。有機重合体組成物中の超微粒子混晶酸化物の濃度は、該組成物全質量に対して、0.01〜８０質量％、好ましくは１〜５０質量％である。
本発明においては、上記重合体組成物を成形することによって成形体が得られる。このような組成物の成形体として、繊維、フィルム、プラスチック成形体等が挙げられる。
These organic polymer compositions containing the ultrafine mixed crystal oxide of the present invention can be used in the form of paint (coating composition), compound, masterbatch and the like. The density | concentration of the ultrafine particle mixed crystal oxide in an organic polymer composition is 0.01-80 mass% with respect to this composition total mass, Preferably it is 1-50 mass%.
In this invention, a molded object is obtained by shape | molding the said polymer composition. Examples of the molded body of such a composition include fibers, films, and plastic molded bodies.
さらに、本発明の有機重合体組成物は、耐久性に優れていることから壁材、ガラス、看板、道路建築用コンクリートなどの構造体のコーティング組成物として使用できる。さら紙やプラスチック、布、木のような構造体（有機物）や、車両などにコーティングしても、塗膜が劣化し破壊されることはない。 Furthermore, since the organic polymer composition of the present invention is excellent in durability, it can be used as a coating composition for structures such as wall materials, glass, signboards, and road building concrete. Even if it is coated on a structure (organic matter) such as paper, plastic, cloth, wood, or a vehicle, the coating film is not deteriorated and destroyed.
以下、実施例を用いて具体的に説明するが、本発明はこれら実施例に何ら限定されるものではない。 Hereinafter, although it demonstrates concretely using an Example, this invention is not limited to these Examples at all.
〈耐焼結性の評価〉
本発明の超微粒子混晶酸化物の耐焼結性の評価として、加熱後のＢＥＴ比表面積減少率を指標として採用する。
原粉１ｇをアルミナ製坩堝に入れ、シリコニットオーブン中、８００℃にて１時間加熱する。室温まで冷却後そのＢＥＴ比表面積を測定する。原粉のＢＥＴ比表面積をＢ１（ｍ2／ｇ）、加熱後のＢＥＴ比表面積をＢ２（ｍ2／ｇ）とする時、ＢＥＴ比表面積減少率は以下の式で定義される。
As an evaluation of the sintering resistance of the ultrafine mixed crystal oxide of the present invention, the BET specific surface area reduction rate after heating is adopted as an index.
1 g of raw powder is put in an alumina crucible and heated at 800 ° C. for 1 hour in a siliconit oven. After cooling to room temperature, the BET specific surface area is measured. When the BET specific surface area of the raw powder is B1 (m 2 / g) and the BET specific surface area after heating is B2 (m 2 / g), the BET specific surface area reduction rate is defined by the following formula.
〈光活性の評価〉
本発明の超微粒子混晶酸化物の光活性の評価として、紫外線照射時の色素吸光度の減少速度を指標として採用する。
９８％グリセリンを溶媒としてサンセットイエロー（アゾ系染料）を0.02％溶解し、それに酸化物を0.067％分散させる。その分散体を石英ガラス製セルに入れ、ＢＬＢランプ（紫外線ランプ）にて1.65ｍＷ／ｃｍ2の強度で紫外線照射する。一定時間ごとに４９０ｎｍにおける吸光度を測定し、その減少速度（ΔＯＤ、単位/hr）を求める。ΔＯＤが小さいものほど、光活性が抑制されていると判断される。
<Evaluation of photoactivity>
As an evaluation of the photoactivity of the ultrafine particle mixed crystal oxide of the present invention, the rate of decrease in dye absorbance upon UV irradiation is employed as an index.
0.02% of sunset yellow (azo dye) is dissolved using 98% glycerin as a solvent, and 0.067% of oxide is dispersed therein. The dispersion is placed in a quartz glass cell and irradiated with ultraviolet rays with a BLB lamp (ultraviolet lamp) at an intensity of 1.65 mW / cm 2 . The absorbance at 490 nm is measured at regular intervals, and the rate of decrease (ΔOD, unit / hr) is determined. It is judged that the smaller the ΔOD is, the more the photoactivity is suppressed.
