JPH0967120A - Low active cerium oxide - Google Patents
Low active cerium oxideInfo
- Publication number
- JPH0967120A JPH0967120A JP7221529A JP22152995A JPH0967120A JP H0967120 A JPH0967120 A JP H0967120A JP 7221529 A JP7221529 A JP 7221529A JP 22152995 A JP22152995 A JP 22152995A JP H0967120 A JPH0967120 A JP H0967120A
- Authority
- JP
- Japan
- Prior art keywords
- cerium oxide
- surface area
- specific surface
- resin
- low active
- 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.)
- Granted
Links
Landscapes
- Cosmetics (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は樹脂、繊維、塗料、
化粧品などに紫外線吸収剤、顔料として添加して用いら
れる低活性酸化セリウムに関する。TECHNICAL FIELD The present invention relates to resins, fibers, paints,
The present invention relates to a low activity cerium oxide used as an ultraviolet absorber or a pigment added to cosmetics and the like.
【０００２】[0002]
【従来技術】酸化セリウムは耐候性、耐光性を付与する
目的で顔料や紫外線吸収剤として樹脂、繊維、塗料、化
粧品等に添加されて用いられている。2. Description of the Related Art Cerium oxide is added to resins, fibers, paints, cosmetics and the like as a pigment or an ultraviolet absorber for the purpose of imparting weather resistance and light resistance.
【０００３】[0003]
【発明が解決しようとする課題】酸化セリウムを上記の
目的で熱可塑性樹脂等に添加し混練する際、樹脂を融点
直下まで加熱し他の成分と共に混練機で混合するが、酸
化セリウムは化学的特性上酸化作用を有している為に樹
脂の焼けを引き起こし、着色や特性の劣化の原因とな
る。そしてこれを防ぐために酸化セリウムの表面にシリ
カやアルミナ等のコーティングを施すことなどが行われ
ているがコスト等の問題がある。When cerium oxide is added to a thermoplastic resin for the above purpose and kneaded, the resin is heated to just below the melting point and mixed with other components in a kneader. Since it has an oxidizing effect due to its characteristics, it causes burning of the resin, which causes coloring and deterioration of characteristics. In order to prevent this, coating of cerium oxide on the surface of silica, alumina or the like is performed, but there is a problem of cost.
【０００４】[0004]
【課題を解決するための手段】本発明は上記の問題点を
改良したもので、本発明者は樹脂等の酸化セリウムに因
る焼け、着色について検討を重ねた結果、酸化セリウム
の比表面積と関係あることを見いだしこれについて種々
検討して本発明を完成させた。すなはち本発明は、比表
面積が理論比表面積の10倍以下であることよりなる低活
性酸化セリウムを要旨とするもので、比表面積を小さく
することに依り樹脂等との反応性が抑えられ、樹脂等の
酸化に因る焼けや特性の劣化を防ぐことができるとする
ものである。Means for Solving the Problems The present invention has improved the above-mentioned problems, and the present inventor has repeatedly studied burning and coloring due to cerium oxide in resins and the like, and as a result, the specific surface area of cerium oxide and The present invention has been completed by finding out that there is a relationship and making various studies on this. That is, the present invention is based on a low activity cerium oxide having a specific surface area of 10 times or less of the theoretical specific surface area, and by reducing the specific surface area, the reactivity with a resin or the like is suppressed. It is said that it is possible to prevent burning and deterioration of characteristics due to oxidation of the resin or the like.
