JP3732265B2 - Spindle-shaped fine particle titanium dioxide and method for producing the same - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、その形状が紡錘状の微粒子二酸化チタン及びその製造方法に関するものであり、特に日焼け止め化粧料、紫外線防止塗料、プラスチックスなどの紫外線防止乃至遮蔽剤として有用なものである。
【０００２】
【従来の技術】
一次粒子径が０．１μｍ以下の微粒子酸化チタンは、樹脂の膜或いは成形物に配合した場合に可視光線を透過させるので透明性を示す一方で、紫外線を遮蔽して紫外線により変色、変質する物質を保護するといったように、一次粒子径が約０．１５〜０．５μｍの顔料級酸化チタンとは異なった有用な性質を示すことから、日焼け止め化粧料、紫外線防止塗料、プラスチックスなどの紫外線防止乃至遮蔽剤としての利用が図られつつある。
【０００３】
【発明が解決しようとする課題】
ところで前記微粒子酸化チタンの透明性と紫外線遮蔽性とは、透明性が粒子径に反比例して増加するのに対して、紫外線遮蔽性は、一定の粒径範囲において最大値を示し、粒子径が前記範囲を逸脱する大きなものであっても、また小さなものであっても、その紫外線遮蔽性は低下する。従って、透明性と紫外線遮蔽性とを同時に満足するような微粒子酸化チタンの出現が望まれている。
【０００４】
しかして、前記の一次粒子の平均粒子径が約０．０５〜０．１μｍの微粒子酸化チタンを製造する方法としては、例えば硫酸チタニル溶液や四塩化チタン溶液を加水分解して得られた含水酸化チタンのチタニアゾル、或いは前記含水酸化チタンを苛性アルカリで処理した後、塩酸存在下で加熱処理して得られたチタニアゾルを、焼成する方法が行われている。しかしながら、前記焼成過程で粒子焼結が著しく惹起し易く、このために種々の用途適用媒体系において、実質的に前記の一次粒子まで分散させることが難しく、その結果十分なる紫外線遮蔽効果をもたらし得ず、その改善が強く希求されている。
【０００５】
また、特開昭63-307119 には、含水酸化チタンをアルカリで処理し、次いで塩酸を添加、熟成することで焼成工程を経ずに分散の良い針状微粒子二酸化チタンが得られるとの記載がある。しかしながら、上記方法で得られる二酸化チタンは、長さ０．０１〜０．１５μｍ、軸比２〜８と微細なものであり、透明性は得られるものの、充分な紫外線遮蔽性を有しないという問題がある。
【０００６】
【課題を解決するための手段】
本発明者らは、前記問題点を解決するべく含水酸化チタンのアルカリ処理、塩酸添加について種々検討した結果、塩酸添加方法を工夫することで粒子の大きさの抑制が可能であること、及び特定条件の下で得られる特定の長さ、特定の太さ、特定の比表面積を有する特定形状の微粒子二酸化チタンが、優れた紫外線遮蔽性を有するとともに、その用途適用系で透明性も良好なものである等の知見を得、本発明を完成した。
【０００７】
即ち本発明は、１）長さが０．１５〜０．２５μｍであり、軸比が３〜９であって、かつ、比表面積が８０〜１２０ｍ2 ／ｇである紡錘状微粒子二酸化チタン、２）その粒子表面にアルミニウム、ケイ素、チタニウム、ジルコニウム、スズ及びアンチモンの群から選ばれる少なくとも一種の含水酸化物又は酸化物の被覆を有する前記１）記載の紡錘状微粒子二酸化チタン、３）含水酸化チタンをアルカリで処理し、次いで得られた反応生成物と塩酸とを、該反応生成物の酸化チタン１モルに対して塩酸０．１〜２モルの割合で瞬時の混合下で反応させ、次いで８０℃以下の温度で加熱熟成し、その後更に酸化チタン１モルに対して塩酸０．１〜２モルの割合で瞬時の混合下で反応させた後８５℃以上で加熱熟成することを特徴とする長さが０．１５〜０．２５μｍであり、軸比が３〜９であって、かつ、比表面積が８０〜１２０ｍ2 ／ｇである紡錘状微粒子二酸化チタンの製造方法、４）前記３）の方法で得られた紡錘状微粒子二酸化チタンをスラリーとし、アルミニウム、ケイ素、チタニウム、ジルコニウム、スズ及びアンチモンの各水溶性塩の群から選ばれた少なくとも一種を添加し、中和して該元素の含水酸化物又は酸化物を該微粒子二酸化チタンの粒子表面に被覆させることを特徴とする紡錘状微粒子二酸化チタンの製造方法、５）前記１）又は２）の紡錘状微粒子二酸化チタンを含有する日焼け止め化粧料、６）前記１）又は２）の紡錘状微粒子二酸化チタンを含有する紫外線防止塗料及び、７）前記１）又は２）の紡錘状微粒子二酸化チタンを含有する紫外線防止プラスチックス組成物、である。