〈混晶状態の評価〉
本発明においては混晶状態の確認方法としては、ＸＰＳ（Ｘ線光電子分光法）を採用する。その詳細については、A.Yu.Stakheev et al, J.Phys.Chem.,97(21), 5668-5672(1993)などに記載されている。
<Evaluation of mixed crystal state>
In the present invention, XPS (X-ray photoelectron spectroscopy) is employed as a mixed crystal state confirmation method. Details thereof are described in A. Yu. Stakheev et al, J. Phys. Chem., 97 (21), 5668-5672 (1993) and the like.
実施例１：
濃度１００体積％のガス状四塩化チタン9.4Ｎｍ2／時間（Ｎは標準状態を意味する。以下同じ）及び濃度１００体積％のガス状四塩化珪素2.4Ｎｍ3／時間を含有するガスを混合後1,000℃に、８Ｎｍ3／時間の酸素及び２０Ｎｍ3／時間の水蒸気の混合ガスを1,000℃にそれぞれ予熱して、同軸平行流ノズルを用いて、それぞれ流速４９ｍ／秒、６０ｍ／秒で反応管に導入した。ただし、反応は図１に示すような反応管を用い、同軸平行流ノズルの内管径は２０ｍｍとし、内管に混合ハロゲン化金属を含有するガスを導入した。
反応管の内径は１００ｍｍであり、反応温度1,300℃における管内流速は計算値で１０ｍ／秒であった。反応管内の高温滞留時間が0.3秒以下となるように、反応後冷却空気を反応管に導入し、その後、テフロン製バグフィルターを用いて製造された超微粒子粉末を捕集した。その後、オーブンにて空気雰囲気下、５００℃×１時間加熱し、脱塩素処理を実施した。
得られた超微粒子混晶酸化物は、ＢＥＴ比表面積が８８ｍ2／ｇ、平均真比重3.7ｇ／ｃｃ、平均一次粒子径0.018μｍ、塩素が0.01％であり、ＸＰＳによって明らかにチタン−酸素−珪素結合が認められた。
また、光活性（以下、ΔＯＤと記す）は0.1／ｈｒ、８００℃×１時間後のＢＥＴ比表面積減少率（以下、ΔＢと記す）は２％、塩素とＢＥＴ比表面積の比率（以下、Ａ／Ｂと記す）は0.0001であった。
Example 1:
After mixing gas containing 100% by volume gaseous titanium tetrachloride 9.4Nm 2 / hour (N means standard condition, the same shall apply hereinafter) and 100% by volume gaseous silicon tetrachloride 2.4Nm 3 / hour to 1,000 ° C., the 8 Nm 3 / time of oxygen and 20 Nm 3 / time of the mixed gas of water vapor with each preheated to 1,000 ° C., using a coaxial parallel flow nozzle, respectively velocity 49m / sec, the reaction tube at 60 m / sec Introduced. However, a reaction tube as shown in FIG. 1 was used for the reaction, the inner tube diameter of the coaxial parallel flow nozzle was 20 mm, and a gas containing a mixed metal halide was introduced into the inner tube.
The inner diameter of the reaction tube was 100 mm, and the flow rate in the tube at a reaction temperature of 1,300 ° C. was 10 m / sec as a calculated value. After the reaction, cooling air was introduced into the reaction tube so that the high-temperature residence time in the reaction tube was 0.3 seconds or less, and then ultrafine powder produced using a Teflon bag filter was collected. Then, dechlorination was performed by heating in an oven in an air atmosphere at 500 ° C. for 1 hour.
The obtained ultrafine particle mixed crystal oxide has a BET specific surface area of 88 m 2 / g, an average true specific gravity of 3.7 g / cc, an average primary particle diameter of 0.018 μm, and chlorine of 0.01%. Silicon bonds were observed.
The photoactivity (hereinafter referred to as ΔOD) is 0.1 / hr, the BET specific surface area reduction rate after 1 hour at 800 ° C. (hereinafter referred to as ΔB) is 2%, and the ratio of chlorine to BET specific surface area (hereinafter referred to as A). (Denoted as / B) was 0.0001.