【０００５】以下に本発明を詳細に説明する。粒子の理
論比表面積CS(m2/g)は平均粒子直径をD(m)とし、密度を
d(g/m3) とすると真球近似から式（１）に依り求められ
る。 CS=4π(D/2)2/[d ×（4/3 ）×π(D/2)3] …（１） 本発明の低活性酸化セリウムは、酸化セリウムの比表面
積が理論比表面積の10倍を超えると樹脂等に混合の際反
応性が大きい為に問題が有るのでこれを10倍以下とする
ことが必要とされるものであり、下限は１倍とするもの
である。比表面積の測定法は例えばBET 法により行えば
良い。The present invention will be described in detail below. The theoretical specific surface area of particles CS (m 2 / g) is the average particle diameter D (m), the density
Assuming d (g / m 3 ), it can be calculated by the equation (1) from the true sphere approximation. CS = 4π (D / 2) 2 / [d × (4/3) × π (D / 2) 3 ] (1) In the low activity cerium oxide of the present invention, the specific surface area of cerium oxide is the theoretical specific surface area. If it exceeds 10 times, there is a problem because it has a large reactivity when mixed with a resin or the like, so that it is necessary to make it 10 times or less, and the lower limit is made 1 time. The specific surface area may be measured by, for example, the BET method.
【０００６】本発明の低活性酸化セリウムの製造方法
は、蓚酸塩、炭酸塩、水酸化物、硝酸塩、酢酸塩、硫酸
塩等のセリウム塩やセリウム塩化物を焼成することによ
り製造されるが、セリウムの塩はこれらに限定されるも
のではなく、焼成して酸化セリウムを生成するものであ
れば他の塩でもよい。これはまた酸化セリウムを再焼成
してもよい。焼成温度は原料により異なるが一般的には
1000℃以上で行うと良いが、この温度は比表面積の値に
依り定まるので、焼成温度は予め実験により求めておけ
ば良い。焼成雰囲気は大気中、または酸化性雰囲気が好
ましいが特に限定されない。The method for producing low activity cerium oxide according to the present invention is produced by firing a cerium salt such as an oxalate, a carbonate, a hydroxide, a nitrate, an acetate and a sulfate or a cerium chloride. The cerium salt is not limited to these, and other salts may be used as long as they can be calcined to produce cerium oxide. It may also re-fire the cerium oxide. The firing temperature depends on the raw materials, but generally
It is better to carry out at 1000 ° C or higher, but this temperature is determined by the value of the specific surface area, so the firing temperature may be determined in advance by experiments. The firing atmosphere is preferably air or an oxidizing atmosphere, but is not particularly limited.
【０００７】また、酸化セリウムの粒度は平均粒径が0.
1 μm 未満では２次凝集等に依る分散性の問題があり、
10μm を超えると紫外線の吸収効率や着色性の問題があ
るので、平均粒径は0.1 μm 〜10μm とすることが必要
である。このような粒度を得る方法としては、微細な原
料を焼成して目的の粒度のものを直接生成させても良い
し、また大きな粒子をジェットミルやビーズミル等の粉
砕、解砕機などで粉砕して目的の粒度にしてもよい。目
標粒度は使用目的により異なるが、小量で効果的に機能
を付与させたい場合、分散性を高めたい場合などは１μ
m 以下が好ましい。粒度の測定方法は特に限定されない
が、本発明においてはマイクロトラック社のレーザ回折
法による測定機を用い、試料を超音波分散後に測定して
得た値である。The average particle size of cerium oxide is 0.
If it is less than 1 μm, there is a problem of dispersibility due to secondary aggregation,
If it exceeds 10 μm, there is a problem with the absorption efficiency of ultraviolet rays and the coloring property. Therefore, it is necessary to set the average particle size to 0.1 μm to 10 μm. As a method for obtaining such a particle size, a fine raw material may be directly fired to obtain a target particle size, or large particles may be crushed by a jet mill or a bead mill, or crushed by a crusher or the like. The desired grain size may be used. The target particle size varies depending on the purpose of use, but if you want to effectively add a small amount of function, or if you want to improve dispersibility, 1μ
m or less is preferred. The method for measuring the particle size is not particularly limited, but in the present invention, it is a value obtained by measuring the sample after ultrasonic dispersion using a measuring device by the laser diffraction method manufactured by Microtrack.