【０００８】
本発明の紡錘状微粒子二酸化チタンは、種々の日焼け止め化粧料や紫外線防止用塗料、紫外線防止プラスチックス組成物に有用なものであり、さらにこのものの粒子表面に、アルミニウム、ケイ素、チタニウム、ジルコニウム、スズ及びアンチモンなどの金属の含水酸化物を沈殿させ、被覆させて、当該二酸化チタンの分散媒体における分散性、耐光性などを一層向上させることもできる。被覆させる前記金属の含水酸化物又は酸化物の量は、酸化チタンに対して当該金属の酸化物換算総量で１〜１００重量％である。
【０００９】
また、本発明の紡錘状微粒子二酸化チタンに導電処理を施した紡錘状微粒子導電性二酸化チタンは、プラスチックス、ゴム、繊維などに導電性付与材或いは基体として配合し、導電性プラスチックス、導電性塗料、磁性塗料、導電性ゴム、導電性繊維などの導電性組成物として利用することができるものである。また、電子写真複写紙、静電記録紙などの記録材料の支持体用導電性付与剤或いはその基体としても有用なものである。導電処理は、紡錘状微粒子二酸化チタンの粒子表面に、アンチモン含有酸化錫或いは錫含有酸化インジウムからなる導電層を形成させる。導電層を形成させるには、前記微粒子二酸化チタンに対し、例えば水溶性錫化合物および水溶性アンチモン化合物を添加処理して、酸化チタン粒子表面に錫の含水酸化物とアンチモンの含水酸化物を被着した後、焼成し、アンチモン含有酸化錫からなる導電層を被着することによって製造される。この場合、酸化錫の量は、ＳｎＯ2 として１０〜１５０重量％、望ましくは３０〜１００重量％である。この範囲より少なすぎると連続した導電層の形成が困難となり、所望の導電性が得られないし、多すぎても量の増加に応じた導電性向上が期待できないので経済的でない。また、導電層中の前記酸化アンチモンの量は、前記酸化錫（ＳｎＯ2 ）に対し、Ｓｂ2 Ｏ3 として５〜４０重量％望ましくは１０〜３０重量％である。この範囲より少なすぎると所望の導電性が得られ難くなり、また多すぎても導電性が低下したり、酸化アンチモンによる着色が強くなったりするので望ましくない。
【００１０】
次に本発明の紡錘状微粒子二酸化チタンの製造方法について説明する。
先ず、含水酸化チタン水性懸濁液にアルカリを添加し、次に９０〜１００℃の温度に加熱処理して反応生成物を得、次いで必要に応じてｐＨを中性に調整して固液分離し、固形分を水洗する。前記アルカリ処理に用いられるアルカリとしては、水酸化ナトリウム、炭酸ナトリウムなどが挙げられるが、水酸化ナトリウム水溶液を使用するのが好ましい。アルカリの量としては、酸化チタン１モルに対して１〜８モルが望ましい。前記の水洗した固形分を水中に懸濁させて懸濁液とし、該懸濁液と塩酸とを、該反応生成物の酸化チタン１モルに対して塩酸０．１〜２モルの割合で瞬時の混合下で反応させ、８０℃以下の温度で加熱熟成し、その後更に酸化チタン１モルに対して塩酸０．１〜２モルの割合で瞬時に混合して反応させる。より具体的には、例えば前記懸濁液中の反応生成物に対して塩酸を遅くとも２モル／秒の急速で添加する。その後、８５〜１００℃、好ましくは９０〜１００℃の温度で１時間以上加熱熟成して、紡錘状微粒子二酸化チタンの水性懸濁液を得、濾過、洗浄、乾燥して粉末を得る。
【００１１】
紡錘状微粒子二酸化チタンのチタン源である含水酸化チタンとしては、例えば硫酸チタニル溶液や四塩化チタン溶液の加水分解や中和加水分解によって得られるものが挙げられる。より具体的には、例えば四塩化チタン水溶液を室温の保持しながら水酸化ナトリウム水溶液で中和してコロイド状の非晶質水酸化チタンを析出させ、このコロイド状水酸化チタンを加熱熟成して得られるルチル型の微小チタニアゾルを使用することができる。
