JPH11209111A - Multiple phosphate - Google Patents
Multiple phosphateInfo
- Publication number
- JPH11209111A JPH11209111A JP2391298A JP2391298A JPH11209111A JP H11209111 A JPH11209111 A JP H11209111A JP 2391298 A JP2391298 A JP 2391298A JP 2391298 A JP2391298 A JP 2391298A JP H11209111 A JPH11209111 A JP H11209111A
- Authority
- JP
- Japan
- Prior art keywords
- phosphate
- solution
- composite phosphate
- composite
- powder
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術的分野】本発明は、化粧料、ペイン
ト、プラスチック等の原材料として有用な紫外線吸収剤
に適した、複合金属燐酸塩に関する。TECHNICAL FIELD The present invention relates to a composite metal phosphate suitable for an ultraviolet absorber useful as a raw material for cosmetics, paints, plastics and the like.
【０００２】[0002]
【従来の技術】紫外線吸収剤は、紫外線から皮膚を保護
したり、プラスチックや塗料の光による劣化を防止した
りする作用を有し、化粧品の分野、プラスチック材料の
分野、ペイントの分野など広く使われている。この様な
紫外線吸収剤としては、たとえば、桂皮酸系化合物、パ
ラアミノ安息香酸系化合物、ベンゾフェノン系化合物等
の有機紫外線吸収剤及び酸化チタン、酸化亜鉛等の無機
系紫外線吸収剤に大別される。この内、有機紫外線吸収
剤には、吸収し得る光量が有限である、化粧料等の直接
皮膚に塗布するものに対しては、アレルギー等の安全性
の点で問題が残ると言う欠点があり、無機紫外線吸収剤
については、有効な量を用いると隠蔽力が大きすぎるた
めに真っ白になったり、厚ぼったくなってしまう、吸収
した光エネルギーによってラジカルを発生し、皮膜を劣
化させるなどの欠点があった。この様な問題を解決する
ために、有機紫外線吸収剤については、より安全性が高
く吸収量の多い骨格の検討がなされたが、未だ紫外線吸
収特性とアレルギー性等の安全性の両者を満足させるよ
うな有望な骨格を発見するには至っていない。無機紫外
線吸収剤については、微粒子化することにより厚ぼった
さや真っ白になることはある程度改善されたが、更に改
善する余地があると言わざるを得ない。この様な観点か
ら、厚ぼったさや真っ白な感じを与えない無機の紫外線
吸収剤が求められていた。2. Description of the Related Art Ultraviolet absorbers have an effect of protecting skin from ultraviolet rays and preventing deterioration of plastics and paints due to light, and are widely used in the fields of cosmetics, plastic materials and paints. Have been done. Such ultraviolet absorbers are roughly classified into organic ultraviolet absorbers such as cinnamic acid-based compounds, paraaminobenzoic acid-based compounds, and benzophenone-based compounds, and inorganic ultraviolet absorbers such as titanium oxide and zinc oxide. Among them, the organic ultraviolet absorber has a drawback that the amount of light that can be absorbed is finite, and there is a problem in that it remains a problem in terms of safety such as allergy to those applied directly to the skin such as cosmetics. The use of an effective amount of an inorganic ultraviolet absorber has disadvantages such as whitening or thickening due to too great a hiding power, and the generation of radicals due to the absorbed light energy to deteriorate the film. Was. In order to solve such problems, with regard to organic UV absorbers, a skeleton having higher safety and a higher absorption amount has been studied, but it still satisfies both UV absorption characteristics and safety such as allergy. Such a promising skeleton has not yet been discovered. With respect to the inorganic ultraviolet absorber, thickening and pure whiteness have been improved to some extent by making the particles finer, but there is still room for improvement. From such a viewpoint, there has been a demand for an inorganic ultraviolet absorber which does not give a thick feeling or a pure white feeling.
【０００３】一方、マンガン、クロム、セリウム、マグ
ネシウム、アルミニウム、チタニウム、亜鉛から選ばれ
る１種以上とカルシウム、ナトリウム、カリウムから選
ばれる１種以上の金属の複合燐酸塩そのものの存在、或
いは、当該複合燐酸塩が紫外線吸収剤として有効である
こと、紫外線吸収剤として化粧料やペイント等の組成物
に配合すること及びこの様な塩を紫外線吸収剤として用
いた場合それを含有する組成物に厚ぼったさがでないこ
とは知られていなかった。On the other hand, the presence or existence of a complex phosphate itself of one or more selected from manganese, chromium, cerium, magnesium, aluminum, titanium and zinc and one or more metals selected from calcium, sodium and potassium Phosphate is effective as an ultraviolet absorber, blended in compositions such as cosmetics and paints as an ultraviolet absorber, and when such a salt is used as an ultraviolet absorber, the composition containing it is thickened. It was not known that there was no time.
【０００４】[0004]
【発明が解決しようとする課題】本発明はこの様な状況
を踏まえて為されたものであり、組成物に配合しても厚
ぼったさのない、紫外線吸収剤として有益な化合物を提
供することを課題とする。SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and provides a compound useful as an ultraviolet absorber which does not become thick even when incorporated into a composition. That is the task.
【０００５】[0005]
【課題を解決するための手段】この様な状況に鑑みて、
本発明者らは、組成物に配合しても厚ぼったさのない紫
外線吸収剤を求めて鋭意研究を重ねた結果、マンガン、
クロム、セリウム、マグネシウム、アルミニウム、チタ
ニウム、亜鉛から選ばれる２種以上の金属の複合燐酸塩
にそのような作用があることを見いだし、発明を完成さ
せた。以下、本発明について、その実施の形態を中心に
詳細に説明する。In view of such a situation,
The present inventors have conducted intensive studies in search of an ultraviolet absorber that is not thickened even when incorporated into the composition, and as a result, manganese,
The inventors have found that a composite phosphate of two or more metals selected from chromium, cerium, magnesium, aluminum, titanium and zinc has such an effect, and completed the invention. Hereinafter, the present invention will be described in detail focusing on its embodiments.