【０００８】本発明における低活性酸化セリウムは、全
希土類元素酸化物を80重量％以上含有し、かつ該希土類
元素酸化物中の酸化セリウムの含有量が50重量％以上で
あるものとするものである。低酸化性酸化セリウム中の
希土類元素酸化物が80重量％未満で、該希土類元素酸化
物中の酸化セリウムの含有量が50重量％未満であると、
紫外線吸収剤や顔料としての効果が劣るという問題が生
じる。セリウムはランタン、プラセオジム、ネオジム等
の元素との混合した化合物として産出するが、それらの
不純物をイオン交換法や用媒抽出法などで分離精製して
本発明の含有量の酸化セリウムが得られる。The low activity cerium oxide according to the present invention contains 80% by weight or more of all rare earth element oxides, and the content of cerium oxide in the rare earth element oxides is 50% by weight or more. is there. The rare earth element oxide in the low-oxidizing cerium oxide is less than 80% by weight, and the content of cerium oxide in the rare earth element oxide is less than 50% by weight,
There arises a problem that the effect as an ultraviolet absorber or a pigment is poor. Cerium is produced as a compound mixed with elements such as lanthanum, praseodymium and neodymium, and these impurities are separated and purified by an ion exchange method or a medium extraction method to obtain cerium oxide having the content of the present invention.
【０００９】本発明の低活性酸化セリウムの１例を示せ
ば、平均粒径１μm の酸化セリウムの真球近似の理論比
表面積は、密度=7.3×106g/m3 とすると式（１）より0.
82m2/gとなり、従って比表面積は0.82×10＝8.2m2/g 以
下となる。また比表面積の下限は0.82×1=0.82m2/gで表
される。比表面積が0.82m2/gより大きい酸化セリウム
は、樹脂特に熱可塑性樹脂（例えばポリプロピレン、ポ
リエチレン、フッ素樹脂など）に添加されて、高温で混
練、成型された場合、操作中に焼けに因り褐色に変色す
る。しかし比表面積を8.2m2/g 以下とすれば着色は無く
なるとするものである。As an example of the low activity cerium oxide of the present invention, the theoretical specific surface area of cerium oxide having an average particle diameter of 1 μm in a true spherical approximation is given by the formula (1), where density = 7.3 × 10 6 g / m 3. Than 0.
82m 2 / g, and the thus the specific surface area is less than or equal to 0.82 × 10 = 8.2m 2 / g . The lower limit of the specific surface area is 0.82 × 1 = 0.82 m 2 / g. Cerium oxide with a specific surface area greater than 0.82 m 2 / g is brown due to burning during operation when it is added to a resin, especially a thermoplastic resin (eg polypropylene, polyethylene, fluororesin, etc.) and kneaded and molded at high temperature. Discolors. However, if the specific surface area is 8.2 m 2 / g or less, coloring will disappear.
【００１０】[0010]
【発明の実施の形態】以下本発明の実施の形態を実施例
及び比較例を挙げて具体的に説明するが、本発明はこれ
らに限定されるものではない。 実施例１ 平均粒径１μm で全希土類元素酸化物の含有量が98重量
％で酸化セリウムの含有量が99.9重量％の酸化セリウム
（理論比表面積0.82m2/g）でBET 法による比表面積が2.
5m2/g （理論比表面積値の3.0 倍）の試料をテトラフル
オロエチレンとエチレンの共重合樹脂に５重量％添加
し、350 ℃で混練したところ樹脂の焼けは見られなかっ
た。BEST MODE FOR CARRYING OUT THE INVENTION The embodiments of the present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Example 1 Cerium oxide having an average particle size of 1 μm, a total rare earth element oxide content of 98% by weight, and a cerium oxide content of 99.9% by weight (theoretical specific surface area 0.82 m 2 / g) and a specific surface area measured by the BET method 2.
When a sample of 5 m 2 / g (3.0 times the theoretical specific surface area value) was added to a copolymer resin of tetrafluoroethylene and ethylene in an amount of 5% by weight and kneaded at 350 ° C., no burning of the resin was observed.
