JP2974266B2 - UV absorber - Google Patents
UV absorberInfo
- Publication number
- JP2974266B2 JP2974266B2 JP3205543A JP20554391A JP2974266B2 JP 2974266 B2 JP2974266 B2 JP 2974266B2 JP 3205543 A JP3205543 A JP 3205543A JP 20554391 A JP20554391 A JP 20554391A JP 2974266 B2 JP2974266 B2 JP 2974266B2
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- Prior art keywords
- hydroxyapatite
- ultraviolet
- acid
- powder
- sample
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、紫外線吸収剤に係り、
詳しくは紫外線吸収能が要求される分野、例えば、プラ
スチックス、塗料、インキ又は化粧品等に配合されうる
無機系の安全な紫外線吸収剤に関する。The present invention relates to an ultraviolet absorber,
Specifically, the present invention relates to a field requiring an ultraviolet absorbing ability, for example, an inorganic safe ultraviolet absorbing agent which can be blended in plastics, paints, inks, cosmetics and the like.
【０００２】[0002]
【従来の技術】従来、プラスチックス、塗料又はインキ
等が光、特に紫外線の吸収により品質が劣化することは
周知のことである。従って、これらの材料には、一般に
有機系又は無機系の紫外線吸収剤を配合して品質劣化を
防ぐ処置が施されている。さらに最近、化粧品の分野で
はＵＶカット性能の高い化粧品素材が強く要請されてい
る。2. Description of the Related Art It is well known that the quality of plastics, paints, inks and the like deteriorates due to absorption of light, particularly ultraviolet rays. Therefore, these materials are generally treated with an organic or inorganic ultraviolet absorber to prevent quality deterioration. More recently, in the field of cosmetics, there is a strong demand for cosmetic materials having high UV-cut performance.
【０００３】これまで紫外線吸収剤には、有機系の物質
として例えばキニーネ塩類、パラアミノ安息香酸誘導
体、サリチル酸誘導体、桂皮酸誘導体、アセトアニリド
等が、また、無機系の物質として酸化チタン、酸化亜
鉛、酸化セリウム等が代表的に知られている。Heretofore, ultraviolet absorbers include organic substances such as quinine salts, paraaminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, acetanilide, and the like, and inorganic substances such as titanium oxide, zinc oxide, and oxides. Cerium and the like are typically known.
【０００４】ところで、ヒドロキシアパタイトは、主に
懸濁重合用安定剤として工業的に利用されてきたが、近
時、その蛋白質親和性に着目して骨補填材のようなバイ
オセラミックスとしての開発が盛んであり、更に、その
カチオン交換能を利用して銀、銅又は亜鉛を担持した無
機質抗菌剤としての開発も盛んに進められている。By the way, hydroxyapatite has been used industrially mainly as a stabilizer for suspension polymerization, but recently, attention has been paid to its protein affinity to develop it as a bioceramic such as a bone replacement material. It is prosperous, and furthermore, its use as an inorganic antibacterial agent carrying silver, copper or zinc utilizing its cation exchange ability is also actively pursued.
【０００５】[0005]
【発明が解決しようとする課題】従来の紫外線吸収剤に
おいて、有機系のものは安全性や安定性の点からその使
用は限られている。他方、無機系の代表的な素材である
二酸化チタンや酸化亜鉛は、最近の微細な粒子制御技術
の開発と相俟って性能改善がなされ、使用価値が高まっ
ているが、物性上に問題がある。その理由の一つは、微
細な無機質粉末の共通した問題として、二酸化チタンや
酸化亜鉛の微粉末は分散性が悪く、そのために紫外線吸
収効果が不充分となることである。また、二酸化チタン
は光の屈折率が非常に大きいため、化粧品などの用途に
おいてはそれが欠点となる場合がある。更に、酸化亜鉛
は微細になると安全性および安定性に問題が生じ、その
使用は限定される。Among the conventional UV absorbers, the use of organic UV absorbers is limited in terms of safety and stability. On the other hand, titanium dioxide and zinc oxide, which are typical inorganic materials, have been improved in performance in conjunction with recent development of fine particle control technology, and their use value has been increased. is there. One of the reasons is a common problem of fine inorganic powders is that fine powders of titanium dioxide and zinc oxide have poor dispersibility, which results in an insufficient ultraviolet absorbing effect. Further, titanium dioxide has a very high refractive index of light, which may be a drawback in applications such as cosmetics. In addition, the fineness of zinc oxide causes safety and stability problems and its use is limited.