【００１２】
前記のようにして得られた紡錘状微粒子二酸化チタンの粒子表面に、アルミニウム、ケイ素、チタニウム、ジルコニウム、スズ及びアンチモンなどの金属の含水酸化物又は酸化物を沈殿、被覆させてもよい。この方法は、例えば紡錘状微粒子二酸化チタンを水に分散させてスラリーとし、必要に応じて湿式粉砕、分級処理した後、この中にアルミニウム、ケイ素、チタニウム、ジルコニウム、スズ及びアンチモンの各水溶性塩の群から選ばれた少なくとも一種を酸化チタンに対して酸化物換算総量で１〜１００重量％添加後、該水溶性塩がスラリー中でアルカリ性を示す場合は硫酸、塩酸等の酸性溶液で、該水溶性塩がスラリー中で酸性を示す場合は水酸化ナトリウム、アンモニア水等のアルカリ水溶液で中和して該酸化チタン粒子の表面に沈殿、被覆させ、このものを分別後、乾燥、粉砕することにより行うことができる。この被覆処理により紡錘状微粒子二酸化チタンの分散媒体における分散性、耐久性などを向上させることができる。
【００１３】
本発明の紡錘状微粒子二酸化チタンは、前記した如く種々の日焼け止め化粧料や紫外線防止用塗料、紫外線防止プラスチックス組成物に有用なものである。
【００１４】
本発明の紡錘状微粒子二酸化チタンを日焼け止め化粧料として利用する場合には、例えば油性成分、保湿剤、界面活性剤、顔料、香料、防腐剤、水、アルコール類、増粘剤等と配合し、ローション状、クリーム状、ペースト状、ステック状、乳液状など、各種の形態で用いることができる。
【００１５】
紫外線防止プラスチックスとして利用する場合には、例えば塩化ビニル樹脂、ＡＢＳ樹脂、ポリエチレン、ポリプロピレン、塩化ビニリデン、ポリスチレン、ポリカーボネート、ナイロン、ＥＶＡ樹脂、ポリアセタール樹脂、ポリアミド樹脂、フェノール樹脂、メラミン樹脂、アクリル樹脂、ポリエステル樹脂、ユリア樹脂、シリコーン樹脂、フッ素樹脂などの合成樹脂に配合される。
【００１６】
紫外線防止用塗料として利用する場合には、例えばポリビニルアルコール樹脂、塩ビ−酢ビ樹脂、アクリル樹脂、エポキシ樹脂、ウレタン樹脂、アルキッド樹脂、ポリエステル樹脂、エチレン酢酸ビニル共重合体、アクリル−スチレン共重合体、繊維素樹脂、フェノール樹脂、アミノ樹脂などに配合され、水または溶媒中で分散される。
【００１７】
また、本発明の紡錘状微粒子二酸化チタンを各種化粧料や塗料として用いる場合には、化粧品分野や塗料分野で使用される種々の有機系処理剤、例えばカルボン酸、ポリオール、アミン、シロキサン、シランカップリング剤等の有機物の少なくとも一種で被覆されても良く、その場合、化粧料、塗料への分散性及び塗膜の耐久性を一層向上させ得ることもある。
【００１８】
【実施例】
実施例１
（１）四塩化チタン水溶液の加水分解により得られた含水酸化チタンを、ＴｉＯ2 換算１００ｇ／リットルの濃度の水性懸濁液とした。この水性懸濁液２リットルに４８％水酸化ナトリウム水溶液１４００ｇを攪拌しながら添加し、９５℃で１２０分加熱後、濾過し、十分に洗浄を行った。洗浄ケーキを水でレパルプし、ＴｉＯ2 換算１００ｇ／リットルの水性懸濁液とし、この水性懸濁液１．５リットルを、還流器付フラスコに入れ、３５％塩酸２９０ｇを攪拌しながら瞬時（４モル／秒）に添加した後、３０分熟成し、その後更に３５％塩酸２９０ｇを攪拌しながら瞬時（４モル／秒）に添加した。その９５℃で１２０分間加熱熟成し、ルチル型結晶の長さ０．１８μｍ、軸比４．５、比表面積９６ｍ2 ／ｇの紡錘状微粒子二酸化チタンを含む水性懸濁液を得た。
【００１９】
（２）前記（１）で得られた紡錘状微粒子二酸化チタンを含む水性懸濁液を濾過、洗浄して、得られた洗浄ケーキを１２０℃で一昼夜乾燥し、粉末（試料Ａ）を得た。
【００２０】
比較例１
