JP2000256014A - Titanium oxide fine powder and its production - Google Patents
Titanium oxide fine powder and its productionInfo
- Publication number
- JP2000256014A JP2000256014A JP11061792A JP6179299A JP2000256014A JP 2000256014 A JP2000256014 A JP 2000256014A JP 11061792 A JP11061792 A JP 11061792A JP 6179299 A JP6179299 A JP 6179299A JP 2000256014 A JP2000256014 A JP 2000256014A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- powder
- fine powder
- alkoxide
- oxide fine
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 62
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims description 40
- 150000004703 alkoxides Chemical class 0.000 claims description 38
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 8
- 239000006096 absorbing agent Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- -1 compound alkoxide Chemical class 0.000 abstract 2
- 238000012216 screening Methods 0.000 abstract 1
- 239000002537 cosmetic Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 11
- 230000000475 sunscreen effect Effects 0.000 description 9
- 239000000516 sunscreening agent Substances 0.000 description 9
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 239000003205 fragrance Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000036284 oxygen consumption Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- AFDXODALSZRGIH-QPJJXVBHSA-N (E)-3-(4-methoxyphenyl)prop-2-enoic acid Chemical compound COC1=CC=C(\C=C\C(O)=O)C=C1 AFDXODALSZRGIH-QPJJXVBHSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Cosmetics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、紫外線遮蔽効果に
優れ、光触媒活性能が抑えられた、例えば日焼け止め化
粧品用として適した、紫外線遮蔽用の酸化チタン微粉
末、およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a titanium oxide fine powder having excellent ultraviolet shielding effect and reduced photocatalytic activity and suitable for, for example, sunscreen cosmetics, and a method for producing the same.
【０００２】[0002]
【従来の技術】一般に、酸化チタン（ＴｉＯ2）粉末は
紫外線を遮蔽する効果が高く、たとえば、日焼け止め化
粧品用などとして用いられている。しかしながら、Ｔｉ
Ｏ2粉末自体の紫外線遮蔽効果は、ＵＶ−Ｂ領域（波
長：２８０〜３２０ｎｍ）の紫外線に対しては優れてい
るが、ＵＶ−Ａ領域（波長：３２０〜４００ｎｍ）の紫
外線に対しては劣っている。2. Description of the Related Art In general, titanium oxide (TiO 2 ) powder has a high effect of shielding ultraviolet rays and is used, for example, for sunscreen cosmetics. However, Ti
The ultraviolet shielding effect of the O 2 powder itself is excellent for ultraviolet rays in the UV-B region (wavelength: 280 to 320 nm), but inferior to ultraviolet rays in the UV-A region (wavelength: 320 to 400 nm). ing.
【０００３】また、ＴｉＯ2粉末の粒径と紫外線遮蔽性
の関係は、次のとおりである。すなわち、ＵＶ−Ｂ領域
の紫外線に対しては、粒径５０ｎｍ付近のＴｉＯ2粉末
が最大の吸収を示すが、この粒径付近では逆にＵＶ−Ａ
領域の紫外線に対する透過率が９０〜１００％となりほ
とんど透過してしまう。他方、ＵＶ−Ａ領域の紫外線の
透過率が最も低くなるＴｉＯ2粉末の粒径は、１００ｎ
ｍ付近である。ところが、透過率が低くなるといって
も、透過率５０〜６０％とＵＶ−Ａ領域の紫外線を半分
以上透過し、またこの粒径付近ではＵＶ−Ｂ領域の紫外
線の透過率が３０％にもなりＵＶ−Ｂ領域の紫外線の遮
蔽効果が悪くなってしまう。したがって、ＴｉＯ2粉末
の粒径管理のみで、ＵＶ−ＢおよびＵＶ−Ａ領域の紫外
線を同時に遮蔽することは不可能である。[0003] The relationship between the particle size of the TiO 2 powder and the ultraviolet shielding property is as follows. That is, the TiO 2 powder having a particle diameter of about 50 nm shows the maximum absorption for the ultraviolet rays in the UV-B region, but the UV-A particles have a reverse absorption in the vicinity of this particle diameter.
The transmittance of the region to ultraviolet rays is 90 to 100%, and the region is almost transmitted. On the other hand, the particle size of the TiO 2 powder having the lowest UV-A transmittance in the UV-A region is 100 n.
m. However, even if the transmittance is low, the transmittance of the UV-A region is at least 50% to 60% and the UV-A region transmits more than half of the UV-B region. The effect of blocking ultraviolet rays in the UV-B region is deteriorated. Therefore, it is impossible to simultaneously block ultraviolet rays in the UV-B and UV-A regions only by controlling the particle size of the TiO 2 powder.
【０００４】そこで、紫外線遮蔽用の酸化チタン粉末と
しては、上記欠点を補うため、以下のように、ＴｉＯ2
粉末に添加剤を加えるなどの処理をしたものが用いられ
ている。[0004] Therefore, the titanium oxide powder for UV shielding, to compensate the above drawbacks, as follows, TiO 2
What has been processed by adding additives to the powder is used.
【０００５】（Ａ）ＵＶ−Ａ領域の紫外線を吸収させる
ために、ＴｉＯ2粉末に有機系の紫外線吸収剤をさらに
添加する。(A) To absorb ultraviolet rays in the UV-A region, an organic ultraviolet absorber is further added to the TiO 2 powder.