【０００６】本発明は上記の問題点を解消するためにな
されたものであって、その目的は従来の無機系紫外線吸
収剤に比べて、より紫外線吸収能に優れ、且つ安全性と
安定性の良い紫外線吸収剤を提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide an ultraviolet absorbing agent which is superior to conventional inorganic ultraviolet absorbing agents, and which has improved safety and stability. It is to provide a good ultraviolet absorber.
【０００７】[0007]
【課題を解決するための手段】上記の目的を達成するた
めの本発明による紫外線吸収剤は、一般式； Ｍｅ(0.5ｍ＋ 1.5ｎ)(Ｘ）ｍ・ (ＰＯ 4 )ｎ （式中、ＭｅはＣａ，Ｍｇ，Ｂａ，Ｚｎ，Ｃｅ，ＸはＯ
Ｈ、Ｃｌ又はＦ、ｎおよびｍは係数、但しＭｅ／Ｐのモ
ル比は 1.4〜1.8 の範囲を表す。）で示されるヒドロキ
シ アパタイトを有効成分とすることを構成上の特徴とし
ている。Means for Solving the Problems] UV absorbers according to the present invention for achieving the above object, the general formula; Me (0.5m + 1.5n) ( X) m · (PO 4) n ( wherein, Me Is Ca, Mg, Ba, Zn, Ce, X is O
H, Cl or F, n and m are coefficients, but the model of Me / P
The ratio represents a range of 1.4 to 1.8. Hydroxy)
The composition is characterized by using sheapatite as an active ingredient.
【０００８】通常、アパタイトと称する場合、代表的に
は一般式Ｃａ（ 0.5ｍ＋ 1.5ｎ) ・（ＯＨ）ｍ・（ＰＯ
4)ｎで表される特徴的な結晶構造をもつものであって、
特にｍ＝２、ｎ＝６の３Ｃａ3(ＰＯ4)2 ・Ｃａ（ＯＨ）
2 で表される三塩基性リン酸カルシウムのヒドロキシア
パタイトである。これに対し本発明におけるアパタイト
は、一般式 Ｍｅ(0.5ｍ＋ 1.5ｎ)(Ｘ）ｍ・（ＰＯ4)ｎ
〔式中、ＭｅはＣａ，Ｍｇ，Ｂａ，Ｚｎ，Ｃｅ、ＸはＯ
Ｈ，Ｃｌ又はＦ、ｎおよびｍは係数〕で表され、且つＭ
ｅ／Ｐが 1.4〜1.8 の組成を有する難溶性の塩基性リン
酸塩および他のイオンとの交換体もしくは他のイオンを
担持した変成物を含めたものをいう。Usually, when referred to as apatite, typically, the general formula Ca (0.5m + 1.5n). (OH) m. (PO
4 ) having a characteristic crystal structure represented by n,
In particular, 3Ca 3 (PO 4 ) 2 .Ca (OH) where m = 2 and n = 6
It is a hydroxyapatite tribasic calcium phosphate represented by 2 . Apatite in the present invention with respect to this, the general formula Me (0.5m + 1.5n) (X ) m · (PO 4) n
[Wherein Me is Ca, Mg, Ba, Zn, Ce, and X is O
H, Cl or F, n and m are coefficients], and M
e / P refers to those containing a sparingly soluble basic phosphate having a composition of 1.4 to 1.8 and an exchanger with other ions or a modified product carrying other ions.
【０００９】上記の一般式で示される本発明のアパタイ
トは、ＢＥＴ比表面積が少なくとも20m2/g以上の表面活
性なものであって、他のカチオンまたはアニオンを吸着
または反応担持し易い特性を有している。特に結晶構造
中のＣａ2+およびＯＨ- が共にイオン交換能を有する代
表的な無機イオン交換体の一つである。従って、上記の
一般式はアパタイトおよびそのイオン交換により変性し
て他のイオンを担持したものを含んで表わしたものであ
る。The apatite of the present invention represented by the above general formula has a BET specific surface area of at least 20 m 2 / g and is surface-active, and has a property of easily adsorbing or reacting with other cations or anions. doing. In particular, both Ca 2+ and OH − in the crystal structure are one of the representative inorganic ion exchangers having ion exchange capacity. Therefore, the above-mentioned general formula includes apatite and a denatured apatite which is modified by ion exchange and carries another ion.