（１）四塩化チタン水溶液の加水分解により得られた含水酸化チタンを、ＴｉＯ2 換算１００ｇ／リットルの濃度の水性懸濁液とした。この水性懸濁液２リットルに４８％水酸化ナトリウム水溶液１４００ｇを攪拌しながら添加し、９５℃で１２０分加熱後、濾過し、十分に洗浄を行った。洗浄ケーキを水でレパルプし、ＴｉＯ2 換算１００ｇ／リットルの水性懸濁液とし、この水性懸濁液１．５リットルを、還流器付フラスコに入れ、３５％塩酸５７０ｇを攪拌しながら３０分間で添加した後、９５℃まで加熱し、９０分間熟成し、ルチル型結晶の長軸０．０７μｍ、軸比７、比表面積９９ｍ2 ／ｇの紡錘状微粒子二酸化チタンを含む水性懸濁液を得た。
【００２１】
（２）前記（１）で得られた紡錘状微粒子二酸化チタンを含む水性懸濁液を濾過、洗浄して、得られた洗浄ケーキを１２０℃で一昼夜乾燥し、粉末（試料Ｂ）を得た。
【００２２】
比較例２
（１）四塩化チタン水溶液の加水分解により得られた含水酸化チタンを、ＴｉＯ2 換算１００ｇ／リットルの濃度の水性懸濁液とした。この水性懸濁液２リットルに４８％水酸化ナトリウム水溶液１４００ｇを攪拌しながら添加し、９５℃で１２０分加熱後、濾過し、十分に洗浄を行った。洗浄ケーキを水でレパルプし、ＴｉＯ2 換算１００ｇ／リットルの水性懸濁液とし、この水性懸濁液１．５リットルを、還流器付フラスコに入れ、３５％塩酸５７０ｇを攪拌しながら瞬時（４モル／秒）に添加した後、９５℃で１２０分間加熱熟成し、ルチル型結晶の長さ０．３０μｍ、太さ０．０５５μｍ、比表面積７９ｍ2 ／ｇの樹枝状又はヒトデ状状微粒子二酸化チタンを含む水性懸濁液を得た。
【００２３】
（２）前記（１）で得られた樹枝状又はヒトデ状状状微粒子二酸化チタンを含む水性懸濁液を濾過、洗浄して、得られた洗浄ケーキを１２０℃で一昼夜乾燥し、粉末（試料Ｃ）を得た。
【００２４】
試験例１
前記実施例１、比較例１及び比較例２で得た試料Ａ、Ｂ及びＣの微粒子二酸化チタンを、それぞれ下記の処方で日焼け止めクリームとした。
（１）ステアリン酸 ５．０重量部
（２）ミツロウ ３．０ 〃
（３）セタノール ３．５ 〃
（４）スクワラン １０．０ 〃
（５）微粒子二酸化チタン ３．０ 〃
（６）モノステアリン酸グリセリン ３．０ 〃
（７）メチルパラベン ０．１ 〃
（８）香料 ０．３ 〃
（９）グリセリン １１．０ 〃
（10）トリエタノールアミン １．０ 〃
（11）精製水 ６０．１ 〃
【００２５】
成分（１）〜（５）を８０℃で加熱混合後、成分（６）〜（８）を加え７０℃に調整し、７０℃で加熱混合した成分（９）〜（11）に加え、ホモミキサーでよく混合し、放置・冷却して日焼け止めクリームを調製した。
【００２６】
評価方法
上記各クリームを石英ガラス上に２５μｍの膜厚になるように塗布し、分光光度計にて７５０〜３００ｎｍの透過光を測定した。以上の評価結果を表１に示す。
【００２７】
【表１】
【発明の効果】
本発明は、含水酸化チタン水性懸濁液をアルカリで処理し、次いで塩酸を急速添加し、加熱熟成する簡潔な方法でもって得られる紡錘状微粒子二酸化チタンであって、当該二酸化チタンは、そのものの粒子表面に各種金属化合物等を被覆乃至被着することによって、優れた透明性と紫外線防止或いは遮蔽機能を有する化粧料や塗料として用いることができるものであり、工業的に極めて大きな効果を奏するものである。
【図面の簡単な説明】
【図１】図１は、実施例１で得た本発明の紡錘状微粒子二酸化チタン粉末（試料Ａ）の粒子構造を示す電子顕微鏡写真（倍率100,000 倍）である。
【図２】図２は、比較例１で得た紡錘状微粒子二酸化チタン粉末（試料Ｂ）の粒子構造を示す電子顕微鏡写真（倍率100,000 倍）である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a spindle-shaped fine particle titanium dioxide and a method for producing the same, and is particularly useful as an anti-UV or shielding agent for sunscreen cosmetics, anti-UV paints, plastics and the like.