実施例２：
ガス状四塩化チタン8.3Ｎｍ3／時間とガス状三塩化アルミニウム2.4Ｎｍ3／時間と窒素６Ｎｍ3／時間を含有するガスを混合後９００℃に、８Ｎｍ3／時間の酸素及び２０Ｎｍ3／時間の水蒸気の混合ガスを1,000℃にそれぞれ予熱して、同軸平行流ノズルを用いて、それぞれ流速６３ｍ／秒、６０ｍ／秒で反応管に導入した。ただし、反応は図１に示すような反応管を用い、同軸平行流ノズルの内管径は２０ｍｍとし、内管に混合ハロゲン化金属を含有するガスを導入した。
反応管の内径は１００ｍｍであり、反応温度1,200℃における管内流速は計算値で１０ｍ／秒であった。反応管内の高温滞留時間が0.3秒以下となるように、反応後冷却空気を反応管に導入し、その後、テフロン製バグフィルターを用いて製造された超微粒子粉末を捕集した。その後、オーブンにて空気雰囲気下、５００℃×１時間加熱し、脱塩素処理を実施した。
得られた超微粒子混晶酸化物は、ＢＥＴ比表面積が４８ｍ2／ｇ、平均真比重3.9ｇ／ｃｃ、平均一次粒子径0.032μｍ、塩素が0.1％であり、ＸＰＳによって明らかにチタン−酸素−アルミニウム結合が認められた。
また、ΔＯＤは1.2／ｈｒ、ΔＢは５％、Ａ／Ｂは0.002であった。
Example 2:
After mixing a gas containing gaseous titanium tetrachloride 8.3 Nm 3 / hour, gaseous aluminum trichloride 2.4 Nm 3 / hour and nitrogen 6 Nm 3 / hour, at 900 ° C., 8 Nm 3 / hour oxygen and 20 Nm 3 / hour The mixed gas of water vapor was preheated to 1,000 ° C. and introduced into the reaction tube at a flow rate of 63 m / second and 60 m / second, respectively, using a coaxial parallel flow nozzle. However, a reaction tube as shown in FIG. 1 was used for the reaction, the inner tube diameter of the coaxial parallel flow nozzle was 20 mm, and a gas containing a mixed metal halide was introduced into the inner tube.
The inner diameter of the reaction tube was 100 mm, and the flow rate in the tube at a reaction temperature of 1,200 ° C. was 10 m / sec. After the reaction, cooling air was introduced into the reaction tube so that the high-temperature residence time in the reaction tube was 0.3 seconds or less, and then ultrafine powder produced using a Teflon bag filter was collected. Then, dechlorination was performed by heating in an oven in an air atmosphere at 500 ° C. for 1 hour.
The obtained ultrafine mixed crystal oxide has a BET specific surface area of 48 m 2 / g, an average true specific gravity of 3.9 g / cc, an average primary particle diameter of 0.032 μm, and chlorine of 0.1%. Aluminum bonding was observed.
Further, ΔOD was 1.2 / hr, ΔB was 5%, and A / B was 0.002.
実施例３：
ガス状四塩化珪素1.2Ｎｍ3／時間とガス状三塩化アルミニウム8.3Ｎｍ3／時間と窒素１０Ｎｍ3／時間を含有するガスを混合後1,000℃に、８Ｎｍ3／時間の酸素及び２０Ｎｍ3／時間の水蒸気の混合ガスを1,000℃にそれぞれ予熱して、同軸平行流ノズルを用いて、それぞれ流速８０ｍ／秒、６０ｍ／秒で反応管に導入した。ただし、反応は図１に示すような反応管を用い、同軸平行流ノズルの内管径は２０ｍｍとし、内管に混合ハロゲン化金属を含有するガスを導入した。
反応管の内径は１００ｍｍであり、反応温度1,200℃における管内流速は計算値で１１ｍ／秒であった。反応管内の高温滞留時間が0.3秒以下となるように、反応後冷却空気を反応管に導入し、その後、テフロン製バグフィルターを用いて製造された超微粒子粉末を捕集した。その後、オーブンにて空気雰囲気下、５００℃×１時間加熱し、脱塩素処理を実施した。
得られた超微粒子混晶酸化物は、ＢＥＴ比表面積が１２０ｍ2／ｇ、平均真比重3.5ｇ／ｃｃ、平均一次粒子径0.014μｍ、塩素が0.004％であり、ＸＰＳによって明らかに珪素−酸素−アルミニウム結合が認められた。
また、ΔＢは２％、Ａ／Ｂは0.00003であった。
Example 3:
The gas containing gaseous silicon tetrachloride 1.2 Nm 3 / time and gaseous aluminum trichloride 8.3 nm 3 / time and nitrogen 10 Nm 3 / time 1,000 ° C. After mixing, the 8 Nm 3 / time of oxygen and 20 Nm 3 / time The mixed gas of water vapor was preheated to 1,000 ° C. and introduced into the reaction tube at a flow rate of 80 m / second and 60 m / second using a coaxial parallel flow nozzle, respectively. However, a reaction tube as shown in FIG. 1 was used for the reaction, the inner tube diameter of the coaxial parallel flow nozzle was 20 mm, and a gas containing a mixed metal halide was introduced into the inner tube.