【００１０】本発明で特に好ましいアパタイトは、カル
シウムヒドロキシアパタイト及び該アパタイトのＣａ2+
とＺｎ2+又は／及びＣｅ2+とをカチオン交換して担持し
た亜鉛置換ヒドロキシアパタイトもしくはセリウム置換
ヒドロキシアパタイトが挙げられる。Particularly preferred apatites in the present invention are calcium hydroxyapatite and Ca 2+ of the apatite.
Substituted cerium-substituted hydroxyapatite or cerium-substituted hydroxyapatite which is carried by cation-exchange with Zn 2+ and / or Ce 2+ .
【００１１】一般にアパタイトの製法は多様であるけれ
ども、本発明に係るアパタイトは、製造履歴は特に限定
されない。また、一次粒子の形状は、粒状、小判状また
は針状など様々であるが、特に限定はなく、用途によっ
て使い分ければよい。In general, there are various methods for producing apatite, but the production history of the apatite according to the present invention is not particularly limited. Further, the shape of the primary particles is various, such as a granular shape, an oval shape, and a needle shape, but is not particularly limited, and may be properly used depending on the application.
【００１２】しかし、アパタイトの粒径は紫外線吸収能
と関係があり、本発明では平均粒径（Ｄ50) が 0.1〜５
μm の範囲にある微粉末が好ましい。特にＤ50の1/2 及
至3/2 の大きさのものが少なくとも60％以上である製粒
された微粉末であることが望ましい。However, the particle size of apatite is related to the ultraviolet absorbing ability, and in the present invention, the average particle size (D50) is 0.1 to 5%.
Fine powders in the range of μm are preferred. In particular, it is desirable that the powder having a size of 1/2 to 3/2 of D50 be at least 60% or more.
【００１３】本発明に係るアパタイト粉末は、高級脂肪
酸等で表面処理を施して分散性やフリーフロー性など粉
体特性を改善したものであってもよい。ここに高級脂肪
酸というのは、炭素数12以上の飽和または不飽和の脂肪
酸もしくはその誘導体であり、例えばラウリン酸、ミス
チリン酸、パルミチン酸、ステアリン酸、アラギジン
酸、ベヘニン酸、エルカ酸、リノール酸、リノレイン
酸、オレイン酸、イワシ酸、リシノール酸などの高級脂
肪酸、その誘導体としてはＣａ，Ｍｇ，Ｂａ，Ｚｎ，Ｐ
ｂまたはＡｌなどで代表される金属塩、アンモニウム塩
またはアミド類が挙げられ、それらは１種または２種以
上配合される。さらに、シランカップリング剤の如き有
機けい素化合物や、ロジン酸（塩）のような他の表面処
理剤も適用することができる。The apatite powder according to the present invention may be subjected to a surface treatment with a higher fatty acid or the like to improve the powder properties such as dispersibility and free flow property. Here, the higher fatty acid is a saturated or unsaturated fatty acid having 12 or more carbon atoms or a derivative thereof.For example, lauric acid, mystyric acid, palmitic acid, stearic acid, aragidine acid, behenic acid, erucic acid, linoleic acid, Higher fatty acids such as linoleic acid, oleic acid, succinic acid and ricinoleic acid, and derivatives thereof such as Ca, Mg, Ba, Zn, P
Examples thereof include metal salts, ammonium salts, and amides represented by b, Al, and the like, and one or more of them are blended. Further, an organic silicon compound such as a silane coupling agent, or another surface treatment agent such as rosin acid (salt) can be applied.
【００１４】本発明に係る紫外線吸収剤は、アパタイト
自体が優れた紫外線吸収能を示すが、その使用に際し、
従来の有機系又は無機系の紫外線吸収剤と併用して使用
しても何ら差支えない。In the ultraviolet absorbent according to the present invention, apatite itself exhibits excellent ultraviolet absorbing ability.
It can be used in combination with a conventional organic or inorganic ultraviolet absorber.