【０００６】[0006]
【発明の実施の形態】（１）本発明の複合燐酸塩 本発明の複合燐酸塩は、マンガン、クロム、セリウム、
マグネシウム、アルミニウム、チタニウム、亜鉛から選
ばれる１種以上とカルシウム、ナトリウム、カリウムか
ら選ばれる１種以上の金属の複合燐酸塩であることを特
徴とする。この様な複合燐酸塩は何れも文献未記載の新
規複合塩である。本発明の複合燐酸塩は、水に不溶性又
は難溶性であることを条件とする。これは、水性担体中
でも紫外線吸収作用を発揮することが必要であるためで
ある。又、本発明の効果を損なわない範囲に於いて、燐
酸根以外のアニオニックな成分を含有することも可能で
ある。この様な成分としては炭酸根や硫酸根等が例示で
きる。この様な燐酸根以外のアニオニックな成分の含有
量は１０重量％以下、より好ましくは５重量％以下が望
ましい。又、本発明の複合燐酸塩に於いては塩のどの部
分に於いても元素構成比が一定なものが好ましい。この
様な塩としては各構成要素別に以下の物が例示できる。
但し、原料の仕込割合や反応条件によって、結晶水を含
んだり、正確なモル比を取らなかったり、各構成塩同志
が固熔する場合があるので下記例示はほんの一例にすぎ
ないことは言うまでもない。例えば、（Ｃｒ，Ｚｎ，Ｎ
ａ）ＰＯ4、（Ｃｒ，Ｃｏ，Ｎａ）3（ＰＯ4）2、Ｃａ
（Ｍｎ，Ｚｎ）5（ＰＯ4）4、（Ｃａ，Ｃｏ）3（Ｐ
Ｏ4）2、Ｋ2（Ｍｎ，Ｍｇ）5（ＰＯ4）4、Ｋ（Ｍｎ，Ｃ
ｅ）（ＰＯ4）、（Ｃｒ，Ｍｇ，Ｎａ）3（ＰＯ4）2、
（Ｍｎ、ＨＮａ）3Ｐ2Ｏ8、Ｎａ2Ｍｎ5（ＰＯ4）4、Ｋ
（Ａｌ，Ｃｒ）ＰＯ4、（Ｃｒ，Ｋ，Ｔｉ）3（ＰＯ4）4
等が挙げられる。更に、例えば（Ｃｒ，Ｚｎ，Ｎａ）Ｐ
Ｏ4を例にとると、クロム、亜鉛及びナトリウムのモル
数の総和とＰＯ4のモル数を夫々ｍ，ｎとし、Ｃｒ，Ｚ
ｎ，Ｎａのモル数をそれぞれａ、ｂ、ｃとすると、ｍ：
ｎ＝１：１で、Ｃｒ，Ｚｎ，Ｎａのモル数はＰＯ4の価
数とバランスする値をとる。即ち、Ｃｒ，Ｚｎ，Ｎａの
価数をそれぞれ３、２、１価であるとすると、仮に、Ｃ
ｒ0.5Ｚｎ0.5Ｎａ0.5ＰＯ4の如く表すことができ、これ
もまた（Ｃｒ，Ｚｎ，Ｎａ）ＰＯ4の範疇である。これ
らは何れも文献未記載の水不溶性塩或いは水難溶性塩で
ある。これら本発明の複合燐酸塩は紫外線Ｂのみならず
紫外線Ａに対しても優れた吸収特性を有し、紫外線吸収
剤として大変有用である。DESCRIPTION OF THE PREFERRED EMBODIMENTS (1) Composite phosphate of the present invention The composite phosphate of the present invention comprises manganese, chromium, cerium,
It is a composite phosphate of at least one selected from magnesium, aluminum, titanium, and zinc and at least one metal selected from calcium, sodium, and potassium. All of these complex phosphates are novel complex salts that have not been described in the literature. The complex phosphate of the present invention is provided on condition that it is insoluble or hardly soluble in water. This is because it is necessary to exhibit an ultraviolet absorbing effect even in an aqueous carrier. Further, as long as the effects of the present invention are not impaired, anionic components other than the phosphate group can be contained. Examples of such components include carbonate groups and sulfate groups. The content of such anionic component other than the phosphate group is preferably 10% by weight or less, more preferably 5% by weight or less. Further, in the composite phosphate of the present invention, it is preferable that the element composition ratio is constant in any part of the salt. Examples of such salts include the following for each component.
However, depending on the charge ratio of the raw materials and the reaction conditions, it is needless to say that the following example is only an example, because it may contain water of crystallization, may not take an accurate molar ratio, or each constituent salt may be solid-dissolved. . For example, (Cr, Zn, N
a) PO 4 , (Cr, Co, Na) 3 (PO 4 ) 2 , Ca
(Mn, Zn) 5 (PO 4 ) 4 , (Ca, Co) 3 (P
O 4 ) 2 , K 2 (Mn, Mg) 5 (PO 4 ) 4 , K (Mn, C
e) (PO 4 ), (Cr, Mg, Na) 3 (PO 4 ) 2 ,
(Mn, HNa) 3 P 2 O 8 , Na 2 Mn 5 (PO 4 ) 4 , K
(Al, Cr) PO 4 , (Cr, K, Ti) 3 (PO 4 ) 4
And the like. Further, for example, (Cr, Zn, Na) P
Taking O 4 as an example, let the total number of moles of chromium, zinc, and sodium and the number of moles of PO 4 be m and n, respectively;
When the number of moles of n and Na is a, b and c, respectively, m:
When n = 1: 1, the mole numbers of Cr, Zn, and Na take values that balance with the valence of PO 4 . That is, assuming that the valences of Cr, Zn, and Na are 3, 2, and 1, respectively, C
It can be expressed as r 0.5 Zn 0.5 Na 0.5 PO 4 , which is also in the category of (Cr, Zn, Na) PO 4 . These are all water-insoluble salts or poorly water-soluble salts which are not described in the literature. These composite phosphates of the present invention have excellent absorption characteristics not only for ultraviolet B but also for ultraviolet A, and are very useful as ultraviolet absorbers.