[0002]
[Prior art]
Fine particle titanium oxide with a primary particle size of 0.1 μm or less is transparent because it transmits visible light when blended in a resin film or molded product, while it is transparent, while it discolors and changes its properties by blocking ultraviolet light. Because it exhibits useful properties different from pigment grade titanium oxide with a primary particle size of about 0.15 to 0.5 μm, such as sunscreen cosmetics, UV protection paints, plastics, etc. It is being used as a preventive or shielding agent.
[0003]
[Problems to be solved by the invention]
By the way, the transparency and the ultraviolet shielding property of the fine particle titanium oxide, while the transparency increases in inverse proportion to the particle diameter, the ultraviolet shielding property shows a maximum value in a certain particle size range, and the particle diameter is Even if it is a big thing and the small thing which deviate from the said range, the ultraviolet-ray shielding property will fall. Therefore, the appearance of fine particle titanium oxide that satisfies both transparency and ultraviolet shielding properties simultaneously is desired.
[0004]
Thus, as a method for producing fine titanium oxide having an average primary particle size of about 0.05 to 0.1 μm, for example, hydrous oxide obtained by hydrolyzing a titanyl sulfate solution or a titanium tetrachloride solution is used. There is a method in which a titania sol of titanium or a titania sol obtained by treating a hydrous titanium oxide with a caustic alkali and then heat-treating in the presence of hydrochloric acid is calcined. However, particle sintering is very likely to occur during the firing process, and for this reason, it is difficult to disperse substantially to the primary particles in various application media systems, and as a result, sufficient UV shielding effect can be obtained. However, there is a strong need for improvement.
[0005]
Further, JP-A-63-307119 describes that acicular fine particle titanium dioxide having good dispersion can be obtained without passing through a firing step by treating hydrous titanium oxide with an alkali, then adding hydrochloric acid and aging. is there. However, the titanium dioxide obtained by the above method has a length of 0.01 to 0.15 μm and an axial ratio of 2 to 8 and is fine, and although it has transparency, it does not have sufficient ultraviolet shielding properties. There is.
[0006]
[Means for Solving the Problems]
As a result of various studies on alkali treatment of hydrous titanium oxide and addition of hydrochloric acid in order to solve the above problems, the present inventors have devised a method for adding hydrochloric acid and can control the size of the particles. Particulate titanium dioxide with a specific shape with a specific length, specific thickness and specific surface area obtained under certain conditions has excellent UV shielding properties and good transparency in its application application system As a result, the present invention was completed.
[0007]
That is, the present invention relates to 1) spindle-shaped fine particle titanium dioxide having a length of 0.15 to 0.25 μm, an axial ratio of 3 to 9, and a specific surface area of 80 to 120 m 2 / g. 1) Spindle-shaped fine particle titanium dioxide as described in 1) above, wherein the particle surface has a coating of at least one hydrous oxide or oxide selected from the group consisting of aluminum, silicon, titanium, zirconium, tin and antimony; 3) hydrous titanium oxide Then, the reaction product obtained and hydrochloric acid are reacted under instantaneous mixing at a ratio of 0.1 to 2 mol of hydrochloric acid with respect to 1 mol of titanium oxide of the reaction product. Heat aging at a temperature of ℃ or less, and further reacting under instantaneous mixing at a ratio of 0.1 to 2 mol of hydrochloric acid with respect to 1 mol of titanium oxide, followed by heating and aging at 85 ° C or more. 0 A 15～0.25Myuemu, a axial ratio 3-9, and a method for producing spindle-shaped particles of titanium dioxide is a specific surface area of 80 to 120 2 / g, obtained by the method of 4) the 3) The spindle-shaped fine particle titanium dioxide is made into a slurry, and at least one selected from the group of water-soluble salts of aluminum, silicon, titanium, zirconium, tin and antimony is added, neutralized, and hydrated oxide or oxide of the element A method for producing spindle-shaped fine particle titanium dioxide, characterized in that a product is coated on the particle surface of the fine particle titanium dioxide, 5) sunscreen cosmetics containing spindle-shaped fine particle titanium dioxide of 1) or 2) above, 6) UV protection paint containing spindle-shaped fine particle titanium dioxide of 1) or 2) and 7) UV protection plus containing spindle-shaped fine particle titanium dioxide of 1) or 2) Box composition, it is.
[0008]
The spindle-shaped fine particle titanium dioxide of the present invention is useful for various sunscreen cosmetics, UV-preventing paints, UV-preventing plastics compositions, and further, aluminum, silicon, titanium, zirconium, It is also possible to further improve the dispersibility, light resistance and the like of the titanium dioxide in a dispersion medium by precipitating and coating a metal oxide such as tin and antimony. The amount of the hydrous oxide or oxide of the metal to be coated is 1 to 100% by weight in terms of the total oxide equivalent of the metal with respect to titanium oxide.