【００１５】[0015]
【作用】本発明により提供されるアパタイト粉末を有効
成分とする紫外線吸収剤は、ＢＥＴ比表面積が20m2/g以
上の表面活性を有しており高度の紫外線吸収能を発揮す
る。特に一般式 Ｍｅ(0.5ｍ＋ 1.5ｎ）（Ｘ）ｍ・（Ｐ
Ｏ4)ｎで表される組成のうち、ＭｅがＣａであるカルシ
ウムヒドロキシアパタイトは従来の無機系紫外線吸収剤
に比べて安全性と安定性に優れる良好な紫外線吸収能を
示し、そのうえ、分散性ならびにフリーフロー性に富む
特徴を備えている。The ultraviolet absorbent provided with an apatite powder as an active ingredient according to the present invention has a BET specific surface area of 20 m 2 / g or more and exhibits a high ultraviolet absorbing ability. In particular, the general formula Me (0.5m + 1.5n) (X) m · (P
Of the composition represented by O 4 ) n, calcium hydroxyapatite, in which Me is Ca, has a good ultraviolet absorbing ability that is superior in safety and stability as compared with a conventional inorganic ultraviolet absorbing agent. In addition, it has a feature that is rich in free flow property.
【００１６】[0016]
実施例１〜４、比較例１〜２ １．試料の調製 (1) 消石灰スラリーとリン酸とをＣａ／Ｐのモル比1.68
にして反応させ、カルシウムヒドロキシアパタイト〔Ca
5.04（OH)(PO4)3 ：10wt% 〕のスラリーを生成した〔日
本化学工業（株）製、商品名「スーパータイト」）。こ
のスラリーを乾燥および粉砕して微粉末〔Ca5.04(OH)(P
O4)3〕（試料１）を得た。この粉末は、平均粒径（Ｄ5
0) ＝0.15μ、Ｄ50の1/2 から3/2 の大きさの粒度部分
は67％であり、また、ＢＥＴ比表面積は25m2/gであっ
た。 (2) 試料１に10wt％の硝酸セリウム溶液を室温にて添加
したのち、２時間撹拌してイオン交換処理を施した。次
いで濾過、水洗して得られた濾過ケーキを105 ℃で３時
間乾燥し、粉砕してセリウム置換ヒドロキシアパタイト
粉末〔Ca4. 7Ce0 .3(OH)(PO4)3〕を得た（試料２）。この
粉末中におけるＣｅ含有量は7.9 wt％、ＢＥＴ比表面積
は23m2/gであった。Examples 1 to 4, Comparative Examples 1 and 2 Preparation of sample (1) Slaked lime slurry and phosphoric acid were mixed at a Ca / P molar ratio of 1.68.
And react with calcium hydroxyapatite (Ca
A slurry of 5.04 (OH) (PO 4 ) 3 : 10 wt%] was produced (trade name “Super Tight” manufactured by Nippon Chemical Industry Co., Ltd.). Fine powder [Ca 5 the slurry was dried and pulverized. 04 (OH) (P
O 4 ) 3 ] (Sample 1) was obtained. This powder has an average particle size (D5
0) = 0.15 μm, the particle size portion having a size of 1/2 to 3/2 of D50 was 67%, and the BET specific surface area was 25 m 2 / g. (2) A 10 wt% cerium nitrate solution was added to Sample 1 at room temperature, and the mixture was stirred for 2 hours to perform an ion exchange treatment. Then filtered and the filter cake obtained was washed with water and dried 3 hours at 105 ° C., to obtain a cerium-substituted hydroxyapatite powders and pulverized [Ca 4. 7 Ce 0 .3 (OH ) (PO 4) 3 ] ( Sample 2). The Ce content in this powder was 7.9 wt%, and the BET specific surface area was 23 m 2 / g.