【０００７】（２）本発明の複合燐酸塩の製造方法 本発明の複合燐酸塩は、通常の燐酸塩の製造方法によっ
て製造することができる。この様な方法としては、例え
ば、単独叉は種々の金属の水酸化物や炭酸塩と燐酸を混
合して焼成する方法や夫々の金属の燐酸塩を混合して焼
成する方法等の固相法及び単独叉は種々の金属の塩化物
や硝酸塩の溶液と燐酸及び／叉は燐酸のアルカリ塩溶液
を混合し、水及び／叉はアルコール溶液中で反応させる
液相法が例示できる。更に、液相法は反応をビーカー等
で行うの解放系とオートクレーブ中で行う密閉系が例示
できる。これらの内最も好ましいのは液相法であり、更
に好ましいのは密閉系での液相法である。これは、固相
法では原料の粒子径が最終製品の粒子径に大きく関与す
る、原料の混合方法によって最終製品の品質が異なる、
焼成の熱によって結晶水が一定にならない等の欠点があ
らわれる場合があるからである。この密閉系での液相法
を具体的に例示するならば、マンガン、クロム、セリウ
ム、マグネシウム、アルミニウム、チタニウム、亜鉛か
ら選ばれる１種以上の金属の水可溶性塩の溶液、カルス
シウム、ナトリウム、カリウムから選ばれる１種以上の
金属の水可溶性塩の溶液、燐酸ナトリウムの様な燐酸の
水可溶塩の溶液をオートクレーブ中で混合し、反応さ
せ、生じた沈澱を乾燥させる方法等がある。オートクレ
ーブ条件は、目的の燐酸塩によって、混合方法、反応温
度、圧力、熟成時間等が適宜選択される。(2) Method for Producing Composite Phosphate of the Present Invention The composite phosphate of the present invention can be produced by an ordinary method for producing phosphate. Such methods include, for example, solid-phase methods such as a method of firing individually or by mixing hydroxides and carbonates of various metals with phosphoric acid, and a method of firing by mixing phosphates of respective metals. And a liquid phase method in which a solution of chlorides or nitrates of various metals alone or a solution of an alkali salt of phosphoric acid and / or phosphoric acid is mixed and reacted in a water and / or alcohol solution. Further, examples of the liquid phase method include an open system in which the reaction is carried out in a beaker or the like and a closed system in which the reaction is carried out in an autoclave. Of these, the most preferable is the liquid phase method, and the more preferable is the liquid phase method in a closed system. This is because, in the solid phase method, the particle size of the raw material greatly affects the particle size of the final product, the quality of the final product differs depending on the method of mixing the raw materials,
This is because the heat of sintering may cause defects such as inconsistent water of crystallization. Specific examples of the liquid phase method in this closed system include a solution of a water-soluble salt of at least one metal selected from manganese, chromium, cerium, magnesium, aluminum, titanium, and zinc, calcium, sodium, and potassium. A method of mixing a solution of a water-soluble salt of at least one metal selected from the group consisting of a water-soluble salt of phosphoric acid such as sodium phosphate in an autoclave, reacting, and drying the resulting precipitate. As for the autoclave conditions, a mixing method, a reaction temperature, a pressure, an aging time and the like are appropriately selected depending on a target phosphate.
【０００８】（３）本発明の組成物 本発明の組成物は、上記本発明の複合燐酸塩を含有する
ことを特徴とする。本発明の組成物としては、例えば、
ファンデーションやチークカラー等の化粧料、抗真菌外
用剤や抗炎症外用剤のような皮膚外用医薬、ペイント等
の塗料、プラスチック製品などが例示できる。本発明の
組成物は、化粧料に於いては、肌を紫外線から保護する
作用に優れ、皮膚外用医薬では有効成分が光劣化をする
のを防ぐ作用に優れ、ペイントに於いては光による皮膜
の劣化を防ぐ作用に優れ、プラスチック等では光による
ひび割れなどを防ぐ作用に優れる。本発明の組成物に於
ける、本発明の複合燐酸塩の好ましい含有量は、０．０
１〜１０重量％であり、更に好ましくは、０．０５〜５
重量％である。これは少なすぎると紫外線防護作用を期
待できない場合があり、多すぎると他の任意成分の配合
量を規制してしまう場合があるからである。この様な組
成物の中では、本発明の複合燐酸塩の安全性の高さから
化粧料や皮膚外用剤に適用するのが特に好適であり、そ
の色材としての特性から化粧料に適用するのが最も好ま
しい。紫外線吸収剤以外の目的、例えば、着色料や気質
粉体などとしてこれら組成物に含有させることも本発明
の技術的範囲に属する。これは、目的が異なっていて
も、結果として本発明の効果を実現してしまうからであ
る。(3) Composition of the Present Invention The composition of the present invention is characterized by containing the composite phosphate of the present invention. As the composition of the present invention, for example,
Examples include cosmetics such as foundation and cheek color, external skin medicines such as antifungal external preparations and anti-inflammatory external preparations, paints such as paints, plastic products and the like. The composition of the present invention is excellent in the action of protecting the skin from ultraviolet rays in cosmetics, is excellent in the action of preventing the active ingredient from being light-degraded in external medicine for skin, and is a film formed by light in paints. It is excellent in preventing deterioration of plastics, and is excellent in preventing cracks due to light in plastics and the like. The preferred content of the composite phosphate of the present invention in the composition of the present invention is 0.0
1 to 10% by weight, more preferably 0.05 to 5% by weight.