The inner diameter of the reaction tube was 100 mm, and the flow rate in the tube at a reaction temperature of 1,200 ° C. was 11 m / sec as a calculated value. After the reaction, cooling air was introduced into the reaction tube so that the high-temperature residence time in the reaction tube was 0.3 seconds or less, and then ultrafine powder produced using a Teflon bag filter was collected. Then, dechlorination was performed by heating in an oven in an air atmosphere at 500 ° C. for 1 hour.
The obtained ultrafine particle mixed crystal oxide has a BET specific surface area of 120 m 2 / g, an average true specific gravity of 3.5 g / cc, an average primary particle diameter of 0.014 μm, and chlorine of 0.004%. Aluminum bonding was observed.
Further, ΔB was 2%, and A / B was 0.00003.
比較例１：
ガス状四塩化チタン10.7Ｎｍ3／時間と窒素１２Ｎｍ3／時間を含有するガスを混合後９００℃に、８Ｎｍ3／時間の酸素及び２０Ｎｍ3／時間の水蒸気の混合ガスを1,000℃にそれぞれ予熱して、同軸平行流ノズルを用いて、それぞれ流速８６ｍ／秒、６０ｍ／秒で反応管に導入した。ただし、反応は図１に示すような反応管を用い、同軸平行流ノズルの内管径は２０ｍｍとし、内管にハロゲン化金属を含有するガスを導入した。
反応管の内径は１００ｍｍであり、反応温度1,200℃における管内流速は計算値で１２ｍ／秒であった。反応管内の高温滞留時間が0.3秒以下となるように、反応後冷却空気を反応管に導入し、その後、テフロン製バグフィルターを用いて製造された超微粒子粉末を捕集した。その後、オーブンにて空気雰囲気下、５００℃×１時間加熱し、脱塩素処理を実施した。
得られた超微粒子酸化物は、ＢＥＴ比表面積が５１ｍ2／ｇ、平均真比重4.0ｇ／ｃｃ、平均一次粒子径0.029μｍ、塩素が0.4％であった。
また、ΔＯＤは２１／ｈｒ、ΔＢは６２％、Ａ／Ｂは0.007であった。これは、実施例１、２と比べて光活性が強く、また焼結しやすい。塩素も多く残っている。
Comparative Example 1:
Gaseous titanium tetrachloride 10.7 Nm 3 / hour and nitrogen 12 Nm 3 / hour are mixed and then preheated to 900 ° C and 8 Nm 3 / hour oxygen and 20 Nm 3 / hour water vapor to 1,000 ° C. Then, they were introduced into the reaction tube at a flow rate of 86 m / sec and 60 m / sec using a coaxial parallel flow nozzle, respectively. However, the reaction tube shown in FIG. 1 was used for the reaction, the inner tube diameter of the coaxial parallel flow nozzle was 20 mm, and a gas containing a metal halide was introduced into the inner tube.