[0009]
Further, the spindle-shaped fine particle conductive titanium dioxide obtained by subjecting the spindle-shaped fine particle titanium dioxide of the present invention to a conductive treatment is blended as a conductivity-imparting material or substrate in plastics, rubber, fiber, etc. It can be used as a conductive composition such as paint, magnetic paint, conductive rubber, conductive fiber, and the like. It is also useful as a conductivity-imparting agent for a support of a recording material such as electrophotographic copying paper and electrostatic recording paper, or a substrate thereof. In the conductive treatment, a conductive layer made of antimony-containing tin oxide or tin-containing indium oxide is formed on the surface of the spindle-shaped fine particle titanium dioxide. In order to form a conductive layer, for example, a water-soluble tin compound and a water-soluble antimony compound are added to the fine particle titanium dioxide to deposit tin hydrated oxide and antimony hydrated oxide on the titanium oxide particle surface. Then, it is baked and manufactured by depositing a conductive layer made of antimony-containing tin oxide. In this case, the amount of tin oxide, a SnO 2 10 to 150 wt%, preferably from 30 to 100 wt%. If the amount is less than this range, it is difficult to form a continuous conductive layer, and desired conductivity cannot be obtained. If the amount is too large, improvement in conductivity according to the increase in the amount cannot be expected, which is not economical. The amount of the antimony oxide in the conductive layer is 5 to 40% by weight, preferably 10 to 30% by weight as Sb 2 O 3 with respect to the tin oxide (SnO 2 ). If the amount is less than this range, it is difficult to obtain desired conductivity. If the amount is too large, the conductivity is lowered or coloring by antimony oxide becomes strong, which is not desirable.
[0010]
Next, the manufacturing method of the spindle-shaped fine particle titanium dioxide of this invention is demonstrated.
First, an alkali is added to a hydrous titanium oxide aqueous suspension, then a heat treatment is performed at a temperature of 90 to 100 ° C. to obtain a reaction product, and then the pH is adjusted to neutral as necessary to perform solid-liquid separation. And the solid content is washed with water. Examples of the alkali used for the alkali treatment include sodium hydroxide and sodium carbonate, but it is preferable to use an aqueous sodium hydroxide solution. The amount of alkali is preferably 1 to 8 mol per 1 mol of titanium oxide. The solid content washed with water is suspended in water to form a suspension, and the suspension and hydrochloric acid are instantaneously added at a ratio of 0.1 to 2 mol of hydrochloric acid with respect to 1 mol of titanium oxide of the reaction product. The mixture is allowed to react at a temperature of 80 ° C. or less, and then further mixed instantaneously at a ratio of 0.1 to 2 mol of hydrochloric acid with respect to 1 mol of titanium oxide. More specifically, for example, hydrochloric acid is rapidly added to the reaction product in the suspension at a rate of 2 mol / second at the latest. Thereafter, it is heated and aged at 85 to 100 ° C., preferably 90 to 100 ° C. for 1 hour or longer to obtain an aqueous suspension of spindle-shaped fine particle titanium dioxide, which is filtered, washed and dried to obtain a powder.
[0011]
Examples of the hydrous titanium oxide that is the titanium source of the spindle-shaped fine particle titanium dioxide include those obtained by hydrolysis or neutralization hydrolysis of a titanyl sulfate solution or a titanium tetrachloride solution. More specifically, for example, an aqueous solution of titanium tetrachloride is neutralized with an aqueous solution of sodium hydroxide while maintaining a room temperature to precipitate colloidal amorphous titanium hydroxide, and the colloidal titanium hydroxide is heated and aged. The resulting rutile microtitania sol can be used.
[0012]
A hydrous oxide or oxide of a metal such as aluminum, silicon, titanium, zirconium, tin, and antimony may be precipitated and coated on the surface of the spindle-shaped fine particle titanium dioxide obtained as described above. In this method, for example, spindle-shaped fine particles of titanium dioxide are dispersed in water to form a slurry, which is subjected to wet pulverization and classification treatment as necessary, and then each water-soluble salt of aluminum, silicon, titanium, zirconium, tin and antimony. After adding at least one selected from the group of 1 to 100% by weight in terms of oxide with respect to titanium oxide, when the water-soluble salt is alkaline in the slurry, an acidic solution such as sulfuric acid or hydrochloric acid, If the water-soluble salt is acidic in the slurry, neutralize it with an aqueous alkali solution such as sodium hydroxide or ammonia water, precipitate and coat the surface of the titanium oxide particles, separate this, dry it and grind it Can be performed. This coating treatment can improve the dispersibility and durability of the spindle-shaped fine particle titanium dioxide in the dispersion medium.