【００１７】(3) 試料１に10wt％硝酸亜鉛を用いた以外
は、試料２の調製と同様な操作条件で亜鉛置換ヒドロキ
シアパタイト粉末〔Ca4.54Zn0.41(OH)(PO4)3〕を調製し
た（試料３）。この粉末中におけるＺｎの含有量は5.3w
t ％、ＢＥＴ比表面積は24m2/gであった。 (4) 試料１のカルシウムヒドロキシアパタイト粉末と試
料２のセリウム置換ヒドロキシアパタイト粉末とを１：
１の重量比で混合し、混合ヒドロキシアパタイト粉末を
調製した（試料４）。 (5) ＢＥＴ比表面積５m2/g、平均粒径 2.5μm の市販酸
化亜鉛を比較試料とした（試料５）。 (6) ＢＥＴ比表面積30m2/gの市販ルチル型二酸化チタン
顔料を同じく比較試料とした（試料６）。(3) A zinc-substituted hydroxyapatite powder [Ca 4.54 Zn 0.41 (OH) (PO 4 ) 3 ] was prepared under the same operating conditions as in the preparation of sample 2, except that 10 wt% zinc nitrate was used for sample 1. (Sample 3). The content of Zn in this powder was 5.3 w
t%, BET specific surface area was 24 m 2 / g. (4) The calcium hydroxyapatite powder of sample 1 and the cerium-substituted hydroxyapatite powder of sample 2 were mixed as follows:
The mixture was mixed at a weight ratio of 1 to prepare a mixed hydroxyapatite powder (sample 4). (5) A commercially available zinc oxide having a BET specific surface area of 5 m 2 / g and an average particle size of 2.5 μm was used as a comparative sample (Sample 5). (6) A commercially available rutile type titanium dioxide pigment having a BET specific surface area of 30 m 2 / g was similarly used as a comparative sample (sample 6).
【００１８】２．紫外線吸収能の評価法 各試料粉末をヒマシ油に１wt％の割合で分散させ、ヒマ
シ油膜厚３μmに光を当て、分光光度計〔日立製作所
（株) 製、Ｕ-3、4001〕にて紫外線透過率及び可視光線
透過率を測定して紫外線吸収能を評価した。2. Evaluation method of ultraviolet absorption ability Each sample powder was dispersed in castor oil at a ratio of 1 wt%, light was applied to a castor oil film thickness of 3 μm, and ultraviolet light was measured with a spectrophotometer (U-3, 4001 manufactured by Hitachi, Ltd.). The transmittance and the visible light transmittance were measured to evaluate the ultraviolet absorbing ability.
【００１９】３．評価結果 評価結果を表１に示した。3. Evaluation results The evaluation results are shown in Table 1.
【００２０】[0020]
【表１】 [Table 1]
【００２１】実施例５〜７ 上記の試料１〜３調製時の置換乃至未置換ヒドロキシア
パタイトスラリー1000重量部にそれぞれ少量の分散剤を
添加し、コロイドミル〔国産精工（株）製〕に通して分
散処理したのち、表２に示す量のオレイン酸ナトリウム
水溶液（11.5wt％）を常温で添加して２時間撹拌を続け
た。スラリーを固液分離したところ母液にはオレイン酸
は殆ど溶出していなかった。ついで水洗および濾過を繰
り返してから100 ℃で濾過ケーキを乾燥し、粉砕してオ
レイン酸塩による表面処理アパタイト粉末を有効成分と
する紫外線吸収剤を製造した。Examples 5 to 7 A small amount of a dispersing agent was added to 1000 parts by weight of the substituted or unsubstituted hydroxyapatite slurry at the time of preparing the above samples 1 to 3, and the mixture was passed through a colloid mill (manufactured by Kokusan Seiko Co., Ltd.). After the dispersion treatment, an aqueous solution of sodium oleate (11.5 wt%) shown in Table 2 was added at room temperature, and stirring was continued for 2 hours. When the slurry was subjected to solid-liquid separation, almost no oleic acid was eluted in the mother liquor. After repeated washing and filtration, the filter cake was dried at 100 ° C. and pulverized to produce an ultraviolet absorber containing apatite powder treated with oleate as an active ingredient.
【００２２】[0022]
【表２】 [Table 2]
【００２３】この粉末は、表３に示す粒度特性を示し、
アパタイト粉末に比べ著しく分散性およびフリーフロー
性に富むものであった。This powder has the particle size characteristics shown in Table 3,
It was remarkably rich in dispersibility and free flow property as compared with apatite powder.
【００２４】[0024]
【表３】 [Table 3]
【００２５】[0025]
【発明の効果】以上のとおり、本発明によればヒドロキ
シアパタイトを有効成分とする優れた紫外線吸収能を有
し、安全性および安定性が高く、且つ分散性とフリーフ
ロー性の良好な紫外線吸収剤を提供することができる。
したがって、プラスチック、塗料、インキ、化粧品等に
配合するための紫外線吸収剤として大きな有用性が期待
される。As described above, according to the present invention, a hydroxyapatite as an active ingredient has an excellent ultraviolet absorbing ability, has high safety and stability, and has excellent dispersibility and free flowability. An agent can be provided.