【０００６】（Ｂ）ＵＶ−Ａ領域の紫外線に対する遮蔽
効果が高いＣｅＯ2粉末を、ＴｉＯ2粉末に添加する。(B) CeO 2 powder having a high shielding effect against ultraviolet rays in the UV-A region is added to the TiO 2 powder.
【０００７】（Ｃ）Ｔｉ4+およびＣｅ4+の混合溶液にア
ルカリなどの沈殿剤を添加して沈殿を生成し、熱処理を
行なうことにより、ＴｉＯ2とＣｅＯ2の混合粉末を得
る。(C) A precipitate is generated by adding a precipitant such as an alkali to a mixed solution of Ti 4+ and Ce 4+ , and heat-treated to obtain a mixed powder of TiO 2 and CeO 2 .
【０００８】[0008]
【発明が解決しようとする課題】ところで、（Ａ）の有
機系の紫外線吸収剤をさらに添加する方法の場合、一般
に、添加する紫外線吸収剤としては、４−ｔｅｒｔブチ
ル−４´−メトキシ−ジベンゾイルメタン、グリセリン
のパラメトキシ桂皮酸エステルなどの化合物が用いられ
る。このため、この紫外線吸収剤がＴｉＯ2の光触媒作
用によって酸化分解するという問題点があった。また、
日焼け止め化粧品用として用いた場合、化粧品中の香
料、薬品、界面活性剤、乳化剤などの有機化合物が、Ｔ
ｉＯ2の光触媒作用によって酸化分解するという問題点
があった。In the case of the method (A) in which an organic UV absorber is further added, generally, the UV absorber to be added is 4-tertbutyl-4'-methoxy-diphenyl. Compounds such as benzoylmethane and paramethoxycinnamate of glycerin are used. For this reason, there is a problem that the ultraviolet absorber is oxidatively decomposed by the photocatalytic action of TiO 2 . Also,
When used for sunscreen cosmetics, organic compounds such as fragrances, chemicals, surfactants and emulsifiers in cosmetics are
There is a problem that the photocatalytic action of iO 2 causes oxidative decomposition.
【０００９】また、（Ｂ）のＣｅＯ2粉末を添加する方
法の場合、ＣｅＯ2は３００〜４００ｎｍの波長を吸収
する特性を有しているため、ＴｉＯ2に添加することに
より、ＵＶ−ＢおよびＵＶ−Ａ領域の紫外線を吸収して
遮蔽することができる。しかしながら、日焼け止め化粧
品用として用いた場合、（Ａ）と同様に、化粧品中の香
料、薬品、界面活性剤、乳化剤などの有機物が、ＴｉＯ
2の光触媒作用によって酸化分解するという問題点があ
った。また、この方法は、ＴｉＯ2粉末とＣｅＯ2粉末を
混合する方式であるため、ミクロ域での均一分散を行な
うことが不可能である。したがって、日焼け止め化粧品
用として用いた場合、化粧品にわずかな色むらが生じて
紫外線遮蔽効率に差が出てく場合があるという問題点が
あった。In the method (B) of adding CeO 2 powder, CeO 2 has a property of absorbing a wavelength of 300 to 400 nm, so that by adding it to TiO 2 , UV-B and Ultraviolet rays in the UV-A region can be absorbed and blocked. However, when used for sunscreen cosmetics, organic substances such as fragrances, chemicals, surfactants, and emulsifiers in the cosmetics are TiO, as in (A).
There was a problem that the catalyst was oxidatively decomposed by the photocatalytic action of 2 . Further, since this method is a method of mixing TiO 2 powder and CeO 2 powder, it is impossible to perform uniform dispersion in a micro region. Therefore, when used for sunscreen cosmetics, there is a problem that slight unevenness in color may occur in the cosmetics, resulting in a difference in ultraviolet shielding efficiency.
【００１０】また、（Ｃ）のＴｉ4+およびＣｅ4+の混合
溶液にアルカリなどの沈殿剤を添加して沈殿を生成し、
熱処理を行なうことにより酸化チタン粉末を得る方法
は、（Ｂ）の方法に比べてＣｅとＴｉの分散性に関して
はいくらか改善されている。しかしながら、Ｔｉ4+とＣ
ｅ4+では、水酸化物が沈殿するｐＨ領域が異なってい
る。低いｐＨ域でＴｉ4+が水酸化物として沈殿し、続い
て高いｐＨ域でＣｅ4+が水酸化物として沈殿する。した
がって、この方法で得られる沈殿物はＴｉ（ＯＨ）4と
Ｃｅ（ＯＨ）4の混合物の状態になっており、熱処理で
得られる酸化チタン粉末はＴｉＯ2とＣｅＯ2の混合物で
あって、（Ｂ）と同じである。したがって、（Ｂ）と同
様に、日焼け止め化粧品用として用いた場合、化粧品中
の香料、薬品、界面活性剤、乳化剤などの有機物が、Ｔ
ｉＯ2の光触媒作用によって酸化分解するという問題
点、および、化粧品にわずかな色むらが生じて紫外線遮
蔽効率に差が出てく場合があるという問題点があった。Further, a precipitant such as an alkali is added to a mixed solution of (C) Ti 4+ and Ce 4+ to form a precipitate,
The method of obtaining the titanium oxide powder by performing the heat treatment has somewhat improved the dispersibility of Ce and Ti as compared with the method of (B). However, Ti 4+ and C
In e 4+ , the pH range in which hydroxide precipitates is different. In a low pH range, Ti 4+ precipitates as a hydroxide, and subsequently, in a high pH range, Ce 4+ precipitates as a hydroxide. Therefore, the precipitate obtained by this method is in the state of a mixture of Ti (OH) 4 and Ce (OH) 4 , and the titanium oxide powder obtained by the heat treatment is a mixture of TiO 2 and CeO 2 , Same as B). Therefore, as in (B), when used for sunscreen cosmetics, organic substances such as fragrances, chemicals, surfactants, and emulsifiers in the cosmetics are converted to T
There is a problem that the photocatalytic action of iO 2 causes oxidative decomposition, and there is a problem that a slight color unevenness occurs in the cosmetics, resulting in a difference in the ultraviolet ray shielding efficiency.