[0013]
The spindle-shaped fine particle titanium dioxide of the present invention is useful for various sunscreen cosmetics, UV protection paints, and UV protection plastic compositions as described above.
[0014]
When the spindle-shaped fine particle titanium dioxide of the present invention is used as a sunscreen cosmetic, it is blended with, for example, an oily component, a moisturizer, a surfactant, a pigment, a fragrance, an antiseptic, water, an alcohol, a thickener and the like. , Lotions, creams, pastes, sticks, and emulsions.
[0015]
In the case of use as an ultraviolet ray preventing plastic, for example, vinyl chloride resin, ABS resin, polyethylene, polypropylene, vinylidene chloride, polystyrene, polycarbonate, nylon, EVA resin, polyacetal resin, polyamide resin, phenol resin, melamine resin, acrylic resin, It is blended in a synthetic resin such as a polyester resin, a urea resin, a silicone resin, or a fluorine resin.
[0016]
When used as a paint for preventing ultraviolet rays, for example, polyvinyl alcohol resin, vinyl chloride-vinyl acetate resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, polyester resin, ethylene vinyl acetate copolymer, acrylic-styrene copolymer , Blended with fiber resin, phenol resin, amino resin, etc. and dispersed in water or solvent.
[0017]
When the spindle-shaped fine particle titanium dioxide of the present invention is used as various cosmetics and paints, various organic treatment agents used in the cosmetics and paint fields, such as carboxylic acids, polyols, amines, siloxanes, and silane cups. It may be coated with at least one organic material such as a ring agent, in which case the dispersibility in cosmetics and paints and the durability of the coating film may be further improved.
[0018]
【Example】
Example 1
(1) Hydrous titanium oxide obtained by hydrolysis of an aqueous titanium tetrachloride solution was made into an aqueous suspension having a concentration of 100 g / liter in terms of TiO 2 . To 2 liters of this aqueous suspension, 1400 g of a 48% aqueous sodium hydroxide solution was added with stirring, heated at 95 ° C. for 120 minutes, filtered, and thoroughly washed. The washed cake is repulped with water to obtain an aqueous suspension of 100 g / liter in terms of TiO 2 , and 1.5 liter of this aqueous suspension is placed in a flask with a reflux condenser, and 290 g of 35% hydrochloric acid is stirred instantaneously (4 The mixture was aged for 30 minutes, and then 290 g of 35% hydrochloric acid was added instantaneously (4 mol / sec) with stirring. The mixture was aged by heating at 95 ° C. for 120 minutes to obtain an aqueous suspension containing spindle-shaped fine particle titanium dioxide having a rutile crystal length of 0.18 μm, an axial ratio of 4.5, and a specific surface area of 96 m 2 / g.
[0019]
(2) The aqueous suspension containing spindle-shaped fine particle titanium dioxide obtained in (1) above was filtered and washed, and the resulting washed cake was dried at 120 ° C. overnight to obtain a powder (sample A). .
[0020]
Comparative Example 1
(1) Hydrous titanium oxide obtained by hydrolysis of an aqueous titanium tetrachloride solution was made into an aqueous suspension having a concentration of 100 g / liter in terms of TiO 2 . To 2 liters of this aqueous suspension, 1400 g of a 48% aqueous sodium hydroxide solution was added with stirring, heated at 95 ° C. for 120 minutes, filtered, and thoroughly washed. The washed cake is repulped with water to obtain an aqueous suspension of 100 g / liter in terms of TiO 2 , and 1.5 liter of this aqueous suspension is placed in a flask equipped with a reflux condenser, and 570 g of 35% hydrochloric acid is stirred for 30 minutes. After the addition, the mixture was heated to 95 ° C. and aged for 90 minutes to obtain an aqueous suspension containing spindle-shaped fine particle titanium dioxide having a major axis of rutile crystals of 0.07 μm, an axial ratio of 7, and a specific surface area of 99 m 2 / g. .
[0021]
(2) The aqueous suspension containing spindle-shaped fine particle titanium dioxide obtained in (1) above was filtered and washed, and the resulting washed cake was dried at 120 ° C. overnight to obtain a powder (sample B). .