The inner diameter of the reaction tube was 100 mm, and the flow rate in the tube at a reaction temperature of 1,200 ° C. was 12 m / sec as a calculated value. After the reaction, cooling air was introduced into the reaction tube so that the high-temperature residence time in the reaction tube was 0.3 seconds or less, and then ultrafine powder produced using a Teflon bag filter was collected. Then, dechlorination was performed by heating in an oven in an air atmosphere at 500 ° C. for 1 hour.
The obtained ultrafine particle oxide had a BET specific surface area of 51 m 2 / g, an average true specific gravity of 4.0 g / cc, an average primary particle diameter of 0.029 μm, and chlorine of 0.4%.
Further, ΔOD was 21 / hr, ΔB was 62%, and A / B was 0.007. This is more photoactive than Examples 1 and 2 and is easy to sinter. A lot of chlorine remains.
比較例２：
ガス状三塩化アルミニウム8.3Ｎｍ3／時間と窒素２０Ｎｍ3／時間を含有するガスを混合後1,000℃に、８Ｎｍ3／時間の酸素及び２０Ｎｍ3／時間の水蒸気の混合ガスを1,000℃にそれぞれ予熱して、同軸平行流ノズルを用いて、それぞれ流速１０７ｍ／秒、６０ｍ／秒で反応管に導入した。ただし、反応は図１に示すような反応管を用い、同軸平行流ノズルの内管径は２０ｍｍとし、内管にハロゲン化金属を含有するガスを導入した。
反応管の内径は１００ｍｍであり、反応温度1,200℃における管内流速は計算値で１２ｍ／秒であった。反応管内の高温滞留時間が0.3秒以下となるように、反応後冷却空気を反応管に導入し、その後、テフロン製バグフィルターを用いて製造された超微粒子粉末を捕集した。その後、オーブンにて空気雰囲気下、５００℃×１時間加熱し、脱塩素処理を実施した。
得られた超微粒子酸化物は、ＢＥＴ比表面積が１１５ｍ2／ｇ、平均真比重3.7ｇ／ｃｃ、平均一次粒子径0.014μｍ、塩素が0.5％であった。また、ΔＢは７％、Ａ／Ｂは0.004であった。
これは実施例３と比べて焼結しやすく、塩素が多く残存している。
Comparative Example 2:
The gas containing gaseous aluminum trichloride 8.3 nm 3 / time and nitrogen 20 Nm 3 / time after the mixing 1,000 ° C., respectively preheat the 8 Nm 3 / time of oxygen and 20 Nm 3 / time of the mixed gas of water vapor 1,000 ° C. Then, they were introduced into the reaction tube at flow rates of 107 m / sec and 60 m / sec, respectively, using coaxial parallel flow nozzles. However, the reaction tube shown in FIG. 1 was used for the reaction, the inner tube diameter of the coaxial parallel flow nozzle was 20 mm, and a gas containing a metal halide was introduced into the inner tube.
The inner diameter of the reaction tube was 100 mm, and the flow rate in the tube at a reaction temperature of 1,200 ° C. was 12 m / sec as a calculated value. After the reaction, cooling air was introduced into the reaction tube so that the high-temperature residence time in the reaction tube was 0.3 seconds or less, and then ultrafine powder produced using a Teflon bag filter was collected. Then, dechlorination was performed by heating in an oven in an air atmosphere at 500 ° C. for 1 hour.
The obtained ultrafine particle oxide had a BET specific surface area of 115 m 2 / g, an average true specific gravity of 3.7 g / cc, an average primary particle diameter of 0.014 μm, and chlorine of 0.5%. Further, ΔB was 7%, and A / B was 0.004.
This is easier to sinter than Example 3, and a lot of chlorine remains.