【００１１】そこで、本発明の目的は、紫外線吸収剤を
新たに添加することなく、ＴｉＯ2粉末を変性すること
で、ＵＶ−ＡおよびＵＶ−Ｂ領域の紫外線を遮蔽する効
果が高く、かつ、光触媒活性能を抑えた酸化チタン微粉
末、およびその製造方法を提供することにある。Therefore, an object of the present invention is to modify the TiO 2 powder without newly adding an ultraviolet absorber, so that the effect of shielding ultraviolet rays in the UV-A and UV-B regions is high, and It is an object of the present invention to provide a titanium oxide fine powder with reduced photocatalytic activity and a method for producing the same.
【００１２】[0012]
【課題を解決するための手段】上記目的を達成するた
め、本発明の紫外線遮蔽用の酸化チタン微粉末は、Ｔｉ
Ｏ2のＴｉ席の一部がＣｅにより置換されていることを
特徴とする。Means for Solving the Problems In order to achieve the above-mentioned object, the titanium oxide fine powder for ultraviolet shielding according to the present invention comprises:
It is characterized in that part of the Ti seat of O 2 is replaced by Ce.
【００１３】また、本発明の紫外線遮蔽用の酸化チタン
微粉末の製造方法は、ＴｉアルコキシドとＣｅアルコキ
シドの溶液を混合し加熱反応させて（−Ｔｉ−Ｏ−Ｃｅ
−Ｏ−Ｔｉ−）の化学結合を有する複合アルコキシド溶
液を得る工程、該複合アルコキシド溶液を６５〜９５℃
に加温した水と反応させ加水分解して酸化チタン粉末を
得る工程、該酸化チタン粉末を４５０〜８００℃で熱処
理する工程、を備えることを特徴とする。In the method for producing a titanium oxide fine powder for shielding ultraviolet rays according to the present invention, a solution of Ti alkoxide and Ce alkoxide is mixed and reacted by heating (-Ti-O-Ce).
-O-Ti-) to obtain a composite alkoxide solution having a chemical bond;
And a step of subjecting the titanium oxide powder to a heat treatment at 450 to 800 ° C.
【００１４】そして、前記複合アルコキシドの加水分解
は、静止型混合器を用いて行なうことを特徴とする。The hydrolysis of the complex alkoxide is performed using a static mixer.
【００１５】[0015]
【発明の実施の形態】本発明の紫外線遮蔽用の酸化チタ
ン微粉末は、上述のとおり、ＴｉＯ2のＴｉ席の一部が
Ｃｅにより置換されているものである。そして、この酸
化チタン微粉末は、ＴｉアルコキシドとＣｅアルコキシ
ドの溶液を混合し加熱反応させて（−Ｔｉ−Ｏ−Ｃｅ−
Ｏ−Ｔｉ−）の化学結合を有する複合アルコキシド溶液
を得た後、この複合アルコキシド溶液を６５〜９５℃に
加温した水と反応させ加水分解して酸化チタン粉末を
得、その後この酸化チタン粉末を４５０〜８００℃で熱
処理して得る。BEST MODE FOR CARRYING OUT THE INVENTION The titanium oxide fine powder for shielding ultraviolet rays according to the present invention is, as described above, one in which part of the Ti site of TiO 2 is replaced by Ce. The titanium oxide fine powder is mixed with a solution of Ti alkoxide and Ce alkoxide and reacted by heating (-Ti-O-Ce-
After obtaining a composite alkoxide solution having a chemical bond of O—Ti—), the composite alkoxide solution is reacted with water heated to 65 to 95 ° C. and hydrolyzed to obtain a titanium oxide powder. Is obtained by heat treatment at 450 to 800 ° C.
【００１６】すなわち、本発明では、まず、Ｔｉアルコ
キシドとＣｅアルコキシドを用いて、溶剤中にわずかに
含まれている水分、またはゲル化しない程度に添加した
水によって部分加水分解および重縮合反応を起こさせ
て、（−Ｔｉ−Ｏ−Ｃｅ−Ｏ−Ｔｉ−）の化学結合を有
する複合アルコキシド溶液を合成する。その後、この複
合アルコキシドを加水分解して、ＴｉＯ2化合物のＴｉ
席の一部をＣｅで置換した酸化チタン粉末を得て熱処理
するというものである。That is, in the present invention, first, partial hydrolysis and polycondensation reaction are caused by the use of Ti alkoxide and Ce alkoxide by the water slightly contained in the solvent or the water added to such an extent that gelation does not occur. Then, a composite alkoxide solution having a chemical bond of (-Ti-O-Ce-O-Ti-) is synthesized. Thereafter, the composite alkoxide is hydrolyzed to form Ti 2 of the TiO 2 compound.