% By weight. If the amount is too small, the protective action against ultraviolet rays may not be expected in some cases. If the amount is too large, the amount of other optional components may be restricted. Among such compositions, the composite phosphate of the present invention is particularly preferably applied to cosmetics and external preparations for skin because of its high safety, and is applied to cosmetics because of its properties as a coloring material. Is most preferred. It is also within the technical scope of the present invention to include in these compositions any purpose other than the ultraviolet absorber, for example, as a coloring agent or a gaseous powder. This is because, even if the purpose is different, the effect of the present invention is realized as a result.
【０００９】本発明の組成物に於いては、上記複合燐酸
塩以外にこれら組成物で通常使用される任意成分を含有
することができる。この様な任意成分としては、例え
ば、化粧料であれば、ワセリンやマイクロクリスタリン
ワックス等のような炭化水素類、ホホバ油やゲイロウ等
のエステル類、牛脂、オリーブ油等のトリグリセライド
類、セタノール、オレイルアルコール等の高級アルコー
ル類、ステアリン酸、オレイン酸等の脂肪酸、グリセリ
ンや１，３−ブタンジオール等の多価アルコール類、非
イオン界面活性剤、アニオン界面活性剤、カチオン界面
活性剤、両性界面活性剤、エタノール、カーボポール等
の増粘剤、防腐剤、紫外線吸収剤、抗酸化剤、色素、粉
体類等等が例示でき、医薬外用剤であれば、賦形剤、結
合剤、被覆剤、滑沢剤、糖衣剤、崩壊剤、増量剤、矯味
矯臭剤、乳化・可溶化・分散剤、安定剤、ｐＨ調整剤、
等張剤、有効成分等が例示でき、ペイントとしては、例
えば、溶剤、分散剤、顔料、皮膜形成剤、可塑剤などが
例示できる。The composition of the present invention may contain, in addition to the composite phosphate described above, optional components commonly used in these compositions. As such optional components, for example, in the case of cosmetics, hydrocarbons such as petrolatum and microcrystalline wax, esters such as jojoba oil and gay wax, triglycerides such as tallow, olive oil, cetanol, oleyl alcohol And the like, fatty acids such as stearic acid and oleic acid, polyhydric alcohols such as glycerin and 1,3-butanediol, nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants , Ethanol, carbopol and other thickeners, preservatives, ultraviolet absorbers, antioxidants, pigments, powders and the like can be exemplified, if the external preparation, excipients, binders, coating agents, Lubricants, sugar coatings, disintegrants, bulking agents, flavoring agents, emulsifying / solubilizing / dispersing agents, stabilizers, pH adjusters,
Isotonic agents, active ingredients and the like can be exemplified, and examples of the paint include solvents, dispersants, pigments, film-forming agents, plasticizers and the like.
【００１０】[0010]
【実施例】以下、本発明について実施例を挙げて更に詳
細に説明を加えるが、本発明がこれら実施例にのみ限定
を受けないことは言うまでもない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but it goes without saying that the present invention is not limited to only these examples.
【００１１】＜実施例１＞次に示す方法に従って、（Ｃ
ｒ，Ｚｎ，Ｎａ）ＰＯ4を作成した。即ち、市販品のＣ
ｒＰＯ4・６Ｈ2Ｏ、Ｚｎ3（ＰＯ4）2・４Ｈ2Ｏ、ＮａＨ
ＣＯ3を夫々３．８ｇ、３６．７ｇ、０．４２ｇ採取
し、ライカイ機で良く混合し、電気炉にて昇温速度１０
℃／１０分、９００℃−１時間係留で焼成した。焼成後
ボールミルにて微粉化した。この粉末の収量は２０ｇで
あり、薄い緑色を呈しており、粉末Ｘ線回折及び蛍光Ｘ
線分析によってＣｒ0.15Ｚｎ0.8Ｎａ0.05ＰＯ4（複合燐
酸塩１）であることを確認した。<Embodiment 1> According to the following method, (C
(r, Zn, Na) PO 4 was prepared. That is, the commercially available C
rPO 4 · 6H 2 O, Zn 3 (PO 4) 2 · 4H 2 O, NaH
3.8 g, 36.7 g, and 0.42 g of CO 3 were collected and mixed well by a raikai machine, and the temperature was increased by an electric furnace at a heating rate of 10 g.
Calcination was performed by mooring at 900 ° C for 1 hour at 900 ° C for 10 minutes. After firing, it was pulverized with a ball mill. The yield of this powder was 20 g, it was pale green, and the powder X-ray diffraction and fluorescence X
It was confirmed by a line analysis that it was Cr 0.15 Zn 0.8 Na 0.05 PO 4 (composite phosphate 1).