実施例４：
実施例１のチタン−酸素−珪素の結合を有する超微粒子混晶酸化物に純水を加え粉末換算で0.5質量％となるようにスラリーを作製した。このスラリーに粉末に対してウレタン樹脂が７０質量％となるように水分散系ウレタン樹脂（VONDIC1040NS、大日本インキ化学工業（株）製）を添加して光機能性粉体とウレタン樹脂を含有した塗工剤を得た。
次に得られた塗工剤を１００μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム（東レ（株）製、ルミラーＴ）の片面に、２５μｍのアプリケーターで塗工し、８０℃で２時間乾燥し、超微粒子混晶酸化物を坦持したポリエチレンテレフタレートフィルムを得た。
得られたポリエチレンテレフタレートフィルムについて分光光度計（島津（株）製、UV-2400PC）で透過率の測定を行った結果、３６０ｎｍの透過率は１％、５５０ｎｍの透過率は８９％であった。
上記のポリエチレンテレフタレートフィルムにフェードメータ（Heraeus製、SUNSET CPS+）で７６ｍＷ／ｃｍ2の光をあて耐光性試験を行い１００時間後にフィルムの着色を調べたが、着色は見られなかった。
Example 4:
Pure water was added to the ultrafine particle mixed crystal oxide having a titanium-oxygen-silicon bond of Example 1 to prepare a slurry so as to be 0.5% by mass in terms of powder. A water-dispersed urethane resin (VONDIC1040NS, manufactured by Dainippon Ink & Chemicals, Inc.) was added to the slurry so that the urethane resin was 70% by mass with respect to the powder, and the photofunctional powder and the urethane resin were contained. A coating agent was obtained.
Next, the obtained coating agent was coated on one side of a 100 μm polyethylene terephthalate (PET) film (Lumirror T, manufactured by Toray Industries, Inc.) with a 25 μm applicator, dried at 80 ° C. for 2 hours, and mixed with ultrafine particles. A polyethylene terephthalate film carrying a crystalline oxide was obtained.
As a result of measuring the transmittance of the obtained polyethylene terephthalate film with a spectrophotometer (manufactured by Shimadzu Corporation, UV-2400PC), the transmittance at 360 nm was 1%, and the transmittance at 550 nm was 89%.
The polyethylene terephthalate film was subjected to a light resistance test by applying light of 76 mW / cm 2 with a fade meter (manufactured by Heraeus, SUNSET CPS +), and the film was examined for coloration after 100 hours, but no coloration was observed.
実施例５：
実施例１のチタン−酸素−珪素の結合を有する超微粒子混晶酸化物２０質量部、ステアリン酸亜鉛（日本油脂（株）製、ジンクステアレートＳ）２質量部、低密度ポリエチレン（ＬＤＰＥ）（日本ポリオレフィン（株）製、JH607C）７８質量部を二軸押出機（池貝鉄工（株）製、ＰＣＭ３０型）を用いて１６０℃（滞留時間約３分）で溶融混練し、ペレット化し、直径２〜３ｍｍφ、長さ３〜５ｍｍの重さ0.01〜0.02ｇの円柱状の超微粒子混晶酸化物を２０％含有する低密度ポリエチレンのコンパウンドを２０ｋｇ造った。
上記で得られた超微粒子混晶酸化物を含有する低密度ポリエチレンコンパウンド１ｋｇと低密度ポリエチレン（ＬＤＰＥ）（日本ポリオレフィン（株）製、JH607C）３９ｋｇをＶ型ブレンダー（池本理化工業（株）、RKI-40）で１０分間混合し、混合ペレットを作製した。
次に、得られた混合ペレットを４０ｍｍφの押出機を有するインフレーションフィルム成形機（吉井鉄工（株）、YEI-S40-40L）を用いて、４０μｍのインフレーションフィルムを作製した。得られたフィルムについて実施例４と同様に透過率と耐光性試験を行い、表１の結果が得られた。
Example 5:
20 parts by mass of an ultrafine mixed crystal oxide having a titanium-oxygen-silicon bond in Example 1, 2 parts by mass of zinc stearate (manufactured by NOF Corporation, Zinc stearate S), low density polyethylene (LDPE) ( 78 parts by mass of Nippon Polyolefin Co., Ltd., JH607C) was melt kneaded at 160 ° C. (residence time of about 3 minutes) using a twin screw extruder (Ikegai Iron Works Co., Ltd., PCM30 type), pelletized, and diameter 2 20 kg of a low density polyethylene compound containing 20% of cylindrical ultrafine mixed crystal oxide having a diameter of ˜3 mmφ and a length of 3 to 5 mm and a weight of 0.01 to 0.02 g was produced.