This is to obtain a titanium oxide powder in which a part of the seat is replaced by Ce and heat-treat it.
【００１７】このように、ＴｉＯ2のＴｉ席の一部をＣ
ｅで置換した酸化チタン微粉末を得ることで、新たに紫
外線吸収剤を添加することなく、ＵＶ−ＡおよびＵＶ−
Ｂの両領域の紫外線吸収、遮蔽効果を向上させることが
できる。また、ＴｉＯ2粉末自身の光触媒活性能を低下
させることができるため、例えば日焼け止め化粧品用と
して用いた場合、化粧品中の香料、顔料、薬剤などの有
機物がＴｉＯ2粉末の光触媒作用で酸化分解するのを抑
えることができる。Thus, a part of the Ti seat of TiO 2 is
e to obtain a fine powder of titanium oxide substituted with UV-A and UV-A without adding a new ultraviolet absorber.
It is possible to improve the ultraviolet absorbing and shielding effects of both regions of B. Further, since the photocatalytic activity of the TiO 2 powder itself can be reduced, for example, when used for sunscreen cosmetics, organic substances such as fragrances, pigments, and chemicals in the cosmetics are oxidatively decomposed by the photocatalytic action of the TiO 2 powder. Can be suppressed.
【００１８】なお、複合アルコキシドを加水分解して得
た酸化チタン粉末の熱処理温度は、４５０〜８００℃の
範囲が好ましい。４５０〜６００℃の熱処理では、ほぼ
１００％アナターゼタイプの酸化チタン微粉末が得られ
る。６００〜７００℃の熱処理では、アナターゼタイプ
とルチルタイプが混合した酸化チタン微粉末が得られ
る。７００℃以上の温度では、ほぼ１００％ルチルタイ
プの酸化チタン微粉末が得られる。熱処理温度が８００
℃を超えると、得られる酸化チタン微粉末の比表面積が
小さくすなわち粒径が大きくなり、例えば日焼け止め化
粧品用として不適当となる。The heat treatment temperature of the titanium oxide powder obtained by hydrolyzing the composite alkoxide is preferably in the range of 450 to 800 ° C. By heat treatment at 450 to 600 ° C., almost 100% anatase type titanium oxide fine powder is obtained. By the heat treatment at 600 to 700 ° C., fine titanium oxide powder in which anatase type and rutile type are mixed is obtained. At a temperature of 700 ° C. or more, almost 100% rutile type titanium oxide fine powder is obtained. Heat treatment temperature is 800
When the temperature exceeds ℃, the specific surface area of the obtained titanium oxide fine powder is small, that is, the particle size is large, and it becomes unsuitable for, for example, sunscreen cosmetics.
【００１９】また、複合アルコキシドの加水分解は、ラ
モンドミキサー（環境科学工業（株）の商品名）やスタ
ティックミキサー（米国ケニックス社の商品名）などの
静止型混合器を用いて行なうことで、より微細な酸化チ
タン微粉末を得ることができる。例えば、ラモンドミキ
サーを用いることにより、２００ｍ2／ｇという大きな
比表面積のアナターゼタイプの酸化チタン粉末が得ら
れ、この粉末を４５０〜８００℃で熱処理した後でも比
表面積が６０〜７０ｍ2／ｇであって、微細かつ分散性
のよい酸化チタン微粉末を得ることが可能となる。これ
は、ラモンドミキサーは、流体を１０23個というアボガ
ドロ数に近い個数に均一分割を行なうことができるよう
に、分割エレメントユニットを組み立てた装置であり、
１個当りの分割反応スポットの容積を計算すると、約３
μｍ径の反応場になり加水分解反応を均一に行なわせる
ことが可能となるためである。The hydrolysis of the complex alkoxide is carried out by using a static mixer such as a Ramond mixer (trade name of Environmental Science Co., Ltd.) or a static mixer (trade name of Kenix Corporation, USA). Finer titanium oxide fine powder can be obtained. For example, by using a ramond mixer, an anatase-type titanium oxide powder having a large specific surface area of 200 m 2 / g can be obtained, and the specific surface area is 60 to 70 m 2 / g even after the powder is heat-treated at 450 to 800 ° C. Thus, it is possible to obtain fine and finely dispersed titanium oxide fine powder. This is a device in which a Lamond mixer is assembled with divided element units so that a fluid can be uniformly divided into a number close to the Avogadro number of 10 23 ,
When the volume of the divided reaction spots per one piece is calculated, about 3
This is because it becomes a reaction field having a diameter of μm and the hydrolysis reaction can be performed uniformly.