【００１２】＜実施例２＞次に示す方法に従って、Ｃａ
（Ｍｎ，Ｚｎ）5（ＰＯ4）4を作成した。即ち、精製水
１ＬにＣａ（ＮＯ3）2・４Ｈ2Ｏ、ＭｎＣＬ2・４Ｈ
2Ｏ、ＺｎＣＬ2を夫々９．８ｇ、４．９ｇ、３０．７ｇ
溶解させてＡ液とする。別に、精製水０．３Ｌに（ＮＨ
4）2ＨＰＯ4、２８％ＮＨ4ＯＨをそれぞれ２６．４ｇ、
１３ｇ溶解させＢ液とする。Ａ液を８５℃に加温し、こ
れに攪拌下Ｂ液を滴下する。滴下修了後８５℃を保って
１時間熟成し、その後、生じた沈澱物を濾取、乾燥して
１９ｇの粉末を得た。この粉末は薄い紫色を呈してお
り、粉末Ｘ線回折、蛍光Ｘ線分及び赤外スペクトル分析
によってＣａ（Ｍｎ0.1，Ｚｎ0.9）5（ＰＯ4）4（複合
燐酸塩２）であることを確認した。<Embodiment 2> According to the following method, Ca
(Mn, Zn) 5 (PO 4 ) 4 was prepared. That is, Ca (NO 3 ) 2 .4H 2 O, MnCL 2 .4H
9.8 g, 4.9 g, 30.7 g of 2 O and ZnCL 2 respectively
Dissolve to obtain solution A. Separately, to 0.3 L of purified water (NH
4 ) 26.4 g of 2 HPO 4 and 28% NH 4 OH,
Dissolve 13 g to obtain solution B. The solution A is heated to 85 ° C., and the solution B is added dropwise thereto with stirring. After completion of dropping, the mixture was aged at 85 ° C. for 1 hour, and the resulting precipitate was collected by filtration and dried to obtain 19 g of a powder. This powder has a pale purple color, and was confirmed to be Ca (Mn 0.1 , Zn 0.9 ) 5 (PO 4 ) 4 (composite phosphate 2) by powder X-ray diffraction, X-ray fluorescence and infrared spectroscopy. did.
【００１３】＜実施例３＞次に示す方法に従って、（Ｃ
ａ，Ｃｏ）3（ＰＯ4）2を作成した。即ち、還流機付き
反応機にエタノール１．５Ｌを入れ、これにＣａ（ＯＣ
2Ｈ5）2、Ｃｏ（ＯＣ3Ｈ7）2を夫々３２．５ｇ、８．８
ｇ溶解させＡ液とする。別に、エタノール０．３Ｌに精
製水０．２ＬとＨ3ＰＯ4を１９．６ｇ混合し、Ｂ液とす
る。反応機中のＡ液還流下Ｂ液を滴下し、滴下後引き続
き１時間還流して熟成させた。冷後、生じた沈澱物を濾
取、乾燥させ、昇温速度１０℃／１０分 ５００℃−１
時間係留で焼成した。焼成物をボールミルで粉砕し、薄
い若草色の粉末２５ｇを得た。この粉末は粉末Ｘ線回折
及び蛍光Ｘ線分析によって（Ｃａ0.83，Ｃｏ0.17）
3（ＰＯ4）2（複合燐酸塩３）であることを確認した。<Embodiment 3> According to the following method, (C
a, Co) 3 (PO 4 ) 2 was prepared. That is, 1.5 L of ethanol was put into a reactor equipped with a reflux machine, and Ca (OC) was added thereto.
2 H 5) 2, Co ( OC 3 H 7) 2 respectively 32.5 g, 8.8
g to dissolve the solution A. Separately, 0.3 L of ethanol is mixed with 0.2 L of purified water and 19.6 g of H 3 PO 4 to obtain a solution B. Solution B was added dropwise under reflux of Solution A in the reactor, and after the addition, the mixture was refluxed for 1 hour to ripen. After cooling, the resulting precipitate was collected by filtration, dried, and heated at a rate of 10 ° C./10 minutes 500 ° C.-1
Fired for mooring for hours. The fired product was pulverized with a ball mill to obtain 25 g of pale green powder. This powder was analyzed by powder X-ray diffraction and fluorescent X-ray analysis (Ca 0.83 , Co 0.17 ).
3 (PO 4 ) 2 (composite phosphate 3).
【００１４】＜実施例４＞次に示す方法に従って、Ｋ2
（Ｍｎ，Ｍｇ）5（ＰＯ4）4を作成した。即ち、精製水
１ＬにＭｎＣＬ2・４Ｈ2Ｏ、ＭｇＣＬ2・６Ｈ2Ｏを夫々
１０ｇ、４０．６ｇ溶解させＡ液とする。別に、精製水
０．２Ｌに（Ｋ）2ＨＰＯ4・３Ｈ2Ｏ、ＫＯＨをそれぞ
れ４５．６ｇ、７ｇ溶解させＢ液とする。Ａ液及びＢ液
をオートクレーブにセットし、Ａ液にＢ液を注入し、反
応温度８５℃、圧力３００Ｋｇ／ｃｍ２で１時間反応せ
せた。冷後、濾取、乾燥させて薄茶色の粉末２７ｇを得
た。この粉末は粉末Ｘ線回折、蛍光Ｘ線及び赤外スペク
トル分析によってＫ2（Ｍｎ0.2，Ｍｇ0.8）5（ＰＯ4）4
（複合燐酸塩４）であることを確認した。<Embodiment 4> According to the following method, K 2
(Mn, Mg) 5 (PO 4 ) 4 was prepared. That is, purified water 1L to MnCL 2 · 4H 2 O, MgCL 2 · 6H 2 O , respectively 10 g, and A was allowed to 40.6g dissolved. Separately, 45.6 g and 7 g of (K) 2 HPO 4 .3H 2 O and KOH were dissolved in 0.2 L of purified water to obtain a solution B. The solution A and the solution B were set in an autoclave, the solution B was poured into the solution A, and reacted at a reaction temperature of 85 ° C. and a pressure of 300 kg / cm 2 for 1 hour. After cooling, the crystals were collected by filtration and dried to obtain 27 g of light brown powder. This powder was analyzed by powder X-ray diffraction, X-ray fluorescence and infrared spectroscopy to determine K 2 (Mn 0.2 , Mg 0.8 ) 5 (PO 4 ) 4
(Composite phosphate 4).