Therefore, great utility is expected as an ultraviolet absorber for blending in plastics, paints, inks, cosmetics and the like.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−200721（ＪＰ，Ａ) 特開 平１−96104（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C09K 3/00 104 A61K 7/42 C01B 25/32 C08K 3/32 ＣＡ（ＳＴＮ)────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-200721 (JP, A) JP-A-1-96104 (JP, A) (58) Fields investigated (Int.Cl. 6 , DB name) C09K 3/00 104 A61K 7/42 C01B 25/32 C08K 3/32 CA (STN)
Claims (5)
(ＰＯ 4 )ｎ（式中、ＭｅはＣａ，Ｍｇ，Ｂａ，Ｚｎ，Ｃ
ｅ，ＸはＯＨ、Ｃｌ又はＦ、ｎおよびｍは係数、但しＭ
ｅ／Ｐのモル比は 1.4〜1.8 の範囲を表す。）で示され
るヒドロキシアパタイトを有効成分とする紫外線吸収
剤。1. The general formula: Me (0.5m + 1.5n) (X) m ·
(PO 4 ) n (where Me is Ca, Mg, Ba, Zn, C
e and X are OH, Cl or F, n and m are coefficients, but M
The molar ratio of e / P represents a range of 1.4 to 1.8. )
Ultraviolet absorber as an active ingredient hydroxyapatite that.
ドロキシアパタイトのＣａ2+とＺｎ2+とをイオン交換し
て担持した亜鉛置換ヒドロキシアパタイトである請求項
１記載の紫外線吸収剤。2. The hydroxyapatite is a zinc-substituted hydroxyapatite in which Ca 2+ and Zn 2+ of calcium hydroxyapatite are ion-exchanged and supported.
2. The ultraviolet absorbent according to 1 .
ドロキシアパタイトのＣａ2+とＣｅ2+とをイオン交換し
て担持したセリウム置換ヒドロキシアパタイトである請
求項１記載の紫外線吸収剤。Wherein hydroxyapatite, ultraviolet absorber of claim 1 wherein the the Ca 2+ and Ce 2+ calcium hydroxyapatite by ion exchange carrying cerium-substituted hydroxyapatite.
0.1〜５μm でかつＢＥＴ比表面積が20m2/g以上の微粉
末である請求項１〜３のいずれか１項記載の紫外線吸収
剤。4. The method according to claim 1, wherein the hydroxyapatite has an average particle size
The ultraviolet absorbent according to any one of claims 1 to 3, which is a fine powder having a BET specific surface area of 0.1 to 5 µm and a BET specific surface area of 20 m 2 / g or more.
その誘導体又は有機けい素化合物で表面処理されたもの
である請求項１〜４のいずれか１項記載の紫外線吸収
剤。5. The method according to claim 1, wherein the hydroxyapatite is a higher fatty acid,
The ultraviolet absorber according to any one of claims 1 to 4, which is surface-treated with a derivative thereof or an organosilicon compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3205543A JP2974266B2 (en) | 1991-07-22 | 1991-07-22 | UV absorber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3205543A JP2974266B2 (en) | 1991-07-22 | 1991-07-22 | UV absorber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0525458A JPH0525458A (en) | 1993-02-02 |
| JP2974266B2 true JP2974266B2 (en) | 1999-11-10 |
Family
ID=16508639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3205543A Expired - Fee Related JP2974266B2 (en) | 1991-07-22 | 1991-07-22 | UV absorber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2974266B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009001335A1 (en) * | 2009-03-04 | 2010-09-09 | Chemische Fabrik Budenheim Kg | Radiation absorbing material |
| IT1393370B1 (en) | 2009-03-23 | 2012-04-20 | Rigano | COSMETIC COMPOSITIONS INCLUDING HYDROXYAPATITIS AS A PHYSICAL SOLAR FILTER |
| JP2013510862A (en) * | 2009-11-10 | 2013-03-28 | ラボラトリー スキン ケア インコーポレイテッド | Sunscreen composition comprising uniform, hard, spherical nanoporous calcium phosphate particles, and methods for making and using the same |
| PT3164106T (en) * | 2014-07-02 | 2021-02-16 | Univ Cata³Lica Portuguesa Ucp | Uv-filters, method of producing the same and their use in compositions, in particular sunscreens |
-
1991
- 1991-07-22 JP JP3205543A patent/JP2974266B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0525458A (en) | 1993-02-02 |
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