[0022]
Comparative Example 2
(1) Hydrous titanium oxide obtained by hydrolysis of an aqueous titanium tetrachloride solution was made into an aqueous suspension having a concentration of 100 g / liter in terms of TiO 2 . To 2 liters of this aqueous suspension, 1400 g of a 48% aqueous sodium hydroxide solution was added with stirring, heated at 95 ° C. for 120 minutes, filtered, and thoroughly washed. The washed cake is repulped with water to obtain an aqueous suspension of 100 g / liter in terms of TiO 2 , and 1.5 liter of this aqueous suspension is placed in a flask equipped with a reflux condenser, and 570 g of 35% hydrochloric acid is stirred instantaneously (4 Mole / second), and then heat-aged at 95 ° C. for 120 minutes to form dendritic or starfish-like fine particles of rutile crystals having a length of 0.30 μm, a thickness of 0.055 μm, and a specific surface area of 79 m 2 / g. An aqueous suspension containing was obtained.
[0023]
(2) The aqueous suspension containing the dendritic or starfish-like fine particles of titanium dioxide obtained in (1) above is filtered and washed, and the resulting washed cake is dried at 120 ° C. overnight to obtain a powder (sample C) was obtained.
[0024]
Test example 1
Samples A, B and C of particulate titanium dioxide obtained in Example 1, Comparative Example 1 and Comparative Example 2 were each made into a sunscreen cream according to the following formulation.
(1) Stearic acid 5.0 parts by weight (2) Beeswax 3.0 〃
(3) Cetanol 3.5 〃
(4) Squalane 10.0 〃
(5) Fine particle titanium dioxide 3.0 ３．０
(6) Glycerol monostearate 3.0 〃
(7) Methylparaben 0.1 〃
(8) Fragrance 0.3 〃
(9) Glycerin 11.0 〃
(10) Triethanolamine 1.0 〃
(11) Purified water 60.1 〃
[0025]
After components (1) to (5) are heated and mixed at 80 ° C., components (6) to (8) are added and adjusted to 70 ° C., and added to components (9) to (11) heated and mixed at 70 ° C. Mix well with a mixer, leave and cool to prepare a sunscreen cream.
[0026]
Evaluation method Each of the above creams was applied on quartz glass so as to have a film thickness of 25 μm, and transmitted light of 750 to 300 nm was measured with a spectrophotometer. The above evaluation results are shown in Table 1.
[0027]
[Table 1]
【The invention's effect】
The present invention is a spindle-shaped fine particle titanium dioxide obtained by a simple method of treating a hydrous titanium oxide aqueous suspension with an alkali, then rapidly adding hydrochloric acid, and aging by heating. By coating or depositing various metal compounds on the particle surface, it can be used as cosmetics and paints having excellent transparency and UV prevention or shielding function, and has an extremely large industrial effect. It is.
[Brief description of the drawings]
1 is an electron micrograph (magnification 100,000 times) showing the particle structure of the spindle-shaped fine particle titanium dioxide powder (sample A) of the present invention obtained in Example 1. FIG.
2 is an electron micrograph (magnification 100,000 times) showing the particle structure of spindle-shaped fine particle titanium dioxide powder (sample B) obtained in Comparative Example 1. FIG.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35140995A JP3732265B2 (en) | 1995-12-25 | 1995-12-25 | Spindle-shaped fine particle titanium dioxide and method for producing the same |
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|---|---|---|---|
| JP35140995A JP3732265B2 (en) | 1995-12-25 | 1995-12-25 | Spindle-shaped fine particle titanium dioxide and method for producing the same |
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| JPH09175821A JPH09175821A (en) | 1997-07-08 |
| JP3732265B2 true JP3732265B2 (en) | 2006-01-05 |
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| AU2001228849A1 (en) * | 2000-01-31 | 2001-08-14 | Ecodevice Laboratory Co., Ltd | Visible light responsive type material and method of manufacturing same |
| JP4631013B2 (en) * | 2003-03-28 | 2011-02-16 | 大阪府 | Acicular titanium oxide fine particles, production method thereof and use thereof |
| JP3801173B2 (en) | 2003-12-10 | 2006-07-26 | コニカミノルタビジネステクノロジーズ株式会社 | Contact charger and image forming apparatus |
| EP1775120A4 (en) * | 2004-06-29 | 2009-12-02 | Mitsui Chemicals Inc | Fine particles of tin-modified rutile-type titanium dioxide |
| JP2010090011A (en) * | 2008-10-10 | 2010-04-22 | Shin-Etsu Chemical Co Ltd | Titanium oxide powder, dispersion liquid, and method of producing the titanium oxide powder |
| CN113896235B (en) * | 2020-07-06 | 2023-09-26 | 宁波极微纳新材料科技有限公司 | Preparation method and device of monodisperse nano titanium dioxide |
| JPWO2022092097A1 (en) | 2020-10-27 | 2022-05-05 | ||
| CN115784297B (en) * | 2022-11-21 | 2024-03-29 | 西安近代化学研究所 | Spindle-shaped In 2 O 3 Preparation method and application of nano material |
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