【００２０】また、複合アルコキシドを得るためのＴｉ
アルコキシドとしては、一般的なＴｉ（ＯＲ）4（但
し、Ｒはアルキル基を表わしＣnＨ2n+1で示される）ア
ルコキシドが挙げられ、Ｔｉ（ＯＭｅ）4、Ｔｉ（ＯＥ
ｔ）4、Ｔｉ（Ｏ・n-Ｐｒ）4、Ｔｉ（Ｏ・i-Ｐｒ）4、
Ｔｉ（Ｏ・n-Ｂｕ）4、Ｔｉ（Ｏ・sec-Ｂｕ）4、Ｔｉ
（Ｏ・tert-Ｂｕ）4などを代表例として列挙できるが、
これらのアルコキシドに限定されるものではない。ま
た、Ｔｉ（ＯＲ）4-n（ａｃａｃ）nとして表わされるも
ので、上記のＯＲの少なくとも一部をａｃａｃで置換し
たアルコキシドも使用できる。また、Ｔｉ（ＯＲ）4-n
（ＲＣＯＯ）nとして表わされるもので、上記のＯＲの
少なくとも一部を脂肪酸に置換えたアルコキシドも使用
できる。さらにＴｉ（ＯＲ）4-n（ａｌｋａｎｏｌａｍ
ｉｎｅ）nとして表わされるもので、上記のＯＲの少な
くとも一部をａｌｋａｎｏｌａｍｉｎｅ（アルカノール
アミン）に置換えたアルコキシドの使用も可能であっ
て、アルカノールアミンとしてはＴＥＡ、ＤＥＡ、ＭＥ
Ａが代表例として列挙できるが、これらのアルカノール
アミンに限定されるものではない。In addition, Ti for obtaining a composite alkoxide
Examples of the alkoxide include alkoxides of general Ti (OR) 4 (where R represents an alkyl group and represented by C n H 2n + 1 ), and Ti (OMe) 4 , Ti (OE)
t) 4 , Ti (O · n-Pr) 4 , Ti (O · i-Pr) 4 ,
Ti (On-Bu) 4 , Ti (O-sec-Bu) 4 , Ti
(O.tert-Bu) 4 and the like can be listed as typical examples,
It is not limited to these alkoxides. An alkoxide represented by Ti (OR) 4-n (acac) n , wherein at least a part of the above OR is substituted with acac, can also be used. Also, Ti (OR) 4-n
An alkoxide represented by (RCOO) n in which at least a part of the above OR is substituted with a fatty acid can also be used. In addition, Ti (OR) 4-n (alkanolam
ine) n , and an alkoxide in which at least a part of the above OR is substituted with an alkanolamine (alkanolamine) can be used. Examples of the alkanolamine include TEA, DEA, ME
A can be listed as a representative example, but is not limited to these alkanolamines.
【００２１】また、複合アルコキシドを得るためのＣｅ
アルコキシドとしては、一般的なＣｅ（ＯＲ）m（但
し、ｍは３または４であり、Ｒはアルキル基を表わしＣ
nＨ2n+1で示される）アルコキシドが挙げられ、Ｃｅ
（ＯＭｅ）m、Ｃｅ（ＯＥｔ）m、Ｃｅ（Ｏ・n-Ｐ
ｒ）m、Ｃｅ（Ｏ・i-Ｐｒ）m、Ｃｅ（Ｏ・n-Ｂｕ）m、
Ｃｅ（Ｏ・sec-Ｂｕ）m、Ｃｅ（Ｏ・tert-Ｂｕ）mなど
を代表例として列挙できるが、これらのアルコキシドに
限定されるものではない。また、Ｃｅ（ＯＲ）m-n（ａ
ｃａｃ）n（但し、ｍは３または４、ｍ≧ｎ）として表
わされるもので、上記のＯＲの少なくとも一部をａｃａ
ｃで置換えたアルコキシドも使用できる。また、Ｃｅ
（ＯＲ）m-n（ＲＣＯＯ）n（但し、ｍは３または４、ｍ
≧ｎ）として表わされるもので、上記のＯＲの少なくと
も一部を脂肪酸に置換えたアルコキシドも使用できる。
さらにＣｅ（ＯＲ）m-n（ａｌｋａｎｏｌａｍｉｎｅ）n
（但し、ｍは３または４、ｍ≧ｎ）として表わされるも
ので、上記のＯＲの少なくとも一部をａｌｋａｎｏｌａ
ｍｉｎｅ（アルカノールアミン）に置換えたアルコキシ
ドの使用も可能であって、アルカノールアミンとしては
ＴＥＡ、ＤＥＡ、ＭＥＡが代表例として列挙できるが、
これらのアルカノールアミンに限定されるものではな
い。Further, Ce for obtaining a composite alkoxide is used.
As the alkoxide, general Ce (OR) m (where m is 3 or 4, R represents an alkyl group, and
n H represented by 2n + 1) include alkoxides, Ce
(OMe) m , Ce (OEt) m , Ce (On-P
r) m , Ce (O-i-Pr) m , Ce (On-Bu) m ,
Ce (O.sec-Bu) m , Ce (O.tert-Bu) m and the like can be listed as typical examples, but are not limited to these alkoxides. Also, Ce (OR) mn (a
cac) n (where m is 3 or 4, m ≧ n), and at least a part of the above OR is aca
Alkoxides substituted with c can also be used. Also, Ce
(OR) mn (RCOO) n (where m is 3 or 4, m
≧ n), and an alkoxide in which at least a part of the above OR is substituted with a fatty acid can also be used.
Further, Ce (OR) mn (alkanolamine) n
(Where m is 3 or 4, m ≧ n), and at least a part of the above OR is akanola
Alkoxides substituted with mine (alkanolamine) can be used, and TEA, DEA, and MEA can be listed as typical examples of alkanolamines.
It is not limited to these alkanolamines.