【００１５】＜実施例５＞次に示す方法に従って、Ｋ
（Ｍｎ，Ｃｅ）（ＰＯ4）を作成した。即ち、精製水１
ＬにＭｎＣＬ2・４Ｈ2Ｏ、Ｃｅ（ＮＯ3）3・６Ｈ2Ｏを
夫々４ｇ、３４．７ｇ溶解させＡ液とする。別に、精製
水０．２Ｌに（Ｋ）2ＨＰＯ4・３Ｈ2Ｏ、ＫＯＨをそれ
ぞれ２２．８ｇ、２．８ｇ溶解させＢ液とする。Ａ液及
びＢ液をオートクレーブにセットし、Ａ液にＢ液を注入
し、反応温度８５℃、圧力３００Ｋｇ／ｃｍ２で１時間
反応させた。冷後、濾取、乾燥させて薄い黄土色の粉末
２４ｇを得た。この粉末は粉末Ｘ線回折、蛍光Ｘ線及び
赤外スペクトル分析によってＫ（Ｍｎ0.2，Ｃｅ0.8）
（ＰＯ4）（複合燐酸塩５）であることを確認した。<Embodiment 5> According to the following method, K
(Mn, Ce) (PO 4 ) was prepared. That is, purified water 1
4 g and 34.7 g of MnCL 2 .4H 2 O and Ce (NO 3 ) 3 .6H 2 O are dissolved in L, respectively, to obtain solution A. Separately, 22.8 g and 2.8 g of (K) 2 HPO 4 .3H 2 O and KOH were dissolved in 0.2 L of purified water to obtain a solution B. The solution A and the solution B were set in an autoclave, the solution B was poured into the solution A, and reacted at a reaction temperature of 85 ° C. and a pressure of 300 kg / cm 2 for 1 hour. After cooling, the crystals were collected by filtration and dried to obtain 24 g of a pale ocher powder. This powder was analyzed by powder X-ray diffraction, fluorescent X-ray and infrared spectrum analysis to obtain K (Mn 0.2 , Ce 0.8 ).
(PO 4 ) (composite phosphate 5) was confirmed.
【００１６】＜実施例６＞以下に示す方法によって、上
記実施例１〜５で製造した、本発明の複合金属酸塩１〜
５の紫外線吸収特性を確認した。紫外線吸収特性は紫外
線吸収能力と紫外線吸収効率について調べた。これらの
特性値は次に示す如く測定した。これらの測定結果は表
１に示す。これより本発明の複合燐酸塩が優れた紫外線
吸収特性を有していることがわかる。 （紫外線吸収能力評価法）光がもはや透過しないほどの
厚さに複合燐酸塩粉体又は比較粉体をタブレット化し、
分光機を用いて、このタブレットの２９０nm〜４００nm
の反射率を測定する。この反射率の２９０nm〜３２０nm
（Ｂ波）及び３２０nm〜４００nm（Ａ波）の平均反射率
を求め、その−ＬＯＧ値をとってＢ波及びＡ波の吸光度
とする。この吸光度を当該粉体の紫外線吸収能力とし
た。 （紫外線吸収効率評価法）タルクの如き体質顔料と複合
燐酸塩粉体又は比較粉体を混合し、混合粉体とする。混
合粉体及び体質顔料のみを、光がもはや透過しないほど
の厚さにタブレット化し、このタブレットの２９０nm〜
４００nmの反射率を測定する。この反射率の２９０nm〜
３２０nm（Ｂ波）及び３２０nm〜４００nm（Ａ波）の平
均反射率を求める。（体質顔料の平均反射率−混合粉体
の平均反射率）／（体質顔料の平均反射率）は体質顔料
の反射率を複合燐酸塩又は比較粉体がどれだけ下げたか
を示しているので、体質顔料中へ混合した複合燐酸塩又
は比較粉体の割合を１Ｖ％に統一して紫外線吸収効率と
した。 （仕事量評価法）紫外線吸収能力は本来その物質が持つ
吸光度であり、紫外線吸収効率は吸収能力をどのくらい
発揮できたかの率である。従って、（能力＊効率）は紫
外線吸収に係わる仕事量であり。この仕事量を複合燐酸
塩又は比較粉体の紫外線吸収特性に関する総合評価とし
た。 ＜表１のサンプルの表示＞ （イ）市販のＺｎＯ （ロ）市販のＴｉＯ２ （ハ）実施例１の複合燐酸塩 （ニ）実施例２の複合燐酸塩 （ホ）実施例３の複合燐酸塩 （ヘ）実施例４の複合燐酸塩 （ト）実施例５の複合燐酸塩<Example 6> The composite metal salts 1 to 5 of the present invention produced in the above Examples 1 to 5 by the following method.
The ultraviolet absorption characteristics of No. 5 were confirmed. Ultraviolet absorption properties were examined for ultraviolet absorption capacity and ultraviolet absorption efficiency. These characteristic values were measured as follows. Table 1 shows the measurement results. This indicates that the composite phosphate of the present invention has excellent ultraviolet absorption properties. (Ultraviolet absorption ability evaluation method) A tablet of the composite phosphate powder or the comparative powder is formed into a thickness such that light is no longer transmitted,
Using a spectrometer, the tablet has a wavelength of 290 nm to 400 nm.
Is measured. 290 nm to 320 nm of this reflectance
(B wave) and the average reflectance of 320 nm to 400 nm (A wave) are obtained, and the -LOG value thereof is taken as the absorbance of B wave and A wave. This absorbance was defined as the ultraviolet absorption capacity of the powder. (Ultraviolet absorption efficiency evaluation method) An extender pigment such as talc and a composite phosphate powder or a comparative powder are mixed to prepare a mixed powder. Only the mixed powder and extender pigment are tabletted to a thickness such that light is no longer transmitted.