1 kg of low density polyethylene compound containing ultrafine mixed crystal oxide obtained above and 39 kg of low density polyethylene (LDPE) (manufactured by Nippon Polyolefin Co., Ltd., JH607C) were mixed with V-type blender (Ikemoto Rika Kogyo Co., Ltd., RKI) -40) for 10 minutes to prepare mixed pellets.
Next, a 40 μm inflation film was produced from the resulting mixed pellets using an inflation film molding machine (Yoshii Tekko Co., Ltd., YEI-S40-40L) having a 40 mmφ extruder. The obtained film was subjected to transmittance and light resistance tests in the same manner as in Example 4, and the results shown in Table 1 were obtained.
比較例３：
市販の超微粒子二酸化チタン（石原産業（株）社製、ST-01）について実施例４と同様にして処理および試験を行い、表１の結果を得た。
Comparative Example 3:
Commercially available ultrafine titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd., ST-01) was treated and tested in the same manner as in Example 4, and the results shown in Table 1 were obtained.
比較例４：
市販の超微粒子二酸化チタン（石原産業（株）社製、ST-01）について実施例５と同様にして処理および試験を行い、表１の結果を得た。
Comparative Example 4:
A commercially available ultrafine particle titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd., ST-01) was treated and tested in the same manner as in Example 5, and the results shown in Table 1 were obtained.
以上、詳しく説明したように、本発明によれば、混合ハロゲン化金属を酸化性ガスで高温酸化することにより超微粒子混晶酸化物を製造する気相法において、混合ハロゲン化金属を含有するガス及び酸化性ガスをそれぞれ５００℃以上に予熱してから反応させることで、超微粒子状で分散性に優れる、ＢＥＴ比表面積が１０〜２００ｍ2／ｇであり、かつ、混晶状態にある一次粒子を含む超微粒子混晶酸化物を得ることができる。
さらに、本発明の超微粒子混晶酸化物は、例えば光活性や焼結性を抑制もしくは調整することができ、かつ、残存塩素を大幅に低減できるものである。また、解砕工程等が不要もしくは極めて軽微な設備で済み、非常に簡便に製造することができ、各種の工業的用途に有用である。
As described above in detail, according to the present invention, in a gas phase method for producing ultrafine mixed crystal oxides by oxidizing a mixed metal halide with an oxidizing gas at a high temperature, a gas containing the mixed metal halide. And the oxidizing gas are preheated to 500 ° C. or more, and then reacted to form ultrafine particles that are excellent in dispersibility, have a BET specific surface area of 10 to 200 m 2 / g, and are in a mixed crystal state. Can be obtained.
Furthermore, the ultrafine particle mixed crystal oxide of the present invention can suppress or adjust photoactivity and sinterability, for example, and can greatly reduce residual chlorine. Moreover, the crushing process etc. are unnecessary or an extremely light installation is sufficient, it can manufacture very simply and is useful for various industrial uses.
Claims (24)
A structure comprising the ultrafine mixed crystal oxide according to any one of claims 1 to 5 on a surface.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005154750A (en) * | 2003-10-30 | 2005-06-16 | Showa Denko Kk | Transparent film-forming composition |
| WO2009101930A1 (en) * | 2008-02-12 | 2009-08-20 | Teijin Techno Products Limited | Flame-retardant resin composition, flame-retardant fiber, flame-retardant cloth, and heat-resistant protective clothing |
| JP2010519393A (en) * | 2007-02-28 | 2010-06-03 | エボニック デグサ ゲーエムベーハー | polymer |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005154750A (en) * | 2003-10-30 | 2005-06-16 | Showa Denko Kk | Transparent film-forming composition |
| JP2010519393A (en) * | 2007-02-28 | 2010-06-03 | エボニック デグサ ゲーエムベーハー | polymer |
| WO2009101930A1 (en) * | 2008-02-12 | 2009-08-20 | Teijin Techno Products Limited | Flame-retardant resin composition, flame-retardant fiber, flame-retardant cloth, and heat-resistant protective clothing |
| JP5580057B2 (en) * | 2008-02-12 | 2014-08-27 | 帝人株式会社 | Flame retardant resin composition, flame retardant fiber, flame retardant fabric and heat resistant protective clothing |
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