【００２２】[0022]
【実施例】まず、出発原料として、Ｔｉアルコキシドの
１種であるＴｉ（ＯＨ7Ｃ3）4と、Ｃｅアルコキシドの
１種であるＣｅ（ａｃａｃ）3を用意した。EXAMPLES First, Ti (OH 7 C 3 ) 4 , a kind of Ti alkoxide, and Ce (acac) 3 , a kind of Ce alkoxide, were prepared as starting materials.
【００２３】その後、表１に示すように、Ｃｅ／Ｔｉ＝
０／１００〜１．５０／９８．５０原子モル比になるよ
うに、これら原料を正確に秤量分取して、２−メトキシ
エタノールを入れたセパラブルフラスコに入れた。この
フラスコにセパラブルカバー、攪拌羽根および冷却器を
取り付けて、１２０℃のオイルバスにセットして２４時
間還流を行なった。還流後、蒸留によってＣ3Ｈ7ＯＨを
除去して、（−Ｔｉ−Ｏ−Ｃｅ−Ｏ−Ｔｉ−）の化学結
合を有する複合アルコキシド溶液を得た。Thereafter, as shown in Table 1, Ce / Ti =
These raw materials were accurately weighed and dispensed so as to have a molar ratio of 0/100 to 1.50 / 98.50, and placed in a separable flask containing 2-methoxyethanol. The flask was equipped with a separable cover, a stirring blade and a cooler, set in a 120 ° C. oil bath, and refluxed for 24 hours. After the reflux, C 3 H 7 OH was removed by distillation to obtain a composite alkoxide solution having a chemical bond of (—Ti—O—Ce—O—Ti—).
【００２４】次に、得られた複合アルコキシド溶液と６
５〜９０℃に加温された水を、静止型混合器の１種であ
るラモンドミキサーを備えた反応装置の溶液タンクに別
々に入れた。溶液タンクのバルブを開き、送液ポンプで
複合アルコキシド溶液と加温された水をラモンドミキサ
ーに送り込みミキサー内で加水分解反応を行ないアナタ
ーゼタイプの酸化チタン粉末のスラリーを得た。得られ
た酸化チタン粉末のスラリーを回収タンクに受け回収し
た。回収したスラリーを送液ポンプで再度ラモンドミキ
サーに送り込みながら熟成処理を行なった。その後、ス
プレードライヤーで乾燥し酸化チタン粉末を得た。Next, the obtained composite alkoxide solution and 6
Water heated to 5 to 90 ° C. was separately charged into a solution tank of a reactor equipped with a type of static mixer, a Ramond mixer. The valve of the solution tank was opened, and the mixed alkoxide solution and warmed water were fed into a ramond mixer by a liquid feed pump to carry out a hydrolysis reaction in the mixer to obtain a slurry of anatase type titanium oxide powder. The obtained slurry of titanium oxide powder was collected in a collection tank. The recovered slurry was subjected to an aging treatment while being sent again to the Ramond mixer by a liquid sending pump. Then, it was dried with a spray dryer to obtain a titanium oxide powder.
【００２５】その後、得られた酸化チタン粉末を５００
℃で１時間熱処理を行ない、目的の酸化チタン微粉末を
得た。Thereafter, the obtained titanium oxide powder was
Heat treatment was performed at 1 ° C. for 1 hour to obtain the desired titanium oxide fine powder.
【００２６】次に、得られた酸化チタン微粉末につい
て、比表面積（ＳＳ）、光触媒活性能、光吸収スペクト
ルの測定を行なった。なお、光触媒活性能はテトラリン
試験により求めた。また、光吸収スペクトルはＭｇＳＯ
4を基準として光吸収度｛ｌｏｇ（Ｉ0／Ｉ）、但しＩ0
は入射光の強さ、Ｉは反射光の強さ｝を測定した。比表
面積および光触媒活性能の測定結果を表１に示す。光吸
収スペクトルの測定結果を図１に示す。Next, the specific surface area (SS), photocatalytic activity, and light absorption spectrum of the obtained fine titanium oxide powder were measured. The photocatalytic activity was determined by a tetralin test. Also, the light absorption spectrum is MgSO
4 , the light absorption Δlog (I 0 / I), where I 0
Is the intensity of incident light, and I is the intensity of reflected light. Table 1 shows the measurement results of the specific surface area and the photocatalytic activity. FIG. 1 shows the measurement results of the light absorption spectrum.
【００２７】なお、テトラリン試験は、一般に、塗料の
耐候性をチェックする方法であり、塗料の光劣化性を加
速して評価する試験である。具体的には、次のような試
験方法により、酸化チタン微粉末の光触媒活性能を求め
た。すなわち、まず、石英製の反応容器に酸化チタン微
粉末および１,２,３,４-テトラヒドロナフタレン（Ｃ10
Ｈ12）を入れ、さらに酸素を充填した。この反応容器を
３７℃に調整したウオーターバスにセットし、高圧水銀
灯を点灯して紫外線を反応容器に３０分間照射し、式１
に示す自動酸化反応を行なわせた。そして、反応による
酸素消費量を、取付た圧力計の圧力変動から求めた。The tetralin test is generally a method for checking the weather resistance of a paint, and is a test for accelerating and evaluating the photo-deterioration of the paint. Specifically, the photocatalytic activity of the titanium oxide fine powder was determined by the following test method. That is, first, a titanium oxide fine powder and 1,2,3,4-tetrahydronaphthalene (C 10
H 12 ) was added, and oxygen was further charged. This reaction vessel was set in a water bath adjusted to 37 ° C., and a high-pressure mercury lamp was turned on to irradiate the reaction vessel with ultraviolet rays for 30 minutes.