The reflectance at 400 nm is measured. 290 nm of this reflectance
The average reflectance at 320 nm (B wave) and 320 nm to 400 nm (A wave) is determined. (Average reflectance of extender pigment-average reflectance of mixed powder) / (average reflectivity of extender pigment) indicates how much the composite phosphate or the comparative powder reduced the reflectivity of the extender pigment. The ratio of the composite phosphate or the comparative powder mixed into the extender was unified to 1 V%, which was defined as the ultraviolet absorption efficiency. (Work evaluation method) The ultraviolet absorption capacity is originally the absorbance of the substance, and the ultraviolet absorption efficiency is a ratio of how much the absorption capacity can be exhibited. Therefore, (capacity * efficiency) is the amount of work related to ultraviolet absorption. This work was used as an overall evaluation of the composite phosphate or the comparative powder for the ultraviolet absorption characteristics. <Display of Samples in Table 1> (a) Commercial ZnO (b) Commercial TiO2 (c) Composite phosphate of Example 1 (d) Composite phosphate of Example 2 (e) Composite phosphate of Example 3 (F) Composite phosphate of Example 4 (g) Composite phosphate of Example 5
【００１７】[0017]
【表１】 [Table 1]
【００１８】＜実施例７〜１１＞下記処方に従って、紫
外線防止化粧料を作成した。即ち、処方成分をダブルプ
ラネタリーミキサーに仕込み、９５℃で良く混練りし、
金型に充填、加温プレスして成形し、容器に装着させて
化粧料を得た。これらは何れも優れた紫外線防護効果を
有していた。 シリコーン処理二酸化チタン １０ 重量部 酸化亜鉛 ２ 重量部 黄色酸化鉄 ３ 重量部 ベンガラ １ 重量部 シリコーン処理セリサイト ２０ 重量部 シリコーン処理マイカ １０ 重量部 シリコーン処理タルク ２０ 重量部 ナイロンパウダー １４ 重量部 オレイン酸オクチルドデシル ５ 重量部 ジメチコン １３ 重量部 カルナウバワックス １ 重量部 キャンデリラワックス ０．８重量部 ソルビタンセスキオレート ０．２重量部 複合燐酸塩＊ １０ 重量部 ＊複合燐酸塩の詳細は表２に示す。<Examples 7 to 11> UV protection cosmetics were prepared according to the following formulations. That is, the prescription ingredients are charged into a double planetary mixer, kneaded well at 95 ° C,
It was filled in a mold, molded by heating press, and mounted in a container to obtain a cosmetic. All of these had an excellent ultraviolet protection effect. Silicone treated titanium dioxide 10 parts by weight Zinc oxide 2 parts by weight Yellow iron oxide 3 parts by weight Bengala 1 part by weight Silicone treated sericite 20 parts by weight Silicone treated mica 10 parts by weight Silicone treated talc 20 parts by weight Nylon powder 14 parts by weight Octyldodecyl oleate 5 parts by weight Dimethicone 13 parts by weight Carnauba wax 1 part by weight Candelilla wax 0.8 part by weight Sorbitan sesquiolate 0.2 part by weight Complex phosphate * 10 parts by weight * Details of the complex phosphate are shown in Table 2.
【００１９】[0019]
【表２】 [Table 2]
【００２０】＜実施例１２〜１６＞下記に示す処方に従
って抗炎症皮膚外用剤を作成した。即ち、処方成分をニ
ーダーで良く混練りし皮膚外用剤を得た。このものはイ
ンドメタシンの光毒性の発現を抑制していた。 インドメタシン １ 重量部 ワセリン ８９ 重量部 複合燐酸塩＊＊ １０ 重量部 ＊＊複合燐酸塩の詳細は表３に示す。<Examples 12 to 16> An anti-inflammatory skin external preparation was prepared according to the following formulation. That is, the ingredients were kneaded well with a kneader to obtain a skin external preparation. It suppressed the onset of phototoxicity of indomethacin. Indomethacin 1 part by weight Vaseline 89 parts by weight Complex phosphate ** 10 parts by weight ** Details of the complex phosphate are shown in Table 3.
【００２１】[0021]
【表３】 [Table 3]
【００２２】＜実施例１７＞下記処方に従ってペイント
を作成した。即ち、処方成分をダイノミルに仕込み、均
一分散させて、水性ペイントを得た。 アクリル酸アルキル樹脂エマルジョン ６０ 重量部 クエン酸トリエチル ５ 重量部 複合燐酸塩＊＊＊ ３５ 重量部 ＊＊＊複合燐酸塩の詳細は表４に示す。Example 17 A paint was prepared according to the following recipe. That is, the ingredients were charged into a Dynomill and dispersed uniformly to obtain an aqueous paint. Alkyl acrylate resin emulsion 60 parts by weight Triethyl citrate 5 parts by weight Complex phosphate *** 35 parts by weight *** Details of the complex phosphate are shown in Table 4.
【００２３】[0023]
【表４】 [Table 4]
【００２４】[0024]
【発明の効果】本発明によれば、組成物に配合しても厚
ぼったさのない、紫外線吸収剤として有益な化合物を提
供することができる。According to the present invention, it is possible to provide a compound which is not thickened even when incorporated into a composition and is useful as an ultraviolet absorber.
Claims (8)
ム、マグネシウム、アルミニウム、チタニウム、亜鉛か
ら選ばれる１種以上とカルシウム、ナトリウム、カリウ
ムから選ばれる１種以上の金属の複合燐酸塩。1. A composite phosphate of at least one selected from manganese, chromium, cobalt, cerium, magnesium, aluminum, titanium, and zinc and at least one metal selected from calcium, sodium, and potassium.
する、請求項１に記載の複合燐酸塩。2. The composite phosphate according to claim 1, wherein the composite phosphate is water-insoluble or hardly soluble.