【００１１】比較例１ 実施例１と同一粒径と含有量で比表面積が20m2/g（理論
比表面積値の24.4倍）の酸化セリウムを実施例１と同一
条件で混練したところ褐色に変化した。Comparative Example 1 Cerium oxide having the same particle size and content as in Example 1 and a specific surface area of 20 m 2 / g (24.4 times the theoretical specific surface area value) was kneaded under the same conditions as in Example 1 and turned brown. did.
【００１２】実施例２ 平均粒径５μm で全希土類元素酸化物の含有量が98重量
％で酸化セリウムの含有量が99.9重量％の酸化セリウム
（理論比表面積0.16m2/g）でBET 法による比表面積が0.
5m2/g （理論比表面積値の3.1 倍）の試料をポリエチレ
ンに５重量％添加し、350 ℃で混練したところ樹脂の焼
けは見られなかった。Example 2 Cerium oxide (theoretical specific surface area 0.16 m 2 / g) having an average particle size of 5 μm and a total rare earth element oxide content of 98% by weight and a cerium oxide content of 99.9% by weight, according to the BET method. Specific surface area is 0.
A sample of 5 m 2 / g (3.1 times the theoretical specific surface area) was added to polyethylene in an amount of 5% by weight and kneaded at 350 ° C. No resin burn was observed.
【００１３】比較例２ 実施例２と同一粒径と含有量で比表面積が5m2/g （理論
比表面積値の31.3倍）の酸化セリウムを実施例２と同一
条件で混練したところ褐色に変化した。Comparative Example 2 Cerium oxide having the same particle size and content as in Example 2 and a specific surface area of 5 m 2 / g (31.3 times the theoretical specific surface area) was kneaded under the same conditions as in Example 2 and turned brown. did.
【００１４】[0014]
【発明の効果】本発明の低活性酸化セリウムは、顔料や
紫外線吸収剤として樹脂等に添加し高温で加熱処理を行
っても、樹脂等の焼けや着色、特性の劣化を起こさなか
ったので、低活性の酸化セリウムであることが確認され
た。EFFECTS OF THE INVENTION The low activity cerium oxide of the present invention does not cause burning or coloring of the resin or the like and deterioration of its characteristics even if it is added to a resin or the like as a pigment or an ultraviolet absorber and heat-treated at a high temperature. It was confirmed to be low activity cerium oxide.
Claims (3)
あることを特徴とする低活性酸化セリウム。1. A low activity cerium oxide having a specific surface area of not more than 10 times the theoretical specific surface area.
し、かつ該希土類元素酸化物中の酸化セリウムの含有量
が50重量％以上である請求項１に記載の低活性酸化セリ
ウム。2. The low activity cerium oxide according to claim 1, wherein the rare earth element oxide is contained in an amount of 80% by weight or more, and the content of cerium oxide in the rare earth element oxide is 50% by weight or more.
請求項１又は２に記載の低活性酸化セリウム。3. The low activity cerium oxide according to claim 1, which has an average particle size of 0.1 μm to 10 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22152995A JP3339997B2 (en) | 1995-08-30 | 1995-08-30 | Low active cerium oxide containing composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22152995A JP3339997B2 (en) | 1995-08-30 | 1995-08-30 | Low active cerium oxide containing composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0967120A true JPH0967120A (en) | 1997-03-11 |
| JP3339997B2 JP3339997B2 (en) | 2002-10-28 |
Family
ID=16768152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22152995A Expired - Fee Related JP3339997B2 (en) | 1995-08-30 | 1995-08-30 | Low active cerium oxide containing composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3339997B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11228135A (en) * | 1998-02-17 | 1999-08-24 | Toray Ind Inc | Cerium oxide powder and cosmetic material, coating material and plastic containing the same |
-
1995
- 1995-08-30 JP JP22152995A patent/JP3339997B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11228135A (en) * | 1998-02-17 | 1999-08-24 | Toray Ind Inc | Cerium oxide powder and cosmetic material, coating material and plastic containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3339997B2 (en) | 2002-10-28 |
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