The autoxidation reaction shown in the following was performed. Then, the oxygen consumption due to the reaction was determined from the pressure fluctuation of the attached pressure gauge.
【００２８】 Ｃ10Ｈ12 ＋ Ｏ2 ＋ ｈν → Ｃ10Ｈ12Ｏ2 ・・・式１ 式１から明らかなように、反応容器内の圧力変動が大き
いほど酸素消費量が多い、すなわち光触媒活性能が高い
ことを示す。C 10 H 12 + O 2 + hν → C 10 H 12 O 2 Equation 1 As is apparent from Equation 1, the greater the pressure fluctuation in the reaction vessel, the greater the oxygen consumption, that is, the photocatalytic activity. Indicates high performance.
【００２９】[0029]
【表１】 [Table 1]
【００３０】表１から明らかなように、Ｃｅ／Ｔｉ原子
モル比が大きくなる、すなわちＴｉＯ2のＴｉ席を占め
るＣｅの割合が高くなるにしたがって、圧力変動が小さ
くなっている。これは、Ｔｉ席を占めるＣｅの割合が高
くなるほど、酸化チタン微粉末の光触媒活性能が低くな
っていくことを示している。さらに、Ｔｉ席に占めるＣ
ｅの割合が１原子モル％を超えると、酸素消費による圧
力差が収束する傾向を示している。ＴｉＯ2のＴｉ席を
１原子モル％以上Ｃｅで置換させることで、光触媒活性
能をＴｉＯ2粉末単体の１／１０以下に低下させること
が可能である。As is apparent from Table 1, the pressure fluctuation decreases as the Ce / Ti atomic molar ratio increases, that is, as the ratio of Ce occupying Ti sites of TiO 2 increases. This indicates that the higher the proportion of Ce occupying the Ti seat, the lower the photocatalytic activity of the titanium oxide fine powder. Furthermore, C in Ti seat
When the proportion of e exceeds 1 atomic mol%, the pressure difference due to oxygen consumption tends to converge. Be to replace Ti seat of the TiO 2 in 1 atomic mol% Ce, it is possible to lower the photocatalytic activity performance than 1/10 of the TiO 2 powder alone.
【００３１】図１に、表１の試料番号１、２、３および
５の酸化チタン微粉末の光吸収ペクトルの測定結果を示
す。図１から明らかなように、ＴｉＯ2のＴｉ席の一部
をＣｅで置換することにより、ＵＶ−Ａ領域（波長：３
２０〜４００ｎｍ）の紫外線の吸収能が高まっている。FIG. 1 shows the measurement results of the light absorption spectrum of the fine titanium oxide powders of Sample Nos. 1, 2, 3 and 5 in Table 1. As is clear from FIG. 1, by substituting a part of the Ti seat of TiO 2 with Ce, the UV-A region (wavelength: 3
(20 to 400 nm).
【００３２】[0032]
【発明の効果】以上の説明で明らかなように、本発明
の、Ｔｉ席の一部をＣｅによって置換した酸化チタン微
粉末は、ＵＶ−Ｂ領域（波長：２８０〜３２０ｎｍ）だ
けでなくＵＶ−Ａ領域（波長：３２０〜４００ｎｍ）の
紫外線をも吸収して遮蔽し、かつ、光触媒活性能が抑え
られる。As is clear from the above description, the titanium oxide fine powder according to the present invention in which a part of the Ti site is replaced by Ce can be used not only in the UV-B region (wavelength: 280 to 320 nm) but also in the UV-B region. It also absorbs and blocks ultraviolet rays in the A region (wavelength: 320 to 400 nm) and suppresses the photocatalytic activity.
【００３３】したがって、本発明の酸化チタン微粉末
を、例えば、日焼け止め化粧品用として用いた場合、紫
外線の遮蔽性に優れ、かつ、化粧品中の香料、顔料、薬
剤などの有機化合物が光触媒作用で酸化分解するのを抑
えた化粧品を得ることができる。Therefore, when the titanium oxide fine powder of the present invention is used, for example, for sunscreen cosmetics, it has excellent ultraviolet shielding properties, and organic compounds such as fragrances, pigments, and chemicals in the cosmetics have a photocatalytic action. Cosmetics with reduced oxidative degradation can be obtained.
【図１】ＴｉＯ2のＴｉ席の一部をＣｅで置換した酸化
チタン微粉末の光吸収スペクトルである。FIG. 1 is a light absorption spectrum of a titanium oxide fine powder in which a part of a Ti site of TiO 2 is substituted by Ce.
Claims (3)
換されていることを特徴とする、紫外線遮蔽用の酸化チ
タン微粉末。1. A titanium oxide fine powder for shielding ultraviolet rays, characterized in that part of the Ti site of TiO 2 is replaced by Ce.