クロム・コバルト・ナトリウム複合燐酸塩、カルシウム
・亜鉛・マンガン複合燐酸塩、カルシウム・コバルト複
合燐酸塩、カリウム・マンガン・マグネシウム複合燐酸
塩、カリウム・マンガン・セリウム複合燐酸塩、クロム
・マグネシウム・ナトリウム複合燐酸塩、ナトリウム・
マンガン複合燐酸塩、カリウム・アルミニウム・クロム
複合燐酸塩、クロム・カリウム・チタニウム複合燐酸塩
の何れかであることを特徴とする、請求項１又は２に記
載の複合燐酸塩。3. A chromium / zinc / sodium composite phosphate,
Chromium-cobalt-sodium complex phosphate, calcium-zinc-manganese complex phosphate, calcium-cobalt complex phosphate, potassium-manganese-magnesium complex phosphate, potassium-manganese-cerium complex phosphate, chromium-magnesium-sodium complex phosphate Salt, sodium
3. The composite phosphate according to claim 1, wherein the composite phosphate is one of a manganese composite phosphate, a potassium-aluminum-chromium composite phosphate, and a chromium-potassium-titanium composite phosphate.
燐酸塩からなる、紫外線吸収剤。4. An ultraviolet absorber comprising the composite phosphate according to claim 1.
る組成物。5. A composition comprising the ultraviolet absorbent according to claim 4.
５に記載の組成物。6. The composition according to claim 5, which is a cosmetic.
燐酸塩を含有する組成物。7. A composition containing the composite phosphate according to claim 1.
７に記載の組成物。8. The composition according to claim 7, which is a cosmetic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2391298A JPH11209111A (en) | 1998-01-21 | 1998-01-21 | Multiple phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2391298A JPH11209111A (en) | 1998-01-21 | 1998-01-21 | Multiple phosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11209111A true JPH11209111A (en) | 1999-08-03 |
Family
ID=12123707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2391298A Pending JPH11209111A (en) | 1998-01-21 | 1998-01-21 | Multiple phosphate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11209111A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011003651A1 (en) | 2011-02-04 | 2012-08-09 | Hochschule für Technik und Wirtschaft Dresden | Producing copper zinc phosphate, useful as UV or infrared absorption materials, comprises e.g. mixing the stoichiometric mixtures of copper and zinc compounds and phosphates, heating to temperature and maintaining under an air atmosphere |
| JP2013513703A (en) * | 2009-12-11 | 2013-04-22 | ラティテュード・１８，インコーポレイテッド | Inorganic phosphate compositions and methods |
| JP2015502325A (en) * | 2011-12-21 | 2015-01-22 | ケミスケ ファブリック ブデンヘイム ケージー | Metal phosphate and its manufacturing process |
| US10422041B2 (en) | 2009-12-18 | 2019-09-24 | Latitude 18, Inc | Inorganic phosphate corrosion resistant coatings |
-
1998
- 1998-01-21 JP JP2391298A patent/JPH11209111A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013513703A (en) * | 2009-12-11 | 2013-04-22 | ラティテュード・１８，インコーポレイテッド | Inorganic phosphate compositions and methods |
| US10422041B2 (en) | 2009-12-18 | 2019-09-24 | Latitude 18, Inc | Inorganic phosphate corrosion resistant coatings |
| DE102011003651A1 (en) | 2011-02-04 | 2012-08-09 | Hochschule für Technik und Wirtschaft Dresden | Producing copper zinc phosphate, useful as UV or infrared absorption materials, comprises e.g. mixing the stoichiometric mixtures of copper and zinc compounds and phosphates, heating to temperature and maintaining under an air atmosphere |
| JP2015502325A (en) * | 2011-12-21 | 2015-01-22 | ケミスケ ファブリック ブデンヘイム ケージー | Metal phosphate and its manufacturing process |
| US9653732B2 (en) | 2011-12-21 | 2017-05-16 | Chemische Fabrik Budenheim Kg | Metal phosphates and process for the preparation thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4030133B2 (en) | Ultraviolet shielding zinc oxide excellent in transparency and composition containing the same | |
| EP0445785B1 (en) | Plate-like barium sulfate and cosmetic composition | |
| US4952245A (en) | Nacreous pigment containing a dye and cosmetic composition comprising the same | |
| KR100569083B1 (en) | Metal oxide doped cerium oxides, Method for the preparation thereof, Resin composition and Cosmetic composition therewith | |
| JP7074058B2 (en) | Zinc oxide phosphor and its manufacturing method | |
| KR101772718B1 (en) | Particulate titanium dioxide | |
| EP0596442B1 (en) | Ultraviolet-shielding agent, method for the preparation thereof and cosmetic composition compounded therewith | |
| TW200806753A (en) | Pigment | |
| WO1995016637A1 (en) | Ultrafine iron-containing rutile titanium dioxide particle and process for producing the same | |
| JP3388592B2 (en) | Ultraviolet shielding flaky pigment, method for producing the same, and cosmetic containing the above ultraviolet shielding flaky pigment | |
| JP2021519846A (en) | Effect pigments based on colored hectorite and coated colored hectorite and their manufacture | |
| EP3854753A1 (en) | White pigment for cosmetics, and cosmetic | |
| JP3267508B2 (en) | Silica / cerium oxide composite particles, method for producing the same, resin composition containing the same, and cosmetics | |
| JPH11209111A (en) | Multiple phosphate | |
| JP3875389B2 (en) | UV absorber | |
| JPH11209110A (en) | Iron/manganese multiple phosphate | |
| US5030445A (en) | Cosmetic composition | |
| JPH11209108A (en) | Multiple phosphate | |
| KR102490404B1 (en) | cosmetic composition | |
| JPH04108716A (en) | Cosmetic | |
| JP2931180B2 (en) | Method for producing iron-containing ultrafine titanium dioxide | |
| JPH11166172A (en) | Ultraviolet absorber and composition containing same | |
| JPH11166173A (en) | Ultraviolet absorber and composition containing same | |
| JPH08127513A (en) | Cosmetic | |
| JPH045215A (en) | Cosmetic |