溶液を混合し加熱反応させて（−Ｔｉ−Ｏ−Ｃｅ−Ｏ−
Ｔｉ−）の化学結合を有する複合アルコキシド溶液を得
る工程、該複合アルコキシド溶液を６５〜９５℃に加温
した水と反応させ加水分解して酸化チタン粉末を得る工
程、該酸化チタン粉末を４５０〜８００℃で熱処理する
工程、を備えることを特徴とする、ＴｉＯ2のＴｉ席の
一部をＣｅで置換した、紫外線遮蔽用の酸化チタン微粉
末の製造方法。2. A solution of Ti alkoxide and Ce alkoxide is mixed and reacted by heating to obtain (-Ti-O-Ce-O-
A step of obtaining a composite alkoxide solution having a chemical bond of Ti-); a step of reacting the composite alkoxide solution with water heated to 65 to 95 ° C to hydrolyze to obtain a titanium oxide powder; A method for producing a titanium oxide fine powder for shielding ultraviolet rays, wherein a part of Ti seats of TiO 2 is replaced by Ce.
止型混合器を用いて行なうことを特徴とする、請求項２
に記載の酸化チタン微粉末の製造方法。3. The method according to claim 2, wherein the hydrolysis of the complex alkoxide is performed using a static mixer.
3. The method for producing a fine titanium oxide powder according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11061792A JP2000256014A (en) | 1999-03-09 | 1999-03-09 | Titanium oxide fine powder and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11061792A JP2000256014A (en) | 1999-03-09 | 1999-03-09 | Titanium oxide fine powder and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000256014A true JP2000256014A (en) | 2000-09-19 |
Family
ID=13181316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11061792A Pending JP2000256014A (en) | 1999-03-09 | 1999-03-09 | Titanium oxide fine powder and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000256014A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7371275B2 (en) | 2004-07-02 | 2008-05-13 | E.I. Du Pont De Nemours And Company | Titanium dioxide pigment and polymer compositions |
| JP2009275111A (en) * | 2008-05-14 | 2009-11-26 | Dainippon Printing Co Ltd | Method for producing gas barrier composition and gas barrier laminated film |
| JP2012111683A (en) * | 2010-11-04 | 2012-06-14 | Shinshu Univ | Method for producing copper-doped titanium oxide |
-
1999
- 1999-03-09 JP JP11061792A patent/JP2000256014A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7371275B2 (en) | 2004-07-02 | 2008-05-13 | E.I. Du Pont De Nemours And Company | Titanium dioxide pigment and polymer compositions |
| JP2009275111A (en) * | 2008-05-14 | 2009-11-26 | Dainippon Printing Co Ltd | Method for producing gas barrier composition and gas barrier laminated film |
| JP2012111683A (en) * | 2010-11-04 | 2012-06-14 | Shinshu Univ | Method for producing copper-doped titanium oxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Agorku et al. | Enhanced visible-light photocatalytic activity of multi-elements-doped ZrO2 for degradation of indigo carmine | |
| Yuranova et al. | Self-cleaning cotton textiles surfaces modified by photoactive SiO2/TiO2 coating | |
| EP2100927B1 (en) | Carbon-containing titanium dioxide photocatalyst and process the production thereof | |
| Mahmoud et al. | Photocatalytic degradation of methyl red dye | |
| JP4635217B2 (en) | Surface treatment agent and material, and surface treatment method | |
| Huixian et al. | Preparation and photocatalytic activity of La3+ and Eu3+ co-doped TiO2 nanoparticles: photo-assisted degradation of methylene blue | |
| JP2001104797A (en) | Method of manufacturing nano-size anatase type titanium dioxide photocatalyst, and photocatalyst produced by using the same | |
| Lim et al. | Simple Route to monodispersed silica− titania core− shell photocatalysts | |
| Zhu et al. | Preparation of high photocatalytic activity TiO2 with a bicrystalline phase containing anatase and TiO2 (B) | |
| Najafidoust et al. | The role of Diethanolamine as stabilizer in controlling morphology, roughness and photocatalytic activity of ZnO coatings in sonophotodegradation of methylene blue | |
| Bassim et al. | Photodegradation of methylene blue with aid of green synthesis of CuO/TiO2 nanoparticles from extract of citrus aurantium juice | |
| JP5447178B2 (en) | Visible light responsive titanium oxide fine particle dispersion and method for producing the same | |
| JP7069814B2 (en) | Structure | |
| JP6961931B2 (en) | Metatitanic acid particles and their production methods, photocatalyst-forming compositions, photocatalysts, and structures | |
| Wattanawikkam et al. | Sonochemical synthesis, characterization, and photocatalytic activity of perovskite ZnTiO 3 nanopowders | |
| Butt et al. | Influence of lanthanum doping via hydrothermal and reflux methods on the SnO2–TiO2 nanoparticles prepared by sol–gel method and their catalytic properties | |
| Hu et al. | Photocatalytic efficiencies of WO3/TiO2 nanoparticles for exhaust decomposition under UV and visible light irradiation | |
| JP5212353B2 (en) | Visible light responsive titanium oxide fine particle dispersion and method for producing the same | |
| JPH11292537A (en) | Preparation of transparent tio2 sol | |
| JP5399017B2 (en) | Hollow inorganic particles and method for producing the same, colorant and paint | |
| TWI291895B (en) | Sol containing titanium oxide, thin film formed therefrom and production process of the sol | |
| JP2000256014A (en) | Titanium oxide fine powder and its production | |
| JP5282735B2 (en) | Visible light responsive titanium oxide fine particle dispersion and method for producing the same | |
| Hofer et al. | Thermally stable and photocatalytically active titania for ceramic surfaces | |
| JP2534492B2 (en) | Titanium oxide fine particles